Explosives
Explosives
Explosives
TM 9-1300-214
DEPARTMENT OF THE ARMY TECHNICAL MANUAL
MILITARY
EXPLOSIVES
TM 9-1300-214
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No. 4 ) Washington, D.C., 25 September 1990
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CARL E. VUONO
General, United States Army
Chief of Staff
Official:
THOMAS F. SIKORA
Brigadier General, United States Army
The Adjutant General
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TM 9-1300-214
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*TM 9-1300-214
MILITARY EXPLOSIVES
REPORTING OF ERRORS
You can help improve this manual. If you find any mistakes or if you know of a way
to improve the procedures, please let us know. Mail DA Form 2028 (Recommended
Changes to Publications and Blank Forms) or DA Form 2028-2 located in the back of
this manual direct to: Commander, US Army Armament, Munitions and Chemical
Command, ATTN: AMSMC-MAY-T(D), Picatinny Arsenal, NJ 07806-5000.
A reply will be furnished to you.
Paragraph Page
CHAPTER 1. INTRODUCTION ............................................................................................... 1-1 1-1
2. HISTORICAL DEVELOPMENT OF ENERGETIC
MATERIAL ........................................................................................................ 2-1 2-1
3. GENERAL CHARACTERISTICS AND CLASSIFICATION OF
ENERGETIC MATERIALS ................................................................................ 3-1 3-1
4. CHEMISTRY AND PHYSICS OF ENERGETIC
MATERIALS ..................................................................................................... 4-1 4-1
5. PROPERTIES AND TESTS OF EXPLOSIVES ................................................. 5-1 5-1
6. PROPERTIES AND TESTS OF PROPELLANTS ............................................. 6-1 6-1
7. UNITED STATES PRIMARY EXPLOSIVES ..................................................... 7-1 7-1
8. UNITED STATES BOOSTER AND SECONDARY
EXPLOSIVES ................................................................................................... 8-1 8-1
9. UNITED STATES PROPELLANTS.................................................................... 9-1 9-1
10. UNITED STATES PYROTECHNICS ................................................................10-1 10-1
11. FOREIGN ENERGETIC MATERIALS...............................................................11-1 11-1
12. TOXICITY OF ENERGETIC MATERIALS .......................................................12-1 12-1
13. DETECTION AND IDENTIFICATION OF ENERGETIC
MATERIALS ....................................................................................................13-1 13-1
14. PACKING, MARKING, STORAGE, AND SHIPMENT OF
ENERGETIC MATERIALS................................................................................14-1 14-1
15. DISPOSAL, DESTRUCTION, DECONTAMINATION, AND
DEMILITARIZATION OF ENERGETIC
MATERIALS ....................................................................................................15-1 15-1
APPENDIX A ............................................................................................................................................ A-1
APPENDIX B ............................................................................................................................................ B-1
INDEX . .......................................................................................................................................Index 1
TM 9-1300-214
CHAPTER 1
INTRODUCTION
1-1. Purpose. This manual is intended for use as a compounds that are used by the United States as
text for instruction or as a reference source in the field booster and secondary explosives. Chapter 9 provides
of energetic materials. Only the materials of interest in a discussion of those mixtures of materials that are used
conventional armaments are covered; nuclear as propellants. Chapter 10 discusses the field of
armaments are not. pyrotechnics. Foreign energetic materials are covered
in Chapter 11. Safety and toxicity considerations are
1-2. Scope. Chapter 2 is a history of the field of discussed in Chapter 12. Basic methods used to
energetic materials. Chapter 3 divides the energetic identify and detect energetic materials are presented in
materials field into three categories: explosives, Chapter 13. Chapter 14 presents information pertinent
propellants, and pyrotechnics. Chapter 4 discusses the to the packing, marking, storing, and shipping of
principles of chemistry and physics pertinent to the energetic materials. Chapter 15 discusses disposal,
energetic materials field. Chapter 5 is a description of destruction, decontamination, and demilitarization of
the tests used to evaluate explosives. Both mandatory energetic materials. Pertinent data on explosives and
safety tests and tests used in the selection of particular propellants are tabulated in Appendix A. Tables A-1
compounds among the many explosive compounds are through A-8 allow rapid comparison of the important
covered. Chapter 6 contains a description of the tests characteristics of the material. The bibliography is
used to evaluate propellants. Chapter 7 presents contained in Appendix B. An index for all material
detailed information about the compounds that are used covered, referencing both paragraph and page numbers,
by the United States as initiating explosives. A concludes the contents of this manual.
discussion of priming compositions is also included.
Chapter 8 presents detailed information about the
1-1(1-2 blank)
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CHAPTER 2
HISTORICAL DEVELOPMENT OF ENERGETIC MATERIAL
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manuscripts as early as 969 AD mention fire arrows, fire Chinese about 1225 AD. Bacon mentioned in his
lances, and incendiary "rockets." But with the exception writings that the ingredients of black powder were used
of Greek Fire, such weapons had little impact on warfare in firecrackers made in various countries of the world.
until World War I.
b. Smoke. While history tells us that screening 2-4. Introduction of Gunpowder In Europe.
smoke was employed in early conflicts, the results of a. Invention of Guns and Gunpowder. The age of
these isolated incidents were always too uncertain to gunpowder began early in the 14th century with the
justify the adoption of smoke as a recognized agent of invention of the gun, which consisted of a metal tube
warfare. In fact, prior to World War I dense clouds of from which a projectile was discharged by the explosive
smoke generated by the black powder used in battle had force of black powder. Guns and gunpowder provided a
become a definite nuisance. These clouds obscured the new means of propelling stone, iron, or lead balls with
field of vision, interfered with aiming and firing, and greater force than catapults or slings. The discovery of
hampered the movement of troops. More recently, the usefulness of black powder for accomplishing
these very same characteristics have been exploited mechanical work may be considered the real beginning
tactically by the planned employment of screening of the history of explosives. When ignited by a torch, a
smoke munitions. loose charge of black powder above the borehole of a
gun served as a priming composition. A train of black
2-3. Invention of Fireworks and Black Powder. powder in the borehole advanced the ignition to set off
a. Fireworks. Fireworks are devices that produce the propellant charge of black powder in the gun tube.
displays of lights, noise, or smoke by the combustion of The Chinese and Europeans evidently became aware of
explosive compositions. Fireworks are managed under this application of black powder about the same time.
that group of ammunition designated as "pyrotechnics." Because Chinese developments did not keep pace with
Those who ply this art are called "artificers." Some those in Europe, the Europeans have been credited with
historians credit the Chinese with being the first true inventing and developing guns and gunpowder. The
artificers. In the reign of Haiao Tsung of Nan Subng earliest mention of black powder on military supply lists
(1169-1189 AD), true fireworks made their debut. They was in 1326 AD. Also at that time, a Latin manuscript
were similar to those used today. The first fireworks called "On the Duties of Kings," written by Walter de
were made of incendiary materials with various Milemete, King Edward Ill's chaplain, included the first
powdered minerals added to color, or to increase the known illustration of a cannon.
light or smoke effect. Not until the invention of black b. Manufacture of Gunpowder. Roger Bacon's
powder were the artificers able to generate the displays black powder recipe was not for gunpowder. Different
with which we have become familiar today, such as proportions of saltpeter, charcoal, and sulfur were
Roman candles, rockets, fire crackers, serpentines, required to propel missiles from the early cannon and
whistles, and stars. The French, in particular, became firearms. In the mid 12th century, John Arderne, an
very adept at civil pyrotechnics by the 17th and 18th Englishman, gave the proportions of saltpeter, charcoal,
centuries. Civil pyrotechnics are generally limited to and sulfur as 6:2:1, the same as recommended by
fireworks used for public display, signaling, or rescuing. Marcus Graecus around 1275 and by Albertus Magnus
b. Black Powder. Authorities differ upon the origin in 1300. The Germans, who some scholars claim
of black powder accrediting in turn the Chinese, Hindus, invented gunpowder and guns around 1313 (i.e., the
and Arabs. In 1249 AD Roger Bacon, an English monk, legendary Berchtold Schwarz), were using a mixture of
recorded a formula for black powder saltpeter (7 parts), 4:1:1 in 1350. The ingredients were ground, mixed, and
charcoal (4 parts), and sulfur (4 parts). Although Bacon used in a fine powder or meal. At first, the materials
was not the inventor, his were probably the first truly were mixed in a mortar using a pestle operated by hand
scientific experiments with this explosive. Sulfur and and were later mixed by horse power. Later,
charcoal had been used in incendiary compositions for improvements in machinery mixed gunpowder with
many centuries. Saltpeter (potassium nitrate) appears rollers on a marble slab and with wooden stamps.
in nature but requires refining to supply the proper Mixing black powder was considered a highly technical
amount of oxygen to ignite the black powder mixture. art and a dangerous one too. Sometimes the final
Bacon's knowledge of purified saltpeter probably came mixing was done at the gun site to reduce the hazard of
from the Arabs who obtained this information from the stores exploding. Nevertheless,
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the records of towns and armies during the early days of c. 1560. Linen or paper bags containing
gunpowder contain many references to accidental gunpowder were used for charging cannons.
explosions. Other mostly useless ingredients, such as d. 1578. An instrument for testing gunpowder was
amber, alcohol, camphor, wine, urine, arsenic, and sal devised by Bourne of England. Until then, the only test
armoniac, were added to the recipe to improve stability, was to burn a small quantity to see how much residue
reduce absorption of moisture, and to prevent would be left. The testing device consisted of a small
crumbling. Depending on the weapon or the use, some metal cylinder with a heavy metal lid on a hinge. The lid
countries varied the proportions of saltpeter, charcoal, was prevented from falling by a ratchet, and the angle to
and sulfur. For example, the French at one time made which the lid rose when powder was fired inside the
six different mixes one strong and one weak each for cylinder measured the strength.
pistols, muskets, and cannons. Different mixes have
e. 1588. Explosive shells were used at the siege
been used for blasting, mining, and sporting weapons.
of Bergen op-Zoom and Wachtendonck, Holland by the
In 1895, most countries, including the USA, adopted the
Dutch. The shells were made from hollow iron balls
English standard 75: 15: 10 (saltpeter: charcoal:
filled with gunpowder. The gunpowder was ignited by a
sulfur), which had been in effect since 1781. This
fuze consisting of a hollow tube filled with slow burning
standard is generally used for all arms, the only
serpentine powder, and timed to burn 14 to 20 seconds,
difference being in the size of the grains.
corresponding to ranges of 914 to 1830 meters (1000 to
2000 yards) for mortar fire. The knowledge for making
2-5. Developments Between the 15th and 18th
this fuze was brought to the Dutch by an Italian deserter
Century. The development of energetic materials from from Parma.
1400 to 1800 were restricted mainly to improvements in
f. 1590. Cartridges with ball and powder
the manufacture of black powder and related
applications. By 1400, iron cannons, bound by iron combined were introduced for small arms.
hoops to keep them from bursting, and iron cannon balls g. 1602-1604. Fulminating gold, later used as a
were coming into use. At the end of the 14th century, a priming explosive, was invented by Johann Tholden, a
hand gun was invented that weighed 4.5 kilograms (10 Dutch chemist in the employ of the British Navy.
lbs) and fired lead shot. One man carried the gun, h. 1611-1632. An improved paper cartridge was
which was mounted on a stand and aimed at the enemy. developed during the rule of Swedish King Gustavus
This weapon evolved into the arquebus or harqebus, a Adolphus, thus increasing the rate of fire for firearms
hand gun with a bent stock and a forked staff to support used in the Thirty Years' War.
the barrel while firing. A lit match or fuse of serpentine i. 1613. Blasting powder is reported to have been
black powder was used to ignite the propellant powder used in German mines to blast rocks. Less saltpeter
charge through a touch hole in the breech (closed end) and more charcoal and sulfur were used in blasting
of the gun barrel. Other important events or powder than in gunpowder.
developments during this period are as follows: j. 1627. An improved instrument for testing black
a. 1425. Corning, a new process for making black powder was devised by Curtenbach. This consisted of a
powder into grains instead of the finer serpentine heavy conical shot, which rested on the mouth of a
gunpowder, was invented. Corning consisted of wetting small mortar and could travel vertically upwards along a
black powder to form a paste, which was then pounded stretched wire provided with a series of catches to stop
into a cake. The cake was broken into small lumps by the shot from falling.
hand and sifted. The resulting pieces, which were called k. 1627. Black powder was used to blast ore in the
corned powder, absorbed less moisture and were more royal mines at Schemnitz, Hungary following
suitable for use in cannons than the serpentine powder. experiments by a Hungarian engineer, Kaspar Weindl.
Flame from the priming powder was distributed more Using black powder for this purpose was slow to be
efficiently by the larger grains. This resulted in a more accepted because saltpeter was expensive, boring
complete explosion and reduced fouling. instruments were not available, and safety hazards from
b. 1540. Standard gunpowder grain sizes for mine gases and cave-ins were increased.
pistols, muskets, and cannons were adopted by the I. 1628. Gold fulminate priming explosives for
French. They discovered that less powder was needed torpedoes were invented by J. Thollen for the British
to propel a projectile if the grain size was controlled. By Navy.
using uniform, slow-burning grains they were able to
control the pressure of the explosion in the gun, and
thereby reduce the hazard of blowing up the gun. This
discovery also led to improvements in gun design.
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m. 1647. Testing the strength of gunpowder, by over 350 years. The discovery of new materials or the
firing a ball from a mortar and measuring the distance practical application of previously known materials (fo
the ball travelled, was proposed by Master-Gunner Nye example, picric acid) greatly influenced the design and
in his "Art of Gunnery." This mortar test was adopted by performance of weapons and ammunition. In turn, the
France and other countries soon afterward. rapid development of weapons and ammunition, and the
n. 1654. Ammonium nitrate was first prepared by increased demands of new and expanding industries
J. R. Glauber, a German chemist. further accelerated the search for more effective, less
expensive materials. During the nineteenth century,
o. 1679. Blasting powder was used on a large
more powerful propellants (such as smokeless powder),
scale in the construction of the Mal pas Tunnel, Canal
better primers, various boosters or detonators, and new
de Midi, France.
high explosives were introduced. There were significant
p. 1684. Glazing process for gunpowder was advancements in the science and technology of
introduced. Rough gunpowder corns were glazed by weapons and ammunition, too. Among these were
tumbling them in large wooden drums until the grain improved explosive (Congreve) rockets (later adapted
surfaces were smooth. Graphite was added to coat the for signaling and illumination), rifled arms, revolvers,
grains. Glazed gunpowder was less hygroscopic and magazine-loading rifles, machine guns, revolving
flowed more easily than the unglazed gunpowder. turrets, armored naval vessels, percussion caps
q. 1735. Antimony sulfide and arsenic sulfide were (encapsulated primers), metallic cartridges, time fuzes
used by Ruggieri of Italy in pyrotechnic mixtures for and impact fuzes for artillery shells, rifled breech-
brilliant fireworks displays at Versailles. loading field artillery, obturation devices, and spring and
r. 1738. The closed bomb for measuring the hydropneumatic recoil mechanisms for artillery. Modern
pressure generated by gunpowder fired in a closed mass production began when Samuel Colt, an American
vessel was designed by d'Antony of Italy. gunsmith, first manufactured standard rifle and revolver
s. 1742. The ballistic pendulum, which determined parts. Mass production of small arms ammunition
the velocity of a projectile's impact by measuring the began when G. Moore Peters used the first cartridge-
recoil of a struck pendulum, was invented by Benjamin loading machinery at his factory in Ohio. Nineteenth
Robins, an English mathematician. Robins showed that century developments of energetic materials follow.
air resistance on a moving projectile at high velocities is
greater than the resistance at low velocities. Robins a. 1800. Mercury fulminate was discovered by
also developed the first practical chronograph, an Edward Howard, an English chemist, who described its
instrument for measuring and recording short durations detonating properties in a paper before the Royal
of time, and improved on a closed bomb for testing the Society.
power of an explosion. b. 1801. Fireworks formulas containing metal salts
t. 1771. Picric acid was first prepared by Pierre and ammonium chloride were published by C. F.
Woulfe, a French chemist, by treating silk with nitric Ruggieri, an Italian artificer. These salts produced
acid. Picric acid is an aromatic nitro compound which brighter flames because volatile metal chlorides were
was used as a yellow dye until its explosive properties formed during the combustion reaction.
were discovered in 1871. c. 1807. The principle of using mercury fulminate
u. 1784-1788. Potassium chlorate was prepared in as a primer was patented by Rev. Alexander J. Forsyth
its pure state by Claude L. Berthollet, a French chemist of Aberdeenshire, Scotland.
who discovered its detonating properties. His idea of d. 1823. Chlorates, discovered by C. F. Berthollet
using potassium chlorate instead of potassium nitrate in in 1786, were first used in fireworks by John Cutbush, an
black powder was abandoned after a disastrous English artificer.
explosion during manufacture in 1788. e. 1825. Benzene, creosote, and naphthalene
Berthollet also prepared fulminating silver in 1788. were isolated from coal tar (obtained from bituminous
v. 1784-1789. Compact black powder grains were coal) by Rev. Dr. Clayton in England. Most of his
obtained by pressing the cakes with screw presses products were later nitrated to produce explosives, such
before corning at Faversham, England. as trinitrobenzene and nitronaphthalenes.
f. 1826. Aniline was first prepared by
2-6. Nineteenth Century Development. Modern Unverdorben. Later, nitration of aniline resulted in the
energetic materials technology began with the very powerful explosive called tetranitroaniline.
nineteenth century. New energetic materials began to
displace the black powder formulas that had been the
choice for use in weapons, ammunition, and blasting for
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u. 1858. Diazo compounds were discovered by 2-6 through nitrating wood, washing the wood with a
Peter Griess, who also prepared dinol or dilute solution of sodium carbonate, and drying.
diazodinitrophenol. dd. 1866-1867. Dynamite was invented by A.
v. 1859. Ethylene oxide, ethylene glycol, and Nobel by absorbing nitroglycerin (75) in kieselguhr
ethylene glycol ether were prepared by Charles A. (diatomaceous earth) (25). Kieselguhr, an inactive
Wurtz. A century later, ethylene oxide was used in ingredient, stabilized the nitroglycerin, and made
fuelair explosives (FAX) developed by the US Armed dynamite a much safer explosive to handle and use.
Forces. Diethylene glycol was also developed ee. 1867. The fulminate blasting cap, a device
simultaneously in 1859 by Wurtz and A. V. Laurenco. consisting of mercury fulminate in a copper tube used to
w. 1860. A caseless propellant, consisting of detonate explosives, was invented by A. Nobel. This
cap was crimped to one end of a safety fuse (e.g.
cakes of compressed black powder cakes or grains with
Bickford fuse), and then inserted into the dynamite
perforations, was developed by T. J. Rodman while
cartridge.
working at Frankford Arsenal, Philadelphia. This led to
ff. 1867. Ammonium nitrate, pulverized and
the use of grains shaped into hexagonal prisms about
2.54 cm (1 inch) long and 2.54 cm (1 inch) across. mixed with sawdust or charcoal, was proposed as an
Perforations and grooves in the grains channel the absorbant for nitroglycerin by J. H. Norribin and C. J.
flame from the explosion. As the grains burn inward Ohlsson, Swedish inventors.
from the prism surfaces and outward from the gg. 1868. Dry compressed guncotton was
perforations, the burning gases flow continuously, detonated with a mercury fulminate detonator by E. A.
thereby permitting the explosive energy to build up Brown, an English chemist, who also discovered that
gradually until the maximum power is exerted as the wet guncotton could be exploded by the initiation of a
projectile leaves the muzzle of the gun. This small quantity of dry guncotton. This important
acceleration imparts a more efficient thrust to the discovery, on the principle of a booster explosive, led to
projectile and extends the range of the gun. the use of large blocks of wet guncotton in naval mines
with comparative safety.
x. 1861. Guanidine was formed by the oxidation hh. 1869. Dynamites with an active base were
of guanine by Strecker. Guanine is a derivative of patented by A. Nobel. To create an active base
guano, which was formed from manure, especially that dynamite, Nobel mixed nitroglycerin with combustibles
of birds and bats. (sawdust, charcoal, rosin, and starch), and oxidizers
y. 1863. Trinitrotoluene (TNT) was prepared by J. (sodium nitrate or potassium nitrate). This led to a more
Willibrand, German scientist. Although TNT was used efficient explosive than guhr dynamite.
for many years in the dye industry, TNT was not used as ii. 1870. Ohlsson and Norribin's patent for
an explosive until 1904. Thereafter, TNT became one ammonium nitrate dynamite was purchased by A.
of the most used high explosives. Nobel, who subsequently began production of
z. 1862-1866. Nitroglycerin production plants were ammonium nitrate dynamite.
designed for commercial applications by Alfred Bernard jj. 1871. Sprengel explosives, which consisted of
Nobel, a Swedish chemist, based on studies conducted mixing various combinations of oxidizing agents
with his father, Emmanuel, in 1859-61. In 1862, they (chlorates, nitrates, and nitric acid) with combustibles
built their first plant at Heleneborg, Sweden. Despite the (nitronaphthalene, benzene, and nitrobenzene), were
tragic loss of his brother Emil in an explosion at that patented by Hermann Sprengel, a German chemist.
plant in 1864, Alfred erected two more plants in 1865 Oxidizing agents and liquid fuel were mixed on site
and another in 1866. before using.
aa. 1865. Magnesium was first used for kk. 1875. The "Explosives Act" was passed by
pyrotechnics. the British Government after a disastrous explosion at
bb. 1865. Nitrocellulose was purified by Sir Birmingham killed 53 persons. The Explosives Act
Frederick A. Abel, an English chemist, who also established Inspectors of Explosives, who were given
successfully manufactured granulated nitrocotton. Abel the power to inspect all magazines and factories to
pulped, washed, and compressed the nitrocellulose into ensure that operations were carried out in a reasonably
blocks, sheets, discs, and cylinders, which were safe manner. As a result, the number of deaths in
particularly useful for blasting. explosives factories was greatly reduced. The
cc. 1865. Smokeless powder, used as a sporting provisions of this act have been adopted by many other
propellant, was invented by Schultze, a Prussian officer, countries.
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ll. 1875. Gelatinous dynamites and blasting discovered that a concave-shaped explosive charge
gelatins were patented by A. Nobel. pierces a steel plate.
mm. 1877. Nitroguanidine was first prepared by yy. 1888. Cyclotrimethylene trinitrosamine was
Jousselin, but was not used in propellants until 1900. discovered by Griess & Harrow and by Mayer, yet was
nn. 1879. Tetryl, a booster explosive, was first not used until the Germans, who called it R-salz, used
prepared by Michler and Meyer of Germany. the composition in World War II.
oo. 1879. Ammonium nitrate gelatins, known as zz. 1888. Ballistite, the first double-base
ammongelatins, were patented by A. Nobel. smokeless propellant, was prepared by Alfred Nobel by
pp. 1882. Brownorcocoagunpowderwasmade by replacing camphor with nitroglycerin. In 1889, Nobel
the Germans using partially burned charcoal from rye prepared ballistite from collodion cotton and
straw. The grains were made in single, perforated nitroglycerin using a solventless method.
hexagonal or octagonal prisms. Brown powder was of aaa. 1888-1889. Cordite, the second successful
higher quality, but was more sensitive to friction than double-base smokeless propellant, was prepared by Dr.
black powder. The United States used brown powder W. Kellner in F. Abel's English laboratory. Sir James
during the Spanish-American War. Dewar, British chemist and physicist, and Abel patented
qq. 1883. Tetryl was synthesized from picryl cordite for the British Government, which adopted
chloride and potassium methylnitramine by van cordite as a military propellant named Cordite Mark I or
Romburgh, a German chemist. CSP (cordite smokeless powder).
rr. 1883-1884. Colloided rifle powder was bbb. 1890. Tetranitrocarbazole, used in igniter
prepared by Max von Duttenhofer by nitrating brown and pyrotechnic compositions, was first prepared by Karl
charcoal before mixing the ingredients. This brown Graebe, a German chemist. The current method of
powder was adopted by the German Army in 1884. preparation was developed in 1912 by the Leopold
ss. 1884. Smokeless powder, for military rifles, Cassella Company in Frankfurt, Germany, a division of
was invented by Paul Vieille of France. This powder the Interessen Gemeinschaft (I. G.) Farben corporation.
was a completely colloided single-base nitrocellulose ccc. 1889-1890. The development of explosive
propellant. The French Army adopted Vieille's Poudre devices was greatly enhanced by the work of Theodor
B. in 1866. Curtius, German Nobel prize laureate, who discovered
tt. 1884-1885. High-speed photographic cameras hydrazine in 1889 and hydrogen azide in 1890. He
were used for ballistic studies by Eugene Mach and P. subsequently suggested to the German military the use
Salcher of Austria. of metal azides for primer application.
uu. 1885. Two flashless powders, ammonpulver ddd. 1892. Tetranitrooxanilide was prepared by
and amidpulver, were patented and made by Gaens of A. G. Perkin, an English scientist, and used as a
Hamburg from ammonium nitrate, potassium nitrate, component in black powder type explosives and
and charcoal. pyrotechnic compositions.
vv. 1885. The Hell Gate blast in New York eee. 1894. Butanetriol trinitrate, used a half
Harbor used 34,000 kg (75,000 lbs) of dynamite, and century later as an explosive plasticizer for
11,000 kg (24,000 lbs) of potassium chlorate soaked in nitrocellulose, was first prepared by Wagner and
nitrobenzene (rack-a-rock) to remove Flood Rock, a Ginsberg.
menace to navigation. This was the largest amount of fff. 1895. Liquid oxygen explosive (LOX), carbon
explosives used in a single blast until then. black packed in porous bags and dipped in liquid
ww. 1885-1888. Eugene Turpin, a French oxygen, was introduced by Karl P. G. von Linde of
scientist, patented the process of melt-pouring picric Germany. LOX was widely used by Germany during
acid into artillery shells as a high explosive filler. World War I, and in the United States Midwest for strip-
Sprengel had discovered that picric acid could be mining in the 1950's.
initiated by a powerful detonator, but had not exploited ggg. 1896. A layered smokeless propellant,
this knowledge. The French Government adopted a which was prepared by glueing and compressing
high explosive shell designed by Turpin using a picric together several layers of different components, was
acid filler. They designated the picric acid filler as patented by A. B. Bofors, Nobelkrut of Sweden. The
melinite. In 1888, the British adopted picric acid, which outer layers were slow-burning, while the burning speed
they called lyddite as an high explosive filler. increased progressively towards the inner layers.
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hhh. 1897-1898. Cheddite, an explosive for Badische Anilin-und Sodafabrik of Germany. This
blasting consisting of potassium chlorate or perchlorate process was less expensive than the chamber method
mixed with a nitro compound and castor oil, was previously used. As such acid was required for mixed
invented in England by E. Street. Cheddite derives its nitric-sulfuric acid to nitrate aromatic hydrocarbons to
name from Chedde, France, where it was made. polysubstitution, trinitrobenzene and trinitrotoluene
iii. 1899. Potassium dinitrobenzfuroxan, used in (TNT) could be inexpensively manufactured.
priming compositions, was first prepared by P. Von d. 1900. Chromatography, a physical method of
Drost. separation in which the components are partitioned
jjj. 1899. Cyclonite (RDX) was first prepared by between two phases, was invented simultaneously and
Henning of Germany. Henning used RDX, which he independently by American geologist D. T. Day and
called Hexogen, for medical purposes. The first to Russian botanist M. S. Tsvet. The qualitative method
recognize the value of RDX as an explosive was E. Von of separation of ingredients by adsorption was known for
Herz of Germany. The first to prepare RDX in quantity centuries.
was G. C. Hale of Picatinny Arsenal, NJ, in 1925. How- e. 1900. Regular-delay electric blasting caps for
ever, it was not until World War II that the most rotational shooting (0.5 to 12 seconds) developed.
important work in manufacturing processes and f. 1901-1904. A trinitrotoluene (TNT) manufacturing
applications of RDX was done. process consisting of three phases was developed by C.
kkk. 1899. Aluminized explosives, containing Haussermann of Germany. This method, which proved
aluminum to increase the performance of explosives, to be more economical than direct nitration of toluene to
were first proposed by R. Escales of Germany and were TNT, was used in the United States until World War II.
patented by G. Roth. Ammonal, their first, contained The German industry adopted this process in 1902,
ammonium nitrate, charcoal, and aluminum. when they adopted TNT as the filler for high explosive
shells. They also used TNT for demolition purposes,
2-7. Twentieth Century Development through World replacing picric acid.
War I (WWI). This period saw the use of cordite g. 1902. Detonating cord, developed in France, was
smokeless powder and repeating rifles by the British improved, leading to adoption in the United States by
during the Boer War (1899-1902) in South Africa; large the Ensign-Bickford Company in 1912.
scale naval battles and full-scale use of machine guns in h. 1902. Antifreeze for dynamite was researched
the Russo-Japanese War (1904-1905); and the extensively in many countries following a disastrous
introduction of submarine warfare, armored tanks, aerial explosion during defrosting dynamite in Greisnau,
bombing of civilians by dirigibles, and strafing and Germany. The problem of producing a satisfactory
bombing by aircraft during World War 1 (1914-1918). antifreeze remained unsolved until S. Nauckhoff of
World War I saw concentrated machine gun fire, artillery Sweden published his work in 1905, listing requirements
barrages, firing long ranges from railroad guns and from for a satisfactory antifreeze, and compounds which met
large guns on battleships, firing torpedoes, laying mines, these requirements.
using depth charges in anti-submarine warfare, and i. 1903. A muzzle-flash suppressor using vaseline with
signaling and illuminating with flares. Soldiers were 1-2% sodium bicarbonate was proposed by Rottweil
issued steel helmets and gas masks for individual Fabrik of Germany. This was replaced in 1905 by soap
protection. or rosin.
a. 1900. Cordite smokeless powder, used by the British j. 1904. The Obermueller Stability Test, which
in the Boer War, caused excessive corrosion in gun consisted of heating 1-2 grams of nitrocellulose in a
barrels. As a result, the formula for cordite was small tube under vacuum at 135-140° and measuring
changed to reduce the amount of nitroglycerin from 58% the pressure of evolved gas by vacuum manometer,
to 300/0 and to increase the amount of nitrocellulose to was introduced.
65% with the amount of mineral jelly remaining at 5%. k. 1904-1905. Methyl picrate (2,4,6trinitroanisole) was
b. 1900. Picric acid (British lyddite) shells were used in patented for use in smokeless propellants. The powder
the Boer War but did not detonate completely. This was consisted of an equal amount of methylpicrate and
attributed to faulty construction of the detonators. pyrocellulose.
c. 1900. The Contact Process for manufacturing
concentrated sulfuric acid and oleum was discovered by
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l. 1905. Nitrostarch was produced in a stable Making propellants into large solventless grains was less
form. Nitrostarch is similar to nitrocellulose but is lower time consuming than making solvent propellants.
in strength. Nitrostarch does not cause headaches from y. 1912. TNT was adopted as the standard
skin contact as do TNT, nitroglycerin, dynamite, and bursting charge in high explosive shells for the field
many other explosives. artillery of the US Army.
m. 1906. Various substituted ureas, called z. 1912. Nitroisobutylglycerol trinitrate or
centralites and akardites, were developed at the Central trimethylol nitromethane trinitrate, used as an explosive
Laboratory for Scientific and Technical Research at gelatinizer for nitrocellulose, was first prepared by
Neubabelsberg, Germany, for chemical stabilizer Hofwimmer.
application in smokeless powders. aa. 1912-1913. Tetranitroaniline (TNA) was
n. 1906. Lead azide was proposed by Col. patented by Dr. B. J. Flurscheim, an English scientist.
A. A. Solonina of Russia for use in compound bb. 1914. Lead styphnate (trinitroresorcinol), an
detonators (initiating explosives) in lieu of mercuric initiating explosive, was first prepared by E. von Herz of
fulminate. Germany. Col. A. A. Solonina of Russia was the first to
o. 1906. Hexanitroazobenzene was prepared by propose using lead styphnate in compound detonators.
E. Grandmougin and H. Lehmann of France, and cc. World War I. The high-explosive technology
recommended by Tenny L. Davis for use in boosters. of the contending powers greatly influenced the conduct
of World War I. At the outbreak of war in the summer of
p. 1907. Diphenylamine, designated as poudre B,
1914, the German General Staff had planned to fight a
was approved as a stabilizer for French naval cannon
high-explosives war of great intensity. Their plan was to
propellants and other large caliber guns. This stabilizer
mount a sudden and overwhelming attack using vast
replaced amyl alcohol after the disastrous explosion in
stores of artillery ammunition accumulated over the
1907 of the battleship lena.
preceding forty years. After the battle of the Marne in
q. 1907. Mixed glycol esters, such as dinitroacetin 1914, the Germans realized that explosives production
with dinitroformin, were patented as dynamite antifreeze must be expanded; and they turned to their dye industry
by Vezio Vender of Italy. for this expansion. When the war began, Germany's
r. 1908. A detonating cord (cordeau detonant) chemical industry was producing 85% of the world's
containing TNT instead of blackpowder was patented in dyes. The Germans were able to rapidly convert their
France. This detonating cord had a detonation velocity plants to production of synthetic ammonia, nitric acid,
of 4,880 meters (16,000 feet) per second. and sulfuric acid, which were required for the
s. 1909. Ammonium picrate (Dunnite or Explosive manufacture of explosives and chemical warfare agents.
D) was standardized in the United States as a bursting When Germany's access to Chilean saltpeter was cut off
charge for armor-piercing (AP) shells. These AP by the Allied blockade, the key to the German war
projectiles could be fired through 12 inches of armor production of explosives was the Haber process for
plate, and could be detonated on the far side by an producing ammonia from atmospheric nitrogen. By
insensitive primer. expanding their nitrogen plants at Oppau and
t. 1909. Low-nitrated aromatic hydrocarbons, Merseburg, Germany was able to become independent
because of their stability and insensitivity to shock and of foreign countries for the supply of ammonia and nitric
to ignition, began to be used in coal mining explosives acid. Because these chemicals were so essential for the
compositions. manufacture of explosives and fertilizer for food
products, it is doubtful if Germany could have continued
u. 1909. Solventless powder (or propellant) was
the war beyond 1916 without the amazing speed with
discovered by Brunswig and Thieme of Germany,
which the I. G. Farben concern was able to convert their
although many others contributed to the development of
dye plants to explosives plants. For example, at
such propellants.
Leverkusen, a TNT plant producing 250 tons per month
v. 1910. Preparation of 2,3,4,6-tetranitroaniline, a was put into operation in six weeks. The major powers
powerful explosive, was patented by Flurscheim. This began accelerating the search for substitutes or
explosive was used during World War II by the supplements to TNT. The most important were mixtures
Germans and Japanese. of high explosives, such as TNT, TNX, and TNN, with
w. 1910. Tetracene was first prepared by K. A. ammonium nitrate and aluminum. By 1914, the French
Hofmann in Germany. More extensive studies of the had already begun
compound were conducted in 1931 by Rinkenbach and
Burton.
x. 1910-1913. Laminated solventless propellants
were prepared by Dr. C. Claessen, a German scientist.
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replacing picric acid (melanite) with TNT. In 1915, the mixture. A hydrogen pilot lamp at the flamethrower
British developed amatol (TNT plus ammonium nitrate) nozzle was used to ignite the flame fuel. The World
to extend the supply of TNT. In 1917, Austrian War I flamethrowers had a range of about 30 meters.
ammonal T (TNT, aluminum, and ammonium nitrate) Although effective for assaulting fortifications, the
was developed by R. Forg to be used in underwater flamethrower was also very hazardous for the operator
explosives, such as torpedoes and depth charges. Lead because of its short range.
azide was introduced as an initiator, and tetryl was used
as a booster explosive for artillery shell charges. About gg. World War I. Smoke munitions were used
2,500,000 tons of high explosives were used by the both on land and sea by the belligerent powers in World
contending powers during the war, resulting in an War I. In July 1915, the British were the first to use
estimated 10 million casualties. smoke pots, which were filled with pitch, tallow, black
powder, and potassium nitrate. The first large-scale
dd. World War I. High-explosive aerial bombs smoke operation occured on 20 September 1915, when
were first dropped from German Zeppelins during the 31 the Canadians fired several thousand smoke shells from
May 1915 raid on London. The Germans continued to trench mortars during the attack against Messines
use these dirigibles, practically unopposed, in their air Ridge. Although very successful against the Germans,
raids on London and Paris until late in 1916. Then the the British and French tanks of World War I were
British and French began to counter these attacks with capable of travelling only four miles per hour, which
anti-aircraft gunfire and fighter aircraft. Soon the made them very vulnerable to artillery fire. The British
Germans began using their large Gotha bombers, which Tank attack at Cambrai on 20 November 1917 was
they employed throughout 1917 and 1918. In supported by intense artillery smoke shelling, which
retaliation, the Allies began producing fleets of larger enabled 350 tanks to break through the German lines.
bombers and various high-explosive bombs. On 15 June 1918, the Austrians used smoke to screen
their crossing of the Piave River, from Vidor into San
ee. World War I. Incendiary bombs were also Giovanni, from Italian machine gun concentrations. The
first used during the German Zeppelin raid over London Allies generally used white phosphorus (WP) to fill their
on 31 May 1915, when one dirigible dropped 90 smoke shells; whereas the Germans, because of a
incendiary bombs. The early incendiaries used by the shortage of phosphorus, used a mixture of sulfur trioxide
Germans in their air raids over London and Paris were in a chlorosulfonic acid solution. The Germans used
made from a mixture containing manganese dioxide and this type of smoke (FS) to successfully screen their
magnesium. Later, the French used sulfur-bound warships during the battle of Jutland in 1916. Later, the
thermite, a mixture of iron oxide and powdered United States adopted FS smoke for use in spotting
aluminum, in an incendiary drop bomb. The British rounds, for liquid chemical agent shots, and in airplane
were the first to develop incendiary bomb clusters, smoke tanks. FS was reclassified obsolete in
which could release either 144 or 272 bomblets. A De November 1975 because WP was considered better for
Haviland bomber could dispense up to 860 of these 6.5 marking targets and FS droplets from aerial spray
oz incendiary bomblets, and a Handley-Page V bomber destroyed the nylon fabric in parachutes. Titanium
could dispense up to 16,000. By flying in formation, tetrachloride (FM) was also used as a filler for spotting
these bombers could cover a large area with a blanket rounds during both world wars, but was removed from
of burning incendiary materials. the US inventory because of its high cost. In 1918,
tanks carried containers filled with chemicals, which
ff. World War I. Flamethrowers were first when injected into the vehicle exhaust system formed a
introduced by the Germans on the French front on 25 cloud of screening smoke. Sulfuric acid, chlorosulfonic
June 1915. Their weapon was a cylindrical steel vessel acid, oleum, and crude oil were used as the smoke
about 61 centimeters (2 feet) high and 38 centimeters screening agent in these early smoke generators. WP
(15 inches) in diameter, fitted with carrying straps. hand and rifle grenades were used by the infantry for
Internally, the cylinder was divided into a compression screening movements. The main disadvantage was the
chamber and an air reservoir. A short hose carried the danger of the user being exposed to falling particles of
fuel to the nozzle where it was ignited. The propellant burning white phosphorus, which is also an incendiary.
was nitrogen. The fiery spurt of burning oil, the roar of WP grenades were reclassified obsolete in November
the flame, and the billowing clouds of black smoke had 1975 by the US Army.
a terrifying effect on troops in trenches. Using this
prototype of the modern portable flamethrower, the
Germans drove back a British rifle brigade from
trenches near Ypres, Belgium, in 1915. The Americans
used a heavy viscous tar and a more fluid, flammable
liquid such as crude benzene for their flame fuel
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hh. World War I. Incendiary artillery shells and and night signals. Four general designs of firework
rifle bullets were introduced in 1915 to set fire to devices were in constant use by the French and the
buildings, supply dumps, and enemy observation British armies. These devices were Very-type signal
balloons. The Germans used sodium in their 17.5 pistols, rifle lights, rockets, and ground or position
centimeter artillery shells. They also used thermite or signals (e.g. candles). (The same type of devices were
an aluminum-thermite mixture in their other artillery used for illumination.) The signal-pistol cartridges used
rounds. The Allies used thermite most frequently. by the French were fitted with delay fuzes, which
Thermite incendiary grenades were issued to raiding effected the ignition when the projectile reached its
parties for hasty destruction of captured enemy weapons maximum height. Some realization of the development
that could not be retrieved. in pyrotechnic construction due to the war may be had
ii. World War l. Pyrotechnics for battlefield by considering the latest production of the French 35-
illumination were used extensively during World War I. millimeter signal cartridge, which included 14 varieties
The British alone used 10 million position light flares per or combinations of signals. Upon entering the war, the
month. The art of making illuminants had been United States adopted many of the French signals for
neglected after the reign of Louis XIV until the twentieth Army use. This was mainly because the American
century. In 1913, the German Krupp Works developed forces were to operate in the French sector, which
an illuminating projectile, which they called a searchlight necessitated an identical system of signals. Generally,
shell and which later became known as the star shell. the fireworks and devices employed by the Germans
The first star shell contained six small tubes, called were similiar to those of the French, but there was an
stars, loaded with an illuminating composition. The important difference in the method of construction for
mixture used was similar to that in the white Bengal the signal-pistol cartridge. The German cartridge was
lights for fireworks displays; but ribbons of magnesium ignited just after emerging from the barrel of the pistol.
were substituted for antimony powder. A folded Rockets mounted on sticks for stabilization during flight
parachute was placed in the bottom of each tube. The were employed by the Allies. The Germans followed
projectile was fired from a cannon or mortar. When the Congreve's construction in the use of metal, but
projectile reached a height of 300 meters, a mechanical modified the design to eliminate the use of a stick. In
time fuze set off a small black powder charge releasing the German rocket, the openings for escaping gas were
the tubes from the shell and igniting the pyrotechnic in the base. Before the outbreak of the war, the art of
mixture. Springs were used to open the parachute pyrotechny had reached such a point that little difficulty
instantly, and the tube with its burning star floated slowly was encountered in securing adequate mixtures for the
to earth. The illuminating material burned very brightly various colors required in signaling. Different colored
for 45 seconds to several minutes depending upon the flares had been used for many years commercially. The
model. The French constructed a similar projectile railroad companies regularly employed pyrotechnic
containing eight cylinders, which was fired from their devices, such as red railroad fusee, while blue light
155 millimeter howitzer. However, they preferred using pyrotechnics were used for signaling at sea. The colors
burning-type fuses to set off the powder charge in their used by the Allies included red, green, yellow, blue,
star shells. Later, the Germans replaced the star tubes black, various numbers of white stars, and changing
with a six-sided prism, which was more compact and colors. The Italians used a tri-color parachute flare,
could be adapted for use with rifles, special pistols, and which emitted red, white, and green colors. The Italians
large caliber carbines. By using plates to retard the fall also developed a hissing flare, which, when suspended
of the star, more space was made available in the star from a parachute, burned with a hissing noise audible
for storing the illuminating mixture; and a light of greater over an area of 3,000 meters (3,284 yards) in diameter.
intensity or longer duration was obtained. The Italians This was found particularly effective as a gas alarm.
used a hand-held, heavy pasteboard tube to discharge a Some of the ingredients used in the WW I pyrotechnics
sheet-iron star shell tube, which expelled its illuminating were aluminum, potassium nitrate, sulfur, antimony
parachute flare. This flare burned about 40 seconds. sulfide, antimony metal, dextrine, meal powder, barium
Many different illuminating devices were developed and chlorate, potassium chlorate, fine charcoal, barium
used by both sides, but perhaps the simplest and most nitrate, red gum, paris green, shellac, sodium oxalate,
useful for trench warfare was the illuminating grenade. magnesium carbonate, strontium carbonate, calomel,
Thus every soldier on night patrol had his own device copper oxychloride, calcium carbonate, sawdust and
for lighting his sector, and exposing the advancing grease mixture, sugar, lamp black, ultramarine blue,
enemy to aimed gunfire. paranitraniline red, lactose, auramine, chrysoidin,
jj. World War l. During World War I, pyrotechnics synthetic indigo, phosphorus, paraffin, and arsenic.
for signaling included colored smoke cartridges, canTM
91300-214 dies, flares, streamers or trails, star signals,
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2-8. Developments after World War I through World improved fire bombs filled with thickened or gelatinized
War II. The most complicated task confronting the US incendiary oil or gasoline mixtures, and large clusters of
Army Ordnance Department at the end of World War I incendiary bomblets filled with thermate (an
lay in the field of ammunition. Combat experience had improvement of the WW I thermite), the US air forces
shown the inadequacies of the ammunition used in were able to literally set fire to cities like Dresden and
1917-1918, which were inaccuracies, failures, lack of Tokyo. Flamethrowers and smoke munitions were used
safety features, and a host of needless complexities. extensively by both sides. Finally, the extensive use of
But whereas the combat arms could specify exactly armor during the war led to the development of anti-tank
what the gun and vehicle requirements should be, their weapons, armor-piercing shells, and shapedcharge
recommendations for the development of explosives, munitions. The application of the shaped-charge
propellants, projectiles, and fuzes had to be couched in principle resulted in the use of special explosives of the
general terms. Here were basic research problems that pentolite type.
ammunition experts had to define. Often they sought a. 1918-1939. Ammunition research in the first
interim solutions, and waited until greater knowledge postwar years was inspired not only by new
could supply better answers. Hence the ammunition requirements, but also by the problems encountered in
designers had free reign within budgetary limits. Over preserving ammunition, especially propellants, stored
the 20 years between the two world wars, the Army after the Armistice. Research proceeded in three areas:
dedicated more money to the ammunition program than determining the stability of smokeless powder, studying
to any other development work. During these two the effects of long term storage on stability, and creating
decades, RDX, PETN, EDNA, DEGN, lead styphnate, more efficient methods of drying. A good deal of
and dextrinated lead azide were developed as military valuable information on these substances was
explosives. The development in the United States of assembled at Picatinny Arsenal, NJ, before 1926,
processes for producing toluene from petroleum notably that on feasibility of the vapor method of drying,
removed limitations on the availability of TNT, and which reduced drying time from months or weeks to
permitted development of the powerful and castable days. But a more permanent solution of some phases
explosives like composition B and pentolite. Flashless of the powder storage problem would be to develop new
propellants were developed in the United States, and non-hygroscopic powders, which because of their
lowerosion DEGN propellants were developed in chemical composition would not absorb enough
Germany and Italy. Diazodinitrophenol was developed moisture to affect their ballistics or chemical stability
as an initiator in the United States, and tetracene was even when stored in a damp atmosphere. If, at the
developed in Germany as a new explosive ingredient of same time, flashless and smokeless qualities could be
priming compositions. World War 11 (1939-1945) saw incorporated, the advantages would be even greater.
the development of rocket propellants based on Thus the search for flashless non-hygroscopic (FNH)
nitrocellulose-nitroglycerin or nitrocellulose-DEG N powders was vigorously pushed. The DuPont Company,
mixtures, and the use of nitroguanidine in artillery under a special agreement with the Ordnance
propellants. New special-purpose binary explosives, Department, followed one route of investigation, while
such as tetrytol and picratol, were developed for use in Picatinny Arsenal followed another. Each achieved
demolitions, chemical bombs, and semi-armor-piercing considerable success. The peacetime development of
bombs. A number of plastic explosives used for complete single-base and double-base non-hygroscopic
demolition work were developed in Great Britain and the powders, flashless in many weapons, was one of the
United States, the most important being the C-3 most useful accomplishments of the Ordnance
composition based on RDX. The discovery and great Department before 1940. Traditionally, British
value of the blast effect of explosives led to the propellants have been of the double-base type
development of tritonal, torpex, and minol, which developed prior to World War II and designated as
contain powdered aluminum and have powerful blast cordites. The cordites were made up of varying
effects. In the spring of 1943, EDNA or haleite was percentages of nitrocellulose, nitroglycerin, and mineral
adopted for testing purposes after the DuPont Company, jelly. The mineral jelly (petroleum jelly or petrolatum)
while under contract, overcame the problem of acted as a stabilizer. A sample of British MD cordite
manufacturing ethylene urea, one of haleite's has been found to be of apparently unchanged stability
intermediates. But it was not until the end of the war after 30 years of temperature-climate storage.
that production of haleite could get started. Incendiaries
were found to be even more effective than high-blast
explosives in the destruction of cities. By using
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The search for a compound that was both smokeless the attendant propellants. This was especially due to
and flashless had its beginning in the requirement the work of Wernher von Braun in the late 1930's.
established by the US Army Ordnance's Westervelt c. 1920. Cardox, a device for breaking coal in
Board in 1919. In the early 1920's, ordnance scientists gaseous mines by the pressure produced on heating
offered the using arms samples of nitroguanidine, which liquefied carbon dioxide, was developed. Similar
to a degree unobtainable in any other known propellant, devices were developed in the United States in 1930,
had both properties. But nitroguanidine gave off such and were improved upon in 1955 (Hydrox) and 1959
noxious ammoniacal fumes in combustion that the Field (Chemecol).
Artillery vetoed its use. The Ordnance Department, with d. 1927. Diethyleneglycol dinitrate was thoroughly
no customers in prospect, then abandoned all thought of examined by W. H. Rinkenbach, and the current
building plants to make nitroguanidine. But ammunition method of preparation was patented in 1928 by A.
specialists found no satisfactory substitutes. Adding Hough.
potassium sulfate to propellants for antiaircraft fire,
e. 1930-1931. Dextrinated lead azide was adopted
where flashlessness was all important, helped to solve
for use by the US Army, and began replacing mercuric
that problem. However, it was no answer to the demand
fulminate in priming compositions.
for a completely smokeless and flashless propellant for
field artillery where smoke would obscure a gunner's f. 1931. 2,4-dinitrotoluene (2,4-DNT), obtained
vision and muzzle flash would reveal the tank or battery earlier as an impurity in crude TNT, was used in some
position. explosive mixtures.
g. 1935. From the 1920's onward, scientists at
Picatinny Arsenal had been trying to find a compound
b. 1918-1939. Between the two world wars very that would have the high brisance of RDX without the
little was done in the United States to develop the art of sensitivity to friction and impact. Research on this
rocketry and rocket propellants. A golden opportunity to problem, principally by Dr.George C. Hale, chief
assume leadership in this field was missed when just chemist, led to the discovery of ethylenedinitramine
before the Armistice in 1918, Dr. Robert H. Goddard, (EDNA or haleite) the first entirely American high
Professor of Physics at Clark University, demonstrated a explosive. More powerful than TNT, EDNA was slightly
shoulder-fired "recoilless gun" or "rocket gun" at less powerful then RDX but was also less sensitive.
Aberdeen Proving Ground, MD. The results of Dr. EDNA's stability gave it an important advantage in
Goddard's demonstration were summarized by considerations of manufacturing, loading, storage,
Ordnance Department witnesses as proving the validity transportation, and field use. Designated haleite, in
of his concept of modern rocketry. However, the lack of honor of Dr. Hale, this new explosive could be press-
suitable powder and the need for further work on the loaded into small shells without a desensitizing agent,
electrical firing mechanism along with the Armistice led and its derivative, ednatol, a mixture containing 42
the Ordnance Department to shelve the project. percent TNT, could be melt-loaded into large shells as
Goddard died without receiving any acclaim for this easily as amatol. These advantages were offset in
pioneering work, although comparison of his rocket gun prewar days by the high manufacturing cost of one of its
with the bazooka adopted 24 years later shows how intermediates, ethylene urea. Delay in solving
closely the 1918 model resembles the later weapon. manufacturing problems prevented haleite from getting
During the 1920's, metriol trinitrate or trimethylolethane into combat in World War II.
trinitrate, used as an ingredient in rocket propellants in h. 1936. Primacord, based on a French patent,
World War II, was prepared in Italy and Germany. In was developed by the Ensign-Bickford Company, CT.
1931, the US Army created a one-man rocket unit by Primacord consisted of PETN covered with textiles,
assigning Captain Leslie A. Skinner to study the waterproofing material, and plastics. This detonating
possible use of rockets. Skinner was handicapped by cord had a velocity of 6,405 meters (21,000 feet) per
limited funds for research, and by the indifference of second, and has been used extensively by the armed
superiors. During the mid-thirties, the British began forces for demolition work.
more intensive research on anti-aircraft rockets in i. 1937. Baratol, a mixture of barium nitrate and
anticipation of massive bomber air raids upon their TNT, was developed by the British and used extensively
cities. In the meantime, the Germans made great in WW II.
strides in the development of rockets and missiles and
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j. World War II. High Explosive Bombs. When 1943, the discovery that German bombs containing
World War II began in September 1939, the standard aluminum were extremely effective spurred research.
United States filler for high explosive bombs was This led to the development of minol, a mixture of
trinitrotoluene (TNT). On 5 June 1940, the United aluminum with amatol, and tritonal, a mixture of
States released 8,000 metric tons (9,000 short tons) of aluminum with TNT. For their 2-ton blockbuster bomb,
TNT to the British under Lend Lease. This came out of the British favored Minol 2, a mixture of 200/o
a manufacturing surplus of only about 9,000 metric tons aluminum, 400/o TNT, and 400/o ammonium nitrate;
(10,000 short tons). Most of the war was fought by the and they requested that Minol 2 be used in their
United States with bombs standardized in 1941.The blockbuster bombs being loaded in the US. The British,
earliest departure from TNT for the fillings was RDX, an by using new methods of blast measurement and
explosive known for its great power and brisance but interpretation, had learned that Minol 2 produced an
generally considered too sensitive. The British had area of demolition approximately 30 percent greater
developed a method of using beeswax to desensitize than the area obtained with a TNT filler. US Army
the RDX, and used this filler with terrible effect in the 2- Ordnance technicians had independently arrived at a
ton "blockbuster" bombs dropped on Berlin in April 1941. similarly high opinion of the blast effect contributed by
During the following summer, Air Marshall Arthur Harris aluminum. They arrived at this conclusion by
had pressed for large-scale production of RDX in comparing the performance of oneand two-ton
America. The United States Navy was also interested in blockbuster bombs loaded with minol, TNT, ednatol, and
the explosive because of its effectiveness under water, the RDX mixtures. In comparing minol and tritonal, they
especially in ; ,nixture with TNT and aluminum called preferred tritonal, because it contained no ammonium
torpex. But the United States Ordnance Department, nitrate. When even the slightest degree of moisture was
while willing to start production for the British and the present in the air, aluminum acted on ammonium nitrate
Navy, held back until May 1943 on the use of RDX in its and produced "spewing" (the evolution of hydrogen gas)
AAF (Army Air Force) bombs, and then adopted only a and explosions. Tritonal was much safer, and the
less sensitive mixture with TNT known as RDX British were won over to it. The AAF adopted tritonal for
Compositon B. This first significant change in bomb- large, light-case bombs for jungle warfare, and for all
loading came about as a result of AAF insistence that general purpose bombs. Other bombs were filled with
the large fragmentation bombs developed in 1943 would explosives suitable to their particular purposes. For
need the greater power of RDX Composition B to burst fragmentation bombs, RDX Composition B continued to
their thick walls with the greatest effect. Henceforth, be the preferred filling because it had more brisance
Composition B was used in only about 40 percent of the than tritonal. The US one-ton semi-armor-piercing
general pupose bombs. The reasons were twofold. bombs developed in early 1944 were loaded with
First, the short supply caused by competition between picratol, a mixture of TNT and ammonium picrate, or
RDX, and high octane gasoline, and synthetic rubber for with Explosive D. Explosive D was the least sensitive to
production facilities and, second, the tendency of shock and friction, which made it the best explosive to
Composition B to detonate high-order without fuze mix with TNT in a bomb that had to withstand severe
action under the shock of impact. RDX was more prone shock and stress before detonating.
than TNT to prematurely deflagrate (decompose rapidly k. World War ll. Reverse Nitration of TNT. During
without detonating) when employed in delayed-action 1941 and 1942 the inadequate supply of TNT for
bombs dropped from high altitudes. In the war-long highexplosive bombs and shells was a major problem
argument over the relative merits of blast and for Ordnance. Because the shortage had been
fragmentation, the pendulum now began to swing back foreseen, plans were made to use a substitute explosive
toward blast partly because by 1944 the AAF would called amatol (a mixture of TNT and ammonium nitrate)
have aircraft capable of delivering larger and heavier for shell or bomb loading until new TNT plants came into
loads. After 1943, the new aluminized fillings were of full production. Even so, a critical shortage of TNT
far greater interest than either RDX Composition B or developed despite these plans. But the shortage
ednatol. Until WW II, the use of aluminum in explosives suddenly disappeared when a new process appeared on
had not been extensive. Tests in 1941 in England had the scene almost by accident. During an inspection of a
failed to indicate any significant difference between small Canadian TNT plant at Beloeil near Montreal in
aluminized explosives and amatol or Composition B. In 1941, LTC John P. Harris of Ordnance discovered that
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the plant was "doing things backward" by putting toluene By then, urgent demand could not allocate facilities to
into the acid instead of putting acid into the toluene. produce nitroguanidine in large quantities, and the
Despite some resistance by US TNT producers, the new Ordnance Department could only procure small lots for
process was tried at the partly built Keystone Plant at testing and experimental firing. Whatever the
Meadville, PA. The result was a trippling of TNT output. advantages of nitroguanidine, neither it nor any other
Lines designed to turn out 16 tons a day produced more composition was ideal for all purposes. Even in
than 50 tons a day. The need for TNT substitutes conventional artillery and small arms ammunition, where
vanished, and the cost per unit was cut in half. ballisticians understood propellant behavior better than
in rockets and recoilless rifle ammunition, compromises
I. World War II. Toluene from Petroleum. were inescapable. The primary requiste for one weapon
Development of a new means of producing toluene, the or one particular use tended to be different from every
basic material from which TNT is made, was another other weapon or use. In addition to these problems,
highly significant technological advance of World War II. World War II introduced the problem of climate
The importance of this chemical stems from the fact that extremes at which firing had to take place when Allied
nearly half of every unit of TNT (trinitrotoluene) must troops were fighting in arid deserts, damp jungle heat, or
come from toluene. In World War I, toluene was in the subzero winter weather of northern Europe and of
derived from coal as a by-product of coke ovens, and the Aleutian Islands. Therefore, a series of propellants
some was extracted from natural gas. Yet the supply in were needed to cover widely varying contingencies.
1917-18 was so limited that the Assistant Secretary of Since basic research as well as prolonged applied
War, Benedict Crowell, later called this shortage "the research was necessary, many problems remained
greatest and most pressing of all the problems in regard unsolved at the end of the war. But the field was
to existing raw materials." In contrast, during World War explored more thoroughly than ever before in the United
II high-explosives production was never seriously States, and lines of investigation were clarified for
hampered by lack of toluene. As early as 1927, postwar development. In processing propellants,
Standard Oil of New Jersey had obtained patent rights industry and the Ordnance Department made
from a German firm to use a process for producing considerable advances during the course of the war.
toluene from petroleum. In 1939, a contract with One new method developed by the Hercules Powder
Standard Oil was placed by Picatinny Arsenal to prepare Company for washing nitrocellulose in a continuous filter
toluene by this process at Baytown Ordnance Works, instead of in large tubs by the old "settle and decant"
which was erected next to the Humble (a Standard Oil system, washed the nitrocellulose more thoroughly and
subsidiary) refinery in Baytown, TX. By October 1942 thus improved the stability of nitrocellulose. The
this plant was producing toluene at the rate of 246 DuPont Company found that using preheated alcohol
million liters (65 million gallons) per year, which when during the winter to dehydrate nitrocellulose reduced the
compared with a total toluene production of less than 34 hydration time cycle, improved the yield, and made for a
million liters (9 million gallons) in the US during 1918 more uniform product. This in turn produced a much
shows us the value of this process. better powder. The Radford Ordnance Works carried on
extensive experiments to improve manufacturing and
testing techniques as well as for finding better chemical
m. World War II. Artillery Propellants. The
compositions. Yet in the spring of 1945, reports from
problem of obtaining artillery propellants that were both
the Combined Intelligence Objectives Subcommittee,
flashless and smokeless continued to plague the U.S.
established to locate data in Europe on Axis research
Army. Early in the war, the Navy seized upon
and manufacturing procedures, indicated that Germany
nitroguanidine as the one feasible answer to novel
had developed several processes more effective than
conditions of combat. For the first time, American ships
those of the United States. The most novel German
in the Pacific were preparing to fight in small harbors
method was one of casting propellant grains by adding a
where maneuvering was all but impossible. Flash at
paste of moist nitrocellulose and diethyleneglycol
night betrayed the vessel's position, and smoke by day
dinitrate (DEGN) to molten TNT and pouring the mixture
made second rounds inaccurate. Negotiations with
into steel molds to cool. Grains as large as 1,000
Canada in 1943 for the purchase of nitroguanidine, from
millimeters were cast this way. After the war, complete
the one plant upon which British and Canadian forces
sets of the German equipment deemed most useful and
were also depending, succeeded in meeting Navy needs
novel went to Picatinny Arsenal for study.
but left no surplus for the US Army. The Army Ground
Forces were not convinced of the value of this
propellant until TM 9-1300-214 shortly before D-Day.
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n. World War II. Wood Pulp and Cotton Linters. tiny crack in a burning grain of powder would create
Before the war, the standard practice for making pressure peaks at particular spots of the encasing rocket
smokeless powder called for the treatment of bleached mortar tube and thus either burst the tube or cause
cotton linters with a mixture of nitric and sulfuric acid. In erratic populsion. Consequently, to get a safe usable
the summer of 1941, it became apparent that even with rocket propellant made by the solvent process meant
a good cotton linters crop and capacity operation of using grains of small cross-section (in technical
bleacheries, the supply of linters for powder would fall phraseology, thinwebbed powder) in which
short of requirements. Ordnance chemists, therefore, malformations occurring in drying would be few and
turned to the use of a special wood pulp that was inspection could be exacting. A method of
available in quantity, was suitable for most kinds of manufacturing solventless double-base propellant by a
powder, and was cheaper than cotton linters. The dry extrusion process had been developed in the late
Hercules Powder Company had made smokeless 1930's by the British. This produced much thicker-
powder from wood pulp for a number of years, and webbed, and therefore longerburning, grains, but
Ordnance found the product completely acceptable. required enormously heavy presses to extrude or
Use of wood pulp as a supplement of, but not a compact, and force out the propellant into the desired
replacement for, cotton linters was approved promptly shape.
except for rifle powder and certain other uses. Soon p. World War II High Explosive Artillery Projectiles.
most plants had one or two lines for nitrating cotton, an Considerable power combined with sensitivity, which
equal number of lines for nitrating wood pulp, and made for easy loading, stability, and safety in handling
several "swing lines", which were adaptable for use of and transport, made TNT and amatol the preferred
either materials. From January 1942 to the end of the highexplosive fillings for most high-explosive artillery
war, Ordnance plants used roughly equal quantities of shells at the outset of World War II. This was largely
cotton linters and wood pulp. There was never a due to their availability in large quantities. As the war
concurrent shortage of both materials, although there progressed and ammunition became more complex in
were times when the supply of one ran low or was design and more specialized in function, demand arose
expected to run low. At such times, Ordnance drew for improved explosives. This demand could not be met
upon its inventories while converting the swing lines to to any extent because the explosives developed
meet the situation. The use of wood pulp doubled the between wars did not get into large-scale production in
existing supply of cellulose for powder, and eliminated a time. Nevertheless, thoughout the war the US Army
serious potential bottleneck in ammunition production. Ordnance Department sought ways of using more
o. World War II. Rocket Propellants. Difficult powerful new explosives, and ways to adapt old ones to
though the US program was for improving propellants special purposes. There were at hand several
for conventional weapons, the question of developing explosives of higher shattering effect, or brisance, than
suitable rocket propulsion was still harder to answer. TNT. The most important were, first, cyclotrimethylene
From the very beginning everyone concerned with trinitramine, which the Americans called cyclonite and
rocket research agreed that single-base powders would the British called RDX ("Research Department
lack the necessary energy and that double-base Explosive"); second, pentaerythritol tetranitrate or
powders, that is nitrocellulose and nitroglycerin PETN; and third, EDNA (later called haleite). RDX and
combined, must be used. Double-base powders, made PETN were too sensitive to be used in the pure state in
by the solvent process, had been manufactured in the a shell. Therefore, to form usable compositions it was
United States for a number of years for use in necessary to combine them with oils or waxes or with
intermediate and large caliber artillery. The method other explosives. The British had managed to
used a solvent of acetone and alcohol to make a colloid, desensitize RDX by adding nine percent beeswax to
from which grains or flakes could then be formed. form Composition A for press-loading into shells; with
About 1939, the Hercules Powder Company found a 39.5 percent TNT and one percent beeswax to form
way of producing a solventless double-base propellant, Composition B, chiefly for bomb loading; and with 11.7
which was plasticized by heat and pressure and then percent of a plasticizing oil to form Composition C, for
rolled out into sheets for mortar increments. But neither demolition work. These formulas were provided by the
was adaptable for rockets where a solid stick or grain, British to the US in 1940, and development work was
not sheet propellant, was needed, and where the undertaken by the DuPont Company under contract of
essential quality of uniform burning precluded using a the Ordnance Department.
grain without so much as a hair crack or fissure. Even a
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The most sensitive of all high explosives was PETN, the binary compositions, PTX-2 was more stable than
which was even more readily detonated than RDX. 50/50 pentolite and less sensitive to impact. Preliminary
PETN was desensitized by mixing with TNT to form a firings at Picatinny indicated that PTX-2 would be
composition named pentolite, which has been particularly adaptable to shaped-charged ammunition;
extensively used in detonators, bazooka rockets, rifle but PTX-2 was still in the testing stage at V-J Day.
grenades, boosting devices, and in the shaped charges r. World War II. Shaped Charges. If no new
of antitank shells. Because of production difficulties, explosive for artillery shell came into use during the war,
haleite, the most promising of the new high explosives, a new way of employing explosives nevertheless did.
never saw much use in World War II except in the form The effect of a hollow-charge or shaped-charge
of ednatol in mixtures with other explosives. projectile against armored targets was first successfully
q. World War II Armor-Piercing and Antitank demonstrated by the bazooka and the rifle grenade.
Projectiles. Much of the work of improving high- The intense forward jet of the charge, serving to focus
explosive compositions was directed toward finding the part of the energy of the explosion in a limited area,
most efficient filling for anti-tank shells. For armor- gave to the light-weight, low-velocity rocket the armor-
piercing projectiles, relatively insensitive ammonium piercing advantages hitherto possessed only by high-
picrate, "Explosive D," had long been preferred. As it velocity artillery. The antitank rifle grenade, containing
was not likely to detonate on impact, the shell could only 113 grams (4 oz) of pentolite, would penetrate up to
penetrate the armor plate before exploding. But 102mm (4 inches) of homogeneous armor plate at a
experience with heavy German tanks in North Africa normal angle of impact. The first rifle grenade to use
showed that something more was needed in the way of this principle was designed by a Swiss inventor, Henri
power and fragment action coupled with greater Mohaupt, whose claims of inventing a "new explosive"
incendiary effect within the tank. Chemists at Picatinny had interested the British in 1939. However, the price
Arsenal accordingly tried several expedients. In armor- Mohaupt quoted for his discovery was considered too
piercing shell, addition of a small amount of powdered high and the British showed no further interest in his
aluminum to cyclotol (a mixture of RDX and TNT), to invention. Mohaupt then offered to show the United
ednatol, or to TNT produced more brisance than States particulars of the construction of his device for a
Explosive D and increased sensitivity to impact. In fee of $25,000 paid in advance. Caution on the
high-explosive antitank shell fillings, conversely, the American part further delayed acquiring the rights until a
difficulty was the exact opposite. The high sensitivity of demonstration by Mohaupt at Aberdeen Proving
pentolite made it liable to detonation on target impact so Ground, MD, was permitted in 1940, doubtlessly
that the problem was to desensitize it to the proper because Mohaupt provided 200 grenades for the
degree. Several possibilities considered were the demonstration. Army and Navy representatives who
addition of wax to the pentolite, the reduction of the witnessed the test firings were convinced that this was
PETN content, and the substitution of ednatol or indeed an important "new form of weapon." A similar
Composition B. None was entirely satisfactory. The proposal by Nevil M. Hopkins, an American inventor,
search for an explosive composition of the greatest for a shaped-charge bomb had been rejected earlier by
possible power and brisance took a new turn after the United States Ordnance Department as not being a
analysis of foreign explosives at Picatinny Arsenal new concept. By citing a 1911 British patent by Egon
during 1943. Hitherto, research had been concentrated Neuman of the "Munroe-Neuman" principle, the
on binary explosive compositions such as pentolite, Ordnance Patent Section thereupon showed Mohaupt's
Composition B, or ednatol. The examination of a Soviet "secret" to be no secret. Thus the Ordnance was able to
76mm high-explosive armorpiercing round suggested conclude a more reasonable contract with Mohaupt's
the possibility of employing ternary mixtures. Tests company than the Swiss had originally demanded. An
revealed that castable ternary explosive mixtures, such adaption of Mohaupt's design later formed the basis for
as RDX-Tetryl-TNT and Haleite-PETN-RDX, offered the M9A1 antitank rifle grenade, and the 2.6-inch
promise not only for armor-piercing projectiles but as antitank "bazooka" rocket. Application of the shaped-
fragmentation ammunition for weapons designed to charge principle to artillery naturally proceeded. The
produce blast, and for demolition charges. Further choice of howitzers was logical because their low
study showed that haleite ternaries were unstable. The velocity made conventional types of armor-piercing
best combination seemed to be a mixture of PETN- projectiles ineffective, whereas for a shaped-charge
RDX-TNT designated PTX-2 (Picatinny Ternary explosive low velocity was an advantage. Before Pearl
Explosive). More brisant than any of TM 9-1300-214 Harbor, in an
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atmosphere of great secrecy, work began on a shaped- projectiles, but also had the undesirable disadvantage of
charge shell, specifically the "HEAT" (highexplosive sometimes becoming an incendiary. Another
antitank) round, for the 76mm howitzer. The designers, disadvantage was that WP tended to melt in hot
paying careful attention to the length of the ogive, the climates, which affected the stability of the round in
filler of 50/50 pentolite, and the striking velocity, came flight. Storage in hot climates also resulted in expansion
up with a round of the same length as the corresponding of the WP and subsequent leakage. Despite these
high-explosive round. The HEAT round, at a muzzle shortcomings, WP was very effective for building up
velocity of approximately 305 meters per second, would smoke screens as particularly demonstrated by the 4.2-
penetrate 76 millimeters (3 inches) of homogenous inch mortar battalions in Europe and the Pacific. Smoke
armor plate. A similar shell for the 105 millimeter bombs filled with WP and PWP were used extensively
howitzer appeared simultaneously. Standarized in late for spotting targets and for screening parachute drops.
1941, HEAT shells were produced in time to take part in Plasticized WP or PWP was developed to reduce the
the North African tank battles early in 1943. The pillaring effect of the exploding munition found with pure
Ordnance Department had high hopes that the HEAT WP. PWP is obtained by mixing WP with a very
rounds would succeed in penetrating the heavy German viscous solution of synthetic rubber to form a
armor plate that had defeated solid armor-piercing homogenous mass. For loading into munitions where a
ammunition. Although sometimes successful, the longer lasting smoke screen is desired, HC
performance of shaped charges was not dependable (hexachloroethane mixture) was preferred, e.g., smoke
enough. In an effort to find out why, the Ordnance pots and base ejection shells. WP was used in rifle
Department, with the help of the National Defense grenades. HC was used in hand grenades. US tanks in
Research Committee (NDRC) and the Navy, intensified North Africa were outfitted with smoke grenade
its research. In some cases, observers in the field had launchers to screen the tanks from antitank fire.
blamed faulty manufacture, but investigators proceeded t. World War II. Pyrotechnics for Illumination. In
on the assumption that design of the round and the 1944, the Army Air Forces (AAF) made an important
principle of operation needed improvement. Because of change in doctrine that affected munition development
the difference in behavior of the nonrotating rocket and requirements when they initiated 24-hour bombing
the rotated shell, the effect of the spin was carefully operations. Night bombing, always favored by the Royal
studied as well as the method of fuzing. One of the Air Force but hitherto opposed by the United States,
most important discoveries was that an increase in plate gave new importance to pyrotechnics. Aircraft flares
penetration was directly proportional to an increase, up came close to the usual bomb design. The AN-M26
to approximately three calibers, in "standoff" distance, aircraft parachute flare, designed to provide illumination
that is, the distance from the base of the cone to the for night bombardment, contained its illuminant mixture
target at the moment of detonation. Yet this finding was in a round-nosed, finned-tail cylinder and developed
only a beginning, and the solution to the puzzling 800,000 candlepower for about three minutes. The
behavior of hollow charge projectilles was not found most important development concerned high-altitude
during World War II. night photography, and markers to identify targets at
s. World War II Smoke Screening Munitions. In night. The prewar M46 photoflash bomb gave only 500
the spring of 1940, the Germans demonstrated the million candlepower. Picatinny Arsenal experimented
value of smoke to screen their advance when they with different combinations of case, filler, and initiating
blitzed the Low Countries. Basic developments in system. The result was a photoflash bomb that
smoke employment during World War II were its use to produced approximately three times as much light as
screen river crossings, beach landings, paratrooper the M46. Target identification bombs grew out of a
assaults, and rear area targets from artillery fire and technique evolved by the British to improve the
aircraft observation and attacks. Prewar versions of the accuracy of their night bombing. Their "Pathfinder
HC smoke pots were enlarged, and floating smoke pots Force" equipped with special navigational aids flew over
were developed for amphibious operations. Aircraft a target in advance of the attacking force and dropped
smoke tanks were developed for spraying liquid smoke various kinds of candies and flares, some to illuminate
mixtures. Smoke generators were developed for the general area and others to mark the special target
screening large areas by vaporizing fog oil. White with color. One munition designed specifically for
phosphorous (WP) was the choice filler for most
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this work was a stabilized bomb that ejected sixty-one After limited testing, the new grenade was type
pyrotechnic candles at a predetermined altitude. In the classified as the M18 smoke grenade and was issued in
United States, the earliest research on target four colors: green, red, violet, and yellow. The M18
identification markers produced five bombs of this type. grenade remains the most widely used signaling device
All were modifications of the 250-lb general purpose for ground troops today, which is a remarkable
bomb and differed one from the other in the type of achievement considering that the M18 was adopted for
candle they contained. The candles were small flares Army use within six weeks of the statement of the
that burned with either red, green, or yellow light for requirement. This same loading technique was later
about three minutes. Each target identification bomb applied to artillery base ejection canisters for marking
released its load of these signal candles, which together boundaries.
made a pattern of colored light approximately 100 v. World War II. Flame and Incendiary Munitions.
meters in diameter around or on the target. These In the intervening years from World War I to World War
signal candles were designed to be visible from altitudes II, the development of flame weapons was studied by
as high as 35,000 feet. To keep the candles from being most nations except the United States. During the
disturbed while they were on the ground, one type of Ethiopian War in 1935 and 1936, the Italians employed
candle had an explosive charge that would detonate at the first armored vehicle-mounted flamethrowers. The
the end of the burning time of the candle, the time being Germans employed a flame tank during the Spanish
from one to two minutes. As the AAF extended its night Civil War and in 1939 used portable flamethrowers in
operations, especially low-level bombing and strafing of Poland. These instances proved to the United States
illuminated targets by fighters and light attack bombers, that the development of flame weapons could no longer
need arose for ground burning flares that would produce be denied. In 1940, the US Army took steps toward
a minimum amount of smoke and thus leave the targets developing a flamethrower and a flamethrower tank.
as clear as possible. For this purpose, the Ordnance These flamethrowers served an important role in the war
Department developed flare bombs loaded with in the Pacific, particularly in dislodging the determined
smokeless units. At the end of the war Army and Navy Japanese soldiers from caves and fortifications. On
experts agreed that future developments must be aimed Okinawa alone, flamethrowers are credited with the
at greatly increasing the candlepower, burning time, and capture or death of 20,000 Japanese soldiers who were
visibility of all pyotechnics, especially the photoflash holed up in the caves while less than 100 American
bomb. flamethrower operators were killed in the operations.
The development of napalm ("nap" for the napthenic
u. World War II. Pyrotechnics for Signaling. With acids and "palm" for the coconut fatty acids which made
the use of massive bombing air raids and close ground up the first type of this thickner) by the United States in
support by the Army Air Forces came the need for better 1941 made possible the greater use of gasoline for use
signaling devices. Especially important were hand in flame weapons. This gelled mixture made it possible
signals for downed fliers. Survival kits were developed for aircraft to deliver fire bombs over hard-to-get
which included colored smoke and flare distress signals pinpointed areas and for flamethrowers to project a
for the aviators to carry. A substantial improvement in flame rod over a greater distance than was previously
the ground signals used by the Armed Forces was made obtainable. By August 1944 the United States AAF
when the US Army Chemical Warfare Service (CWS), Board had come to the conclusion that "where there is
now the Chemical Corps, made a change in the method vulnerability to fire, the damage by fire is greater than
of consolidating the colored smoke mixtures in the by demolition," a conclusion, to be sure, that observers
grenades used for this purpose. The prewar M1 colored had reached during the London blitz of 1940 but which
smoke grenades used a slow-burning mixture that had not been acted upon. The decision of the Board in
burned about two minutes. In 1942, the Army Ground 1944 was to increase the incendiary bomb program to
Forces established a requirement for a colored smoke the highest priority. The United States Army CWS
grenade that would form a smoke visible at a slant provided the Army Air Force with about 48 million
range of 3,050 meters ( 10,000 feet) and last about one incendiary bombs, which were effectively used,
minute. By devising a method of consolidating the especially on the large cities of Japan. Most of these
pyrotechnic smoke mixture with heavy presses, CWS bombs were clustered bomblets containing thermate
engineers were able to provide a grenade meeting the (TH3 and TH4), a new
Army TM 9-1300-214 Ground Forces' requirements.
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incendiary mixture, which replaced the original thermite Frankford Arsenal and was standardized for United
mixture. When ignited, thermate burns intensely at States use.
2,2000C. Molten iron from burning thermate will melt
metal, burn through steel plate, and ignite flammable 2-9. Post-World War II Developments. The nuclear
materials. Oil and metal incendiary mixtures, such as bombs that ended World War II did not end
PT1 and PTV, were also used as fillings in large requirements for conventional explosives and
thincased bombs. PT1 is a complex mixture based on ammunition. As was shown by the Korean War (1950-
"goop," a paste comprised of magnesium dust, 1953) and the Vietnam War (1964-1973), the need for
magnesium oxide, and carbon, with a sufficient amount the United States to develop even more effective
of petroleum distillate and asphalt to form the paste. munitions and more powerful explosives or energetic
PTV is an improved oil and metal incendiary mixture of materials became more apparent than ever. In spite of
polybutadiene, gasoline, magnesium, sodium nitrate, intensive effort, chemists at the Army's laboratories and
and p-aminophenol. However, napalm proved to be one arsenals failed during World War II to develop a new
of the most effective aerial incendiary agents in the war. explosive composition for shell loading that was both
On the evening of 9 March 1945, more than 300 satisfactory and readily available in quantity. The
superforts (B29 bombers) swarmed over Tokyo dropping obstacles were often disheartening. The characteristics
about 2,000 tons of incendiaries, mostly clusters of M69 of an explosive might be considerably affected by
six-pound bomblets. The M69 bomblet was a tube impurities that existed in the raw material or which were
which contained a black powder propellant charge that admitted during manufacture. For example, the
ignited and projected the napalm filling from the tube. instability of PETN was probably due to impurities in the
Aerial photos indicated 16 square miles had been raw material, pentaerythritol. Other variables that had
burned out. Tokyo police records, examined after the to be taken into account were the different methods of
war, showed that more than 250,000 buildings were testing compositions and the differences in interpreting
destroyed about one fourth of Tokyo in this one raid. results. Assuming a composition had been found that
More than 100,000 tons of incendiaries were dropped on promised to combine greater brisance with less
the cities of Japan during World War II. Most of these sensitivity, there was still the question of whether it
were M69 bomb clusters. For destroying materiel to could be economically manufactured, safely handled,
prevent enemy use, the CWS developed a thermate and made unchanging in character in temperatures
grenade, which was standardized as the AN-M14 TH3 ranging from arctic cold to tropical heat. In the search
incendiary grenade for use by the Army and Navy. for explosives with special properties, much work had
Harvard University also developed a napalm fire starter been done in the field of aluminized explosives, but,
(MI), for use by troops to ignite fires in wet climates. although aluminized TNT (tritonal) was used in bombs,
The armament of the American heavy bombers was much remained to be done. At the end of the war the
usually the .50 caliber machine gun. During World War Ordnance Department felt that deeper study of the
II, enemy fighter aircraft did not have armor plating fundamental properties of all high explosives was
capable of deflecting a .50 caliber bullet, although, bullet essential to effective developments in the future. Some
penetration of the plane's armor did not necessarily of the problems of finding suitable high explosives and
knock out aircraft. The enemies use of self-sealing fuel propellants have been resolved in the decades following
tanks necessitated the development of effective World War II. Other problems have cropped up as the
incendiary ammunition. Most urgently needed was an expanding techniques of modern warfare lead to more
effective .50 caliber incendiary round. The first and more specialized requirements for explosives and
acceptable design was the work of the Remington Arms propellants. Future developments may be expected to
Company whose staff already had considerable take the direction chiefly of mixtures of currently known
experience in working on Swiss patents for incendiary explosives and other materials. But in some cases, the
ammunition. The Remington development was based requirements can be satisfied only by new and more
upon the British .303 B Mark VI Z, and was adopted in powerful explosives which are presently being sought.
September 1941. The bullet was a flatbase type with As seen by the experience of the two world wars,
lead base closure and steel body, and was charged with scientists engaged in the field of energetic materials
35 grains of a incendiary mixture consisting of 50 must keep abreast of foreign technology and be
magnesium alloy and 50 percent barium nitrate. An prepared to exploit technical intelligence. The
improved design was developed shortly thereafter by everchanging and rapid advance of
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technology makes it necessary to shorten the lead time desensitizer of explosives like HBX-1, was developed.
from research and development to deployment of new Composition D-2 consists of 84 percent wax, two
ammunition and explosives. But research and percent lecithin, and 14 percent nitrocellulose.
development is only the tip of the iceberg; the biggest f. 1950-1953. When World War II ended,
expenditures for materiel in the Army go to the the United States had a tremendous inventory of
procurement and management of ammunition. An Army ammunition on hand, but unfortunately it was not a
cannot fight for long without the right kinds of balanced stock. There were enormous quantities of
ammunition being available in the necessary mix and some types of ammunition, and only small amounts of
quantities needed to perform its mission. A responsive, others. The hasty mobilization of manpower for the
flexible, viable production base and balanced Korean conflict stripped the Ordnance Department of
inventories must be maintained to assure a strong the military and civilian personnel that might have
readiness posture. With continuing budget restraints, all properly assessed and cared for the huge inventories of
those in the armaments research and development ammunition in its custody. During the years preceding
community must consider these restrictions and the Korean War, powder packed in cotton bags and
exercise close control of the limited resources allocated fuzes made of substitute metals deteriorated. The Army
to them for this purpose. Therefore, scientists and drew too freely upon the large ammunition stockpile for
technicians working in this field must direct their training purposes, yet made no real effort to replace
priorities for research and development to those projects consumption or balance the items in stock. The lack of
with the best prospects of being beneficial to armed postwar orders sent the ammunition industry into an
forces materiel readiness, and avoid projects that may eclipse. When the United States entered the Korean
have only marginal applications to wars of the future. struggle so suddenly in 1950, ammunition facilities and
a. 1945. PLX (Picatinny Liquid Explosive), plants were at a low ebb, and businessmen were
consisting of 95 percent nitromethane and five percent reluctant to reconvert their factories to wartime effort.
ethylenedinitramine, was developed at Picatinny Arsenal Another element that restrained a shift to the immediate
by L. H. Eriksen and J. W. Rowan for use in mine production of ammunition was the prevalent belief that
clearing. The Germans had used similar liquid the Korean War would be short, and did not warrant a
explosives during World War II under the name Myrol. sizeable dislocation of the United States industrial effort.
b. 1945. Tripentaerythritol octanitrate was Even after this fallacy was shattered by the entry of the
patented by J. A. Wyler of Trojan Powder Company, Chinese into the war in late 1950, the policy of butter
PA, for use as a high explosive and possible gelatinizer and guns continued, and no large scale mobilization of
for nitrocellulose. industry took place. Compounding the situation of
unbalanced stocks, the lack of industrial mobilization
c. 1946-1949. Composition C-4, known as
that normally follows the outbreak of war led to further
Harrisite, was developed by K. G. Ottoson at Picatinny
setbacks in the battle for ammunition production. By the
Arsenal as a replacement for Composition C1, C-2, and
time funds budgeted in 1951 were translated to
C-3. Composition C-1, C-2, and C-3 were the United
production in 1953, the war was practically over. In the
States standard plastic RDX demolition explosives, and
meantime, the answer to the shortages in Korea was for
were originally derived from Britian's Composition C,
the Army to reduce the authorized ammunition required
which was developed during World War II.
supply rates in the belief that the combat units were
d. 1946-1949. Benite, a black powder wasting their ammunition. The net result was a war in
substitute, was developed at Picatinny Arsenal for use in which American firepower could not be used to its best
igniter compositions of artillery primers, or in base advantage. The lesson learned from this is that a need
igniter bags for separate-loading ammunition. Benite is for better industrial mobilization planning, and for closer
in the form of extruded strands consisting of ingredients contact with industry in the development and
of black powder in a matrix of nitrocellulose. maintenance of a viable production base exists.
e. 1946-1949. Composition D-2, which is
not an explosive but serves as an emulsifier and
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and continued to rise until the ammunition supply rates Ammunition Proliferation Study Committee staffed with
for the grenades were as much as 100 times the World representatives from the developing arsenals (Picatinny,
War II and Korea rates. Due to ammunition shortages, Frankford, and Edgewood), the National Inventory
terrain, climate, and guerrilla warfare, the United States Control Point, and the United States Army Training and
troops were often forced to rely upon field expedients Doctrine Command (TRADOC). This committee,
during their missions. A new development program chaired by DCSLOG, was assigned to review every
called ENSURE (Expedited Non-Standard Urgent conventional ammunition item with a stock number or
Requirement), whose function was to meet troop every ammunition item in development, and
demands for special items needed to support SEA recommend deletion of all items considered not
operations, was established by the Defense Department. essential to the mission of the Army. Hundreds of
Many of the ENSURE items fielded under this program obsolescent and non-essential items of ammunition and
were ammunition related and are now standard items for explosives were eliminated. Among these were FS
Army use. For example, although flamethrowers were smoke and M1 thickener. Ammunition supply rates
used extensively in SEA, a stand-off capability to project were considered. For example, because of a low usage
flame was needed to reduce the vulnerability of the factor, the AN-M14 TH3 incendiary grenade was
operator to enemy fire. From this ENSURE considered for elimination until it was established that
requirement, a 66mm multishot flame rocket launcher the incendiary grenade was used only when necessary
(M202 and M202A1) was developed. The resulting M74 to destroy equipment to prevent enemy use; therefore,
incendiary TPA incendiary 66mm rocket was fielded and ammunition supply rates are not applicable to this item.
is now a standard item. The rocket is filled with TPA Retention of the M18 violet smoke grenade was justified
(thickened pyrophoric agent), which consists of triethyl because violet was the second most used color for
aluminum (TEA) thickened with polyisobutylene (PIB). signaling in Vietnam; and more colors, not less, were
Other significant ENSURE developments were a broad needed to prevent the enemy from guessing the
range of various 40mm cartridges and signaling purpose of the signal.
devices, improved mines, and pyrotechnics for s. 1973-1976. To protect tanks, the United States
battlefield illumination. Army devoted considerable attention to the problem of
rapidly screening tanks from enemy antitank rounds and
missiles. A DARCOM Project Manager for Smokes and
r. 1973. The problem of managing a rapidly Obscurants was appointed to manage a program of
increasing number of conventional ammunition items in developing and fielding countermeasures. One of the
the Army inventory was addressed at the conclusion of first items adopted for Army use was a British smoke
the war in Vietnam. Although.many items developed as grenade launcher, which fires salvos of red phosphorous
a result of the ENSURE program had justified their (RP) UK L8A1 smoke screening grenades from armored
existence in combat, others were, by their very nature vehicles. After launch, these grenades detonate in the
"field expedients" or were advance prototypes from air to form an immediate, dense white smoke cloud that
ongoing development programs' In addition, many of the obscures the tank from enemy view. Smoke grenade
items in the inventory were obsolescent left over from launchers have been developed for use in many of the
Korea, World War II, and even pre-World War II assets. armored vehicles in use or development today,
Accordingly, the Deputy Chief of Staff for Logistics including the M1 tank.
(DCSLOG), Department of the Army, established an
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CHAPTER 3
GENERAL CHARACTERISTICS AND CLASSIFICATION OF
ENERGETIC MATERIALS
3-1. Types of Energetic Materials. Energetic supersonic speed proceeds through the explosive
materials are chemical compounds, or mixtures of causing decomposition of the explosive material. The
chemical compounds, that are divided into three classes reaction rate is determined by the velocity of the shock
according to use: explosives, propellants, and wave, not by the rate of heat transfer. The velocity of
pyrotechnics. Explosives and propellants that have the shock wave depends on the physical characteristics
been properly initiated evolve large volumes of hot gas of the individual explosive material. The range of
in a short time. The difference between explosives and velocities is from about 2,000 meters per second to
propellants is the rate at which the reaction proceeds. In about 9,000 meters per second. The factors that affect
explosives, a fast reaction produces a very high the velocity include density, degree of confinement, and
pressure shock in the surrounding medium. This shock geometric configuration of the charge.
is capable of shattering objects. In propellants, a slower
reaction produces lower pressure over a longer period of 3-3. General Behavior of Pyrotechnic
time. This lower, sustained pressure is used to propel Compositions. Pyrotechnics is the technology of
objects. Pyrotechnics evolve large amounts of heat but utilizing exothermic chemical reactions that, generally
much less gas than propellants or explosives. speaking, are non-explosive, relatively slow, self-
sustaining, and self-contained. Pyrotechnic
3-2. Characteristics of Burning and Detonation. compositions are generally finely divided fuels such as
Burning and detonation of energetic materials are metals, alloys, and hydrocarbons mixed with oxidizers.
exothermic redox reactions. The reaction is
selfsustaining after an initial activating energy has been 3-4. Classification of Energetic Materials. There is
applied. On the basis of mass, the amount of energy considerable variation among the properties of the
released by propellants and explosives is comparable. compounds that constitute each of the three major
However, this energy is considerably less than is classifications of energetic materials.
produced by common fuels such as carbon burning in
air. Propellant burning, or deflagration, is the very rapid a. The variation in the properties of explosives is
burning that results from having a fuel and an oxidant in put to practical use in armaments by an arrangement
very close contact. In some propellants such as called an explosive train (figure 3-1). An explosive train
nitrocellulose, the fuel (which consists mainly of consists of elements arranged according to decreasing
hydrogen and carbon) and oxygen are parts of the same sensitivity and increasing potency. The first element,
chemical compound. In other propellants, finely divided the initiator, consists of a small quantity of highly
discreet fuels and oxidents are mixed. The fuel may be sensitive material. The highly sensitive material
a hydrocarbon or other readily oxidizable material such consists of a primary explosive and other ingredients.
as aluminum. The oxidizer is usually an inorganic Primary explosives are easily detonated by heat, spark,
compound such as ammonium perchlorate or impact, or friction. In large quantities these materials
ammonium nitrate which contain oxygen in excess of are extremely hazardous because of their great
the amount required for their own oxidation. sensitivity. The other ingredients in the priming
Deflagration of propellants proceeds the same as composition increase the sensitivity of the mixture to the
normal burning. Combustion takes place on the surface desired property, such as percussion or heat. The
and proceeds into the grain. The rate determining second element, the booster, contains a larger quantity
factors in the reaction are the rate of heat transfer into of less sensitive but more powerful material called a
the propellant grain from the burning surface and the secondary or high explosive.
rate of decomposition of the propellant formulation. The
rate of heat transfer depends on the pressure of the The booster is used either as an intermediate stage to
combustion products. The burning rate is defined as the detonate material that is too insensitive to be detonated
rate at which the burning surface consumes a propellant by the relatively weak initiator or to ensure complete
grain in a direction normal to the grain surface. detonation of the main charge. The main or bursting
Detonation of explosives is a completely different
process than deflagration. A shock wave moving at
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charge, also a secondary explosive, is the least composition may be suitable for use in several
sensitive material but comprises the bulk of the applications.
explosive charge. Secondary explosives differ from
primary explosives in three major ways. Small,
unconfined charges (one to two grams) of secondary
explosives, even though ignited, do not transfer easily
from a burning or deflagration reaction to a detonation.
Except in the case of dust clouds, ignition by
electrostatic spark is difficult. The shock required for
ignition is much greater for a secondary explosive than
for a primary explosive. In some cases, two other
elements, a delay and a relay, may be added to the
explosive train between the initiator and booster. The
delay is calibrated to prevent detonation of the booster
for a specified length of time. A delay is considered a Figure 3-2. Ignition train.
pyrotechnic device. A relay may be required to
strengthen the relatively weak output of the delay to (1) Single-base. These compositions contain
detonate the booster. nitrocellulose as their chief ingredient. In addition to a
stabilizer, they may contain inorganic nitrates,
nitrocompounds, and nonexplosive materials, such as
metallic salts, metals, carbohydrates, and dyes.
(2) Double-base. This term has been applied
generally to compositions containing both nitrocellulose
and nitroglycerin. However, since other gelatinizers
such as DEGN are used by other countries, a better
definition of a double-base composition is one
containing nitrocellulose and a liquid organic nitrate
which will gelatinize nitrocellulose. Like single-base
Figure 3-1. Explosive train. propellants, double-base propellants frequently contain
additives in addition to a stabilizer.
(3) Triple-base. This term is applied to
propellants containing three explosive ingredients with
b. An ignition train, which is used to ignite
nitroguanidine as the major ingredient. The other two
propellant charges, is shown in figure 3-2. The primer
explosive ingredients are usually nitroglycerine and
contains a priming composition which consists of a
nitro-cellulose. As in the double-base propellant, other
mixture of fuels and oxidants that are sensitive to stimuli
gelatinizers may be substituted for the nitroglycerine.
such as impact, heat, or spark. Application of the
The nitroguanidine in the formulation produces a lower
appropriate stimulus causes ignition. The primer ignites
flame temperature and a greater amount of gaseous
the igniter which in turn ignites the propellant charge.
combustion products. The lower flame temperature
The igniter is considered a pyrotechnic device.
considerably reduces erosion of gun barrels and the
c. Propellants are divided into four classes: greater amounts of gas produce a greater force on the
single-base, double-base, triple-base, and composite.
projectile. Triple-base propellants also contain additives
Division of the propellants into these classes is on the
in addition to a stabilizer.
basis of composition, not use. Single-base
compositions are used in cannons, small arms, and (4) Mixed nitrate esters. Two propellant
grenades; double-base compositions are used in compositions were developed in the United States to
cannons, small arms, mortars, rockets, and jet replace the triple-base formulation due to the shortage
propulsion units; and triple-base compositions are used of nitro-guanidine. The XM35 composition contains
in cannon units. Composite compositions are used nitrocellulose, TMETN, TEGDN and DEGDN. The
primarily in rocket assemblies and jet propulsion units. higher force XM34 formulation contains nitrocellulose,
The choice of a propellant for a specific use is BTTN, TMETN and TEGDN. The combination of mixed
determined by ballistic and physical requirements rather nitrate esters give higher gas volumes and lower flame
than on the basis of composition. A given propellant temperatures than nitroglycerin alone.
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(5) Composite. Most composite propellants 3-5. Chemical Nature of Energetic Materials.
contain neither nitrocellulose nor an organic nitrate. Chemical properties of individual energetic materials are
They generally consist of a physical mixture of a fuel discussed in the appropriate chapters of this manual.
such as metallic aluminum, a binder which is normally The properties discussed for these materials include the
an organic polymer (generally a synthetic rubber which following:
is also a fuel), and an inorganic oxidizing agent such as
ammonium perchlorate. These are heterogeneous a. Heat of Fusion. The heat of fusion is the
physical structures. amount of heat necessary to transform (melt or fuse) a
unit of solid into a liquid at the same temperature and
d. Pyrotechnic compositions are divided into the standard pressure. This quantity is usually expressed in
following categories according to use. terms of calories per gram.
b. Heat of Vaporization. The heat of vaporization
(1) Flares and signals. Flares burn to is the amount of heat necessary to convert a unit of
produce intense light that is used for illumination. liquid to vapor at the same temperature. This quantity is
Signals produce colored flames that are used as usually expressed in terms of calories per gram.
semaphores. c. Heat of Sublimation. The heat of sublimation is
(2) Colored and white smoke. Colored the amount of heat necessary to convert a weight of
smoke is used for signaling while white smoke is used solid directly into vapor in a constant temperature
for screening. process. This quantity is usually expressed in calories
(3) Tracers and fumers. Tracers and fumers per gram.
are small, smoke producing charges that are placed in d. Heat of Detonation. Two quantities are usually
projectiles. During the flight of the projectile, the charge given for the heat of detonation, one with liquid water in
burns. In a tracer, the smoke is used to track the flight the reaction products and one with gaseous water in the
of the projectile. A fumer produces smoke at the proper reaction products. The test used to determine these
rate to fill the partial vacuum that movement through the quantities uses a standard calorimeter. When the water
air creates behind the projectile. This cuts drag and is allowed to condense to liquid, the total heat produced
increases range. by the detonation reaction is measured. The heat of
(4) Incendiaries. Incendiaries produce large detonation with gaseous water more accurately reflects
amounts of heat that cause fires. the process of detonation in a non-laboratory setting.
(5) Delays and fuses. A delay is an element However, the results are less reproducible.
that consists of an initiator, a delay column, and an e. Heat of Combustion. The heat of combustion is
output charge or relay in a specially designed inert the amount of heat produced when a material is burned.
housing. The delay column burns for a predetermined This differs from the heat of detonation because the
amount of time. Delays are used to provide an interval products formed are different. Generally, the products
between initiation and functioning of a device. A fuse is formed in combustion are at a lower energy level than
a cord of combustible material commonly used in the products formed during detonation. For example,
demolition. carbon monoxide and carbon dioxide may be products
(6) Photoflash composition. Photoflash of both detonation and combustion for a particular
powders are loose mixtures of oxidizers with metallic explosive. However, the detonation process might
fuels. When ignited, these mixtures burn with explosive produce more carbon monoxide, while combustion
violence in a very short time. The mixtures are used to might produce more carbon dioxide.
provide light for military aerial photography, and in f. Sensitivity. Various external stimuli can cause
simulator devices. release of the energy contained in energetic materials.
(7) Igniters and initiators. These devices are Knowing the response of individual energetic materials
used to ignite propellant charges and initiate detonation to specific stimuli is important from the point of view of
in explosive charges. safety and in determining the suitability of a material for
a specific application.
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(1) The response to a blow is called impact proximity to a metal plate, is also used to measure
sensitivity. Traditionally, explosives have been brisance. The size of the dent is proportional to the
subjected to falling weights to measure impact brisance. Another method of measurement involves
sensitivity. The results are then reported as the distance detonating a sample of explosive on top of a cylinder
a given weight must fall to produce detonation 50 made of copper and measuring the contraction in length
percent of the time. The physical significance of this of the cylinder. The number, size distribution, and
type of test has recently been questioned. The results velocity of fragments produced by an explosive in a
are more qualitative than quantitative. For example, projectile is also related to the brisance of the explosive.
there is no question that lead azide is much more h. Detonation Velocity. The detonation velocity is
impact sensitive than TNT and that TNT is much safer simply the rate at which the detonation reaction
to handle than lead azide. But the quantitative meaning proceeds through an explosive. This quantity is closely
of "much more impact sensitive" is ill-defined. The related to the brisance. With a limited number of
results of this test should be considered for general exceptions, increased detonation velocity increases
comparisons among explosive compounds. These brisance.
same remarks are also valid for sensitivity to friction. i. Power. The power of an explosive is the total
Tests which are more applicable to specific hazards and energy available to do work. This is a different quantity
applications such as the SUSAN test and 40-foot drop than brisance, even though on the surface they appear
test are discussed in Chapter 5. rather similar. Consider two explosives, ammonium
(2) Sensitivity of an explosive to shock is a nitrate and RDX. If a charge of each is placed beneath
very reproducible quantity. Shocks generated by a a boulder, the ammonium nitrate might hurl the boulder
donor explosive can cause detonation in another many meters but the RDX might pulverize the boulder
explosive material. The strength of the shock wave into many fragments. The former quality is power
required is a relative measure of the sensitivity of the whereas the latter quality is brisance. Power is
material under test. In practice, a strong shock is measured by the Trauzl lead block test in which a
produced and attenuated in an inert medium. The width sample of the explosive is detonated in a cavity in a
of the medium that will allow detonation in 50 percent of lead block. The expansion of the cavity is a measure of
the trials is reported as the test result. These tests are the power of the explosive. The ballistic pendulum and
called gap tests. Gap test results are much more ballistic mortar tests are also used to measure power. A
reliable data than impact test results, although there is heavy weight is accelerated by the detonation of an
some dependence on the geometry of the test explosive. The swing of the pendulum or movement of
apparatus. Gap test procedures are covered in detail in the mortar's weight is a measure of the power of the
Chapter 5. explosive. The oxygen balance of the explosive is
(3) Electrostatic sensitivity is an important closely related to the power. The oxygen balance is the
quantity because of safety. Some explosives can be ratio of oxygen contained in the explosive material to
detonated from the shock of a person charged with the amount of oxygen required for complete oxidation of
static electricity. The test procedure used to determine the explosive material. Explosive compositions with
electrostatic sensitivity is covered in Chapter 5. better oxygen balances are more powerful.
(4) Thermal sensitivity is an important j. Stability. Stability is the ability of energetic
quantity which needs to be determined in considering materials to retain, unaltered, such properties as
explosives for applications. In some cases, such as in detonation velocity and sensitivity after long periods of
the warhead of a high speed intercepting missile, the storage under adverse conditions. All energetic
heat generated during flight can cause detonation of materials are unstable to some extent. The degree of
explosive charges that are not highly resistant to heat. instability varies greatly. TNT can be stored for 20
years with no change in stability while other explosives,
g. Brisance. Brisance is the shattering capability which are not used by the military or commercially,
of an explosive. Several tests are commonly used to decompose and/or detonate in a matter of days or
determine brisance. In the sand test 0.400 grams of the minutes. Several tests are used to measure stability of
explosive are placed in 200 grams of sand and explosives. In the heat tests, a sample of the explosive
detonated. The amount of sand crushed by the is subjected to a specified temperature for a given
explosive is a measure of brisance. The plate dent test, amount of time. The
in which a sample of the explosive is detonated in close
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sample is then weighed and any loss of weight above reported as the amount of time from the start of heating
the evaporation of moisture indicates volatility or to the end of the test. A blank is run at the same time to
decomposition. The heat tests are usually carried out at ensure the test results are greater than the time required
75°C or 100°C. In the 75±C test a ten gram sample is for the blank to indicate. This test is of limited
heated for 48 hours then cooled and weighed. In the applicability. The discoloration is caused by acidity, so
100°C heat test two samples of the explosive weighing the major application is testing nitrocellulose at 65.5°C
0.60 grams each are heated to 100°C. One of the and nitroglycerin at 82.2°C for purity. A test that is
samples is withdrawn after 48 hours, cooled, weighed, performed on explosives to determine stability is the
and replaced in the oven. This sample is then LLNL reactivity test. In this test a sample of explosive is
withdrawn after an additional 48 hours of heating, cooled heated at 120°C for 22 hours. A two stage
and weighed again. The second sample is left in the chromatography unit is used to measure the individual
oven for 100 hours and any detonation or ignition is volumes of N2, NO, CO, NO2, and CO2. The result is
reported. The 100°C heat test is a more accurate the sum of the volumes of these gasses per 0.25 gram
predictor of stability than the 75° test. The currently of sample. A test that yields a great deal of useful
preferred test of this type, however, is Thermal information is the Differential Thermal Analysis (DTA).
Gravimetric Analysis (TGA). A TGA can be run in two Detailed testing procedures for explosives are given in
ways. The temperature can be held constant and the Chapter 5. In the usual DTA analysis, identical
weight is monitored continuously. The data is then containers are set up. The sample under test is placed
plotted as weight or percentage of weight change versus in one of the containers and a reference substance is
time. The other method commonly employed is to vary placed in the other. The containers are placed in
the temperature at a specified rate and plot the weight identical thermal geometries with temperature sensors
or percentage of weight change versus temperature. arranged to give both the temperature of each container
The results reported in this manual use a sample size of and the difference in temperatures between containers.
approximately 10 milligrams and a heating rate of 10°C The data are displayed as DTA thermograms; the
per minute. The vacuum stability test is used temperature difference is plotted against the
extensively to measure stability. In this test a sample of temperature of the sample. The standard reference
an explosive is subjected to both elevated temperatures material chosen is one with thermal behavior that does
and vacuum. The amount of gas evolved after a not change rapidly. Such a plot is nearly a straight line
specified time is recorded as the test result. The test if the sample under test also has no rapidly changing
may be run at any temperature but between 100°C and thermal behavior. A straight line is also produced if the
150°C is the most common temperature range. In test sample has thermal characteristics similar to the
Chapter 5 the test procedure is given in detail. A test reference substance. Excursions above and below a
that is sometimes performed is the KI (potassium iodide) background line result from endothermic or exothermic
test. In this test a strip of potassium iodide starch test changes. The DTA analyses permit interpretation for
paper is suspended in a test tube with the material under phase changes, decomposition and kinetic information,
test. The top of the strip is saturated with a 50 percent melting points, and thermal stability. Another very
water 50 percent glycerin solution. The sample is useful test is pyrolysis. A sample is placed in a pyrolysis
heated. As the heating continues, moisture condenses chamber that is then flushed with helium. When the air
on the test tube up to a certain point. The position of has been swept out, the temperature of the chamber is
the test paper is moved up so the line of demarcation raised at a constant rate. Gas evolution is measured as
between the dry and glycerin-water soaked portions is a function of temperature by a bridge formed by two
kept level with the ring of condensation. The thermal conductivity cells. The pyrolysis test results are
appearance of discoloration of the upper half of the test plotted with the DTA results for each explosive.
paper indicates the test is finished. The results are
3-5(3-6 blank)
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CHAPTER 4
CHEMISTRY AND PHYSICS OF ENERGETIC MATERIALS
4-1. Introduction. This chapter contains a discussion initiation and propagation in homogeneous liquid
of the physical processes involved in the detonation and explosives or defect-free single crystals.
deflagration of energetic materials. The initiation e. Heating by plastic deformation at a sharp point
phenomenon, blast effects in surrounding media, and can cause hot spots. This mode is operative in the
shaped charge principles are also discussed. shock initiation of solid explosive compacts and
explosive liquids containing inhomogeneities.
4-2. The Ignition-lnitiation Process. Direct ignition or f. Hot spots can be formed by the mutual
initiation of explosives by an external stimulus is caused reinforcement of relatively weak shock waves at
by the thermal decomposition of the explosive involved. inhomogeneities in the shocked medium. This mode is
Impact, friction, electrostatic discharge, gap, and other operative in the shock initiation of solid explosive
sensitivity tests produce hot spots in the material under compacts and explosive liquids containing
test. A hot spot is a localized region of higher than inhomogeneities.
average temperature. Existence of the hot spots is g. Particles which are spalled off crystallite by an
confirmed by the lag time between the application of the incoming shock wave can form hot spots by impact on
stimulus and the detonation or ignition. For example, if the opposite wall of a void. This mode is operative in
a two kilogram weight falls 30 centimeters on a 20 the shock initiation of solid explosive components or
milligram sample of RDX, ignition occurs within several liquid explosives containing inhomogeneities.
hundred microseconds. Assuming that the impact
energy heated the sample uniformly and that no heat h. Micro shaped charged jets which are formed by
loss occurred, the temperature of the RDX would be shock waves acting on concave walls of bubbles,
about 250°C. At that temperature, the ignition lag for cavities, or voids can cause hot spots. This mode is
RDX is about one second. In solid explosives, energy is operative in the shock initiation of solid explosive
transferred out of the hot spot in the form of shock and compacts or liquid explosives containing
rarefication waves. The shock wave heats the inhomogeneities.
surrounding explosive. Some hot spots fail to detonate
the surrounding material. Whether or not an explosion 4-3. The Deflagratlon Process. Deflagration of a
occurs depends upon the initial strength of the shock propellant proceeds in a direction normal to the surface
wave and how rapidly the shock decreases at the hot of the propellant grain. Material is consumed in parallel
spot interface. Several modes of hot spot generation layers, so the geometry of the grain does not change as
which have been proposed include: the burning takes place. Propellant is volatized by heat
transfer from the flame zone which is in the gas phase
above the propellant surface. An increase in the
a. Adiabatic heating due to compression of gas
ambient pressure causes the flame zone to move closer
spaces can operate in impact and friction initiation of
to the propellant surface. This increases the rate of heat
pressed solid and liquid explosives.
transfer. The more rapid heat transfer causes an
b. Frictional heating on a confining surface or on a increase in the rate of volatilization of the propellant
grit particle can cause a hot spot. This mode of which correspondingly increases the rate of deflagration.
initiation can operate in impact and friction initiation of If the flow pattern of the hot combustion gases is
pressed solid and liquid explosives. perturbed and penetrates the flame zone, an increase in
c. Hot spots can be caused by the intercrystalline the rate of heat transfer may occur. An increase in the
friction of the energetic material. This mode of initiation flame temperature also causes an increase in the rate of
can operate in impact and friction initiation of pressed heat transfer. The flame temperature is a function of
solid explosives. the propellant composition. Propellants tend to burn
d. Viscous heating at high rates of shear can more smoothly at high pressure than at low pressure.
create hot spots. This mode of initiation is operative
only at strong shock inputs. This is the main mode of
4-1
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4-4. Deflagration to Detonation Transfer (DDT). In This will cause 4-2 the rate of change of the pressure
some energetic materials deflagration can build to with respect to time to be slightly higher than for the cast
detonation. In a DDT, local ignition forms a convective material. If an explosive does not undergo DDT at
flame front. A convective flame front is an ignition wave crystal density, then there would probably not be a DDT
which is propagated by the passage of hot combustion at this density.
gases through the pores of the charge. The hot gases c. As the porosity increases, the fraction of pores
are forced into the pores of the charge by the pressure which are interconnected increases rapidly. However,
built up as a result of charge confinement. The hot the permeability of the charge should remain small.
gases heat the pore walls and are consequently cooled. Under these conditions a convective flame front can be
A continuous flow of gases is required to raise the established. Establishment of the front will depend on
temperature of the pore walls to the point of ignition. the permeability of the charge, the adiabatic flame
Ignition of the pores causes the convective flame front temperature of the explosive, ignition characteristics of
to advance and as the convective flame front advances, the explosive, and the ability of the confinement to allow
the pressure increases linearly with time. The pressure a critical driving pressure to be established. The onset
increase causes compaction of most porous charges. of convective burning indicates that nonnegligible
Formation of a post convective or compressive wave amounts of energy can be transported by gas flow
marks the beginning of accelerated pressure buildup. beyond the ignition region. However, only very small
Subsequent coalescence of the compressive waves into quantities of gas can flow out of the ignition area over a
a shock wave completes the DDT. The degree of time period as long as 100 microseconds. The runup
compaction of the explosive determines how much distance for DDT in this case would be less than for
material is consumed before the DDT occurs. The charges with either lesser or greater porosity.
runup distance is defined as the length of material which d. As more porosity is introduced into the charge,
will deflagrate before detonation occurs. The following the gas flow can no longer be described as choked.
subparagraphs describe the physical phenomenon Enough pores are connected to permit flow which may
involved in the variation of runup distance with density be described as steady state. The increased
of the explosive material. permeability for this case leads to smaller rates of
pressure increase near the ignition point. Burning for a
a. At crystal density and in cast charges there is no longer period of time is required before the rate of
porosity and the explosive is impermeable. A pressure increase begins to accelerate. DDT occurs
convective flame front cannot form. A DDT can occur only after the acceleration occurs. A sharp rate of
only if the explosive is relatively sensitive and there is a pressure increase is required to produce compressive
rapid pressure rise in the ignition region that produces a waves which can coalesce into shock waves. The runup
sufficiently strong shock wave. Some high explosives distance is correspondingly increased.
when unconfined at this density will burn without e. For very permeable charges, the runup distance
detonation. Under sufficient confinement, however, increases with increasing porosity. Energy losses from
these explosives will detonate. Other more sensitive the burning region can be great enough to prevent a
explosives will explode even without confinement. rapid enough rate of pressure rise to cause DDT. In this
b. The introduction of porosity into a charge does case, the pressure builds relatively slowly (in one to two
not mean that the charge will be permeable since the hundred microseconds) to a high level. The high
pores may or may not be interconnected. If the pores pressure crushes the porous material immediately
are not connected, permeability is very low and around the ignition region. The greater density crushed
essentially negligible. The criteria for DDT in this case material, upon combustion, may then produce a rapid
will be the same as for cast charges. The runup enough pressure rise to cause DDT. The runup distance
distance will be smaller, however, because the porosity for this case is the longest of any of the cases
will increase the exposed surface area of the explosive. discussed.
4-2
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4-4
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4-5
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The rate of increase of energy per unit time is the (4) Equations -6, 4-7, and 4-8 are called jump
difference between the rate of change of the sum of the equations because the state variables jump from one
internal and kinetic energies in the initial and final state: value to another very rapidly across the shock. To
these, another relationship tying together any of two
increase energy /t = state variables (P, v, u, e, t, p) which is specific for a
[ (p1AL1e1 +0.5p1AL1u12 ) - (p0AL0e0 + 0.5p0AL0u02) ] /t given material is needed. An equation of state, which
completely describes the material is more than is
Using equations 4-1 through 4-5 the increased energy
needed. A simpler relationship called the Hugoniot
can be expressed as:
equation suffices. The Hugoniot is determined
[ (Atp1 (e1 +0.5u12) (v-u1) - Atp0 (e0 +0.5u02) (V - u02) ] /t experimentally. The relationship can be obtained by
Equating the work done on the system with the rate of measuring shock pressure and velocities at various
energy increase and canceling the t’s: shock states, or shock velocity and particle velocity, or
any two of the state variables simultaneously. The
p1u1A - p0u0A = Hugoniot which describes the relationship between the
Ap1 (v - u1) (e1 +0.5u12) - Ap0 (v - u0) (e0 +0.5u02) shock velocity, v, and particle velocity, u, has been
Canceling the A’s yields: found to be:
p1u1 - p0u0 = v =co +su (4-9)
p1 (v - u1) (e1 +0.5u12) - p0 (v - u0) (e0 +0.5u02) where co is the sound velocity in the medium and s is a
constant that is related to the specific heat and thermal
Rearranging terms yields: expansivity of the material. This relationship is not a
p1u1 - p1 (v - u1) (e1 + 0.5u12) = path along which the variables change, but is actually a
p0u0 - p0 (v - u0) (e0 +0.5u02) locus of solutions or discreet shock states. Table 4-1
(4-8) lists the values of co and s for several explosives in the
unreacted state.
Density cc Range of u
in grams in millimeters (by experiment)
per cubic Temperature per in millimeters
Explosive centimeter °C microsecond s per
microsecond
4-6
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By substituting terms from equations 4-6, 4-7, and 4-8 Figure 4-4 shows a simple collision of two materials.
into equation 4-9 and solving, we can obtain more forms (1) is the surface of the target and (2) is the front
of the Hugoniot, for example: surface of a flyer plate which is a small mass that
impacts the target at a very high velocity. The slope of
2 (2) is the plate velocity, (3) is the impact point when the
P = p0(c0u +su ) (4-10)
two materials meet, (4) is the forward going shock in the
(5) Three planes or two dimensional plots are target, (5) is the interface of the plate and target moving
used to describe the shock properties and shock slowly to the right, (6) is the left going shock driven back
histories of materials. They are the distance-time (x-t) into the flyer, and (7) is the back surface of the flyer. All
plane, the pressure-particle velocity plane (P-u) slopes on this plot are velocities. As the shocks reflect
described by equation 4-10, and the pressure-specific and rarefications fan out and the surfaces move, the x-t
volume (P-vs) curve. plot is used to keep track of the variables.
(a) The -t plane is used to display the
positions of shocks, material surfaces, and rarefications
(the opposite of a shock) in time and distance.
4-7
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(b) The P-u plane is where the Hugoniots are normally plotted. An example is shown in figure 4-5. This plot is used
to perform graphical solutions to impact problems (uniaxial). Intersections of Hugoniots represent simultaneous solutions
of two Hugoniot equations. Chords drawn from initial to final states on this plot have slopes proportional to the shock
velocities of the final state in that particular material. Figure 4-5 shows the solution of an impact problem where a flyer,
material N at a velocity of u0 impacts a stationary target, material M. The final pressure and particle velocity after the
impact are the same in both flyer and target and are P1and u1 respectively. (1) is the chord drawn from the initial state to
the final state of the flyer. The slope is equal to P0vt, the initial density times the shock velocity in the flyer. (2) is the
chord drawn from the initial state to the final state of the target, the slope of the chord is P0vr, the initial density of the
target times the shock velocity in the target. The negative slope of P0vf indicates the shock in the flyer is traveling
toward the left. The lines N and M are the P-u Hugoniots of two individual materials. The P-u Hugoniot is not fixed on
the plane. The position of the plot relative to the P and u axis is not unique. The physical explanation for that is, a
material specimen can exist at any pressure state regardless of bulk or particle velocity. The shape of the Hugoniot and
the relation of slope to the axis is unique.
4-8
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(c) The specific volume Vs is defined as the c. A detonation shock wave is self-sustaining
reciprocal of the density. Plots in the P-Vs plane, as because the energy added by the chemical reaction
shown in figure 4-6, are useful in describing the taking place behind the wave balances the losses due to
thermodynamics of the shock because areas on this normal attenuation. Figure 4-7 shows the pressure
plane represent work or energy per unit mass: distribution of a detonation wave that is moving through
Force Volume explosive material. Chapman and Jouquet (CJ)
Force X distance
PVs = developed the theory of shock wave propagation
Area Mass mass
through explosive materials. The CJ conditions for each
The Hugoniot position on this plane is unique. explosive are unique for that explosive at some unique
or specified density. If we change the initial density, we
will change the CJ conditions. The theory is based on
these assumptions: that pressure is constant from the
shock wave to the CJ point, that the pressure decays in
a Taylor wave beyond the CJ point, that the reaction is
complete and the products are in equilibrium at the CJ
point, and that the energy in the Von Neuman spike is
negligible in comparison to the energy in the reaction
zone and so can be ignored. Figure 4-8 shows a
representative plot of the Hugoniots of unreacted
explosive and decomposition products under detonation
conditions. The Rayleigh line connects the initial
unshocked state, Vs0, with the final shocked state, VF.
Table 4-2 lists the reaction zone length (i.e., the length
of the zone between the shock wave and the CJ point)
for various explosives. Table 4-3 lists the detonation
pressure in the reacting zone for various explosives.
The pressure of the Von Neuman spike can be
explained by referring to figure 4-8. The point that the
Rayleigh line crosses the unreacted explosive Hugoniot,
Figure 4-6. Shock properties in the P-Vs plane. VF, corresponds to the high pressure in the Von Neuman
spike. This is obviously at a higher pressure than the CJ
point.
4-9
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Table 4-2. Reaction Zone Length d. Several computer programs are available
that predict the detonation characteristics of a
Approximate compound from basic chemical and physical properties.
Density, in grams length, in One such program is based on the Becker-Kistiakowsky-
Explosive per cubic centimeter millimeters Wilson (BKW) equation of state. The BKW program
requires information about the initial state of the
Amatol 80/20 1.67 4 explosive and about the state of the detonation
Composition B 1.67 0.13
products. The information required for the initial
HBX-1 1.60 0.19
explosive is elemental composition, heat of formation,
density, and formula weight. The information required
Nitroglycerin -- 0.21 for the detonation products is elemental composition,
heats of formation, co-volumes (the effective size of the
RDX 0.826 molecules), and fits of each products ideal gas entropy
(microporous) 1.30 1.82 as a function of temperature. If any solid detonation
(single crystal) 1.80 2.90 products are present, the density, molecular weight, and
an equation of state are required. From this information
TNT 0.36 the BKW program computes the equilibrium
1.00 0.32 composition of the detonation products at specified
1.55 0.18
temperatures and pressures, the Hugoniot curve, the CJ
-- 0.13
-- 0.21
pressure, the CJ temperature, the CJ density, the
1.59 0.70 detonation velocity, and the isentrope of the detonation
(pressed) 1.63 0.3 products through the CJ point. The values of pressures
(cast) 1.615 0.42 at 291°K and temperatures obtained from the program agree to
1.70 0.55 at 77.4°K within 20 percent of the values observed experimentally
1.71 0.62 at 20.4°K and the detonation velocity agrees to within 10 percent.
(liquid) -- 0.9 at 100°C This margin of error is caused by the assumption of the
-- 1.1 at 100°C BKW equation that detonation is steady state. To
perform time-dependent flow calculations of the
TNT/RDX 1.67 0.12 detonation process, other programs are used. These
50/50
include SIN, EIC, 2DL, and 2DE. These programs
require an equation of state of the detonation products
(such as BKW), an equation of state for the unreacted
explosive, an equation of state for mixtures of unreacted
and totally decomposed explosive, and an equation of
state that describes the rate at which the explosive
decomposes into detonation products.
4-10
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(2) While the duration of the positive (4) As the shock front moves outward, the
pressure portion of the blast wave is about one-fourth peak pressure decreases and the duration of the
that of the portion at less than atmospheric pressure, the positive pressure phase increases. The rates of these
amplitude of the pressure at the shock front is much changes vary with the magnitude of the peak pressure,
greater than the amplitude of the decrease in pressure but the net effect is decrease in impulse. With increase
below atmospheric. The duration of the positive phase in distance from the bomb, impulse decreases
varies with the explosive charge and distance from the approximately as the reciprocal of the radius.
point of origin. In one case, the duration of the positive
phase is of the order of 0.006 second at a distance of (5) In general, two criteria must be satisfied in
15.5 meters from the bomb. A wall struck by such a order to demolish any structure. Both peak pressure
blast wave is first pushed forward by the short, sharp, and impulse must exceed certain minimum values
hammer-like blow of the positive pressure phase and which depend upon the type of structure. Window glass
then pulled backward by the much longer negative requires a moderately high peak pressure but only a low
phase. Whether the wall falls forward or backward impulse value since the positive pressure need not last
depends upon circumstances. long to cause fracture. On the other hand, a brick wall
withstands only a small peak pressure, but the pressure
(3) Blast effect is measured by two criteria, must be of relatively long duration and therefore the
peak pressure and impulse. Peak pressure is the impulse value must be high. The blast from almost any
pressure increase at the shock front or the highest charge that develops sufficient peak pressure will have
pressure in the shock wave minus atmospheric sufficient impulse to break glass. Most bomb charges
pressure. Impulse is mathematically equal to the area that develop sufficient impulse to demolish a brick wall
under the time pressure curve for the duration of the also develop sufficient peak pressure to do so. A
positive phase (figure 4-9). This is approximately half general rule is that structures that are strong and light in
the peak pressure multiplied by the duration of the weight, with respect to the area presented to the shock
positive phase. Peak pressure represents a measure of front, require high peak pressure but no great impulse
the maximum force exerted against a surface by a blast for demolition. Heavy but relatively weak structures
wave, since force is equal to the product of pressure and require considerable impulse but not such a high peak
area. Impulse represents a measure of the force pressure.
multiplied by the duration.
Figure 4-9. Typical pressure-time record for the blast from a bomb.
4-12
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(6) Blast waves are reflected from solid If a bomb detonates within a building, there is
surfaces but not in the same manner as sound and light considerable reflection of the blast wave from the walls,
waves are reflected. When the incident and reflected even if they are demolished. The rapid reflection of the
waves intersect on the ground, they do not make equal wave from various walls, in such a case, results in a
angles with the ground as do sound waves. Refer to multiple punch effect on another wall. The overall effect
figure 4-10. At small angles of incidence (the angle of confinement is increased in the vulnerable radius of
between the normal to the blast front and the normal to demolition of the bomb charge. The analogous
the reflecting surface), the angle of reflection is smaller vulnerable radius of visible damage (as detected by
than the angle of incidence, and the pressure behind the aerial observation) is also used to evaluate the effects
reflected wave is greater than behind the incident wave. of bombing.
Such reflection of a blast wave from a bomb that has
detonated above the ground gives rise to an increased b. Blast Effects Underground. An explosive
pressure wave at ground level. When the angle of charge, if detonated while buried, exerts pressure on the
incidence (a) is greater than an extreme angle (ae) (40 surrounding earth and causes movement effects over a
degrees for strong to a value approaching 90 degrees distance known as radius of rupture. If the depth of
for very weak shocks), the incident and reflected waves burial is less than the radius of rupture, the explosion
do not intersect on the ground. This is known as products blow through the surface of the ground and
irregular or Mach reflection. Reflection that occurs form a roughly circular depression known as a crater.
when the angle of incidence occurs at the extreme angle An explosion on the surface of the ground makes a
is known as the extreme regular reflection, whereas, shallow crater which may be a greater diameter than
reflection occurring where the angle of incidence is that produced when the explosive is buried. This is due
smaller than the extreme is known as regular reflection. to the scouring action of gases projected downward from
When the incident angle exceeds the extreme angle, the the explosive charge. Important factors in crater
reflected and incident waves intersect at some point formation are the type of earth cratered and the type of
above the ground. The lower portion of the reflected explosive used. Explosives of a moderate charge in
and the incident waves fuse into one wave which is swampy ground make a relatively huge crater, while in a
known as the Mach stem (M, figure 4-10), the point of rock formation only a small crater will be formed. An
intersection being known as the triple point (TP, figure 4- explosive of low detonation rate that produces a large
10). The resulting existence of three waves, termed the volume of gases, may form a larger crater than TNT if
Mach reflection, causes a density discontinuity and a the charge is well below the surface and the ground is
region of high pressure termed the Mach region is not too hard or rocky. If the charge is on the surface, a
formed. The pressure behind the front of the Mach low-rate explosion makes a smaller crater than TNT
region is approximately twice that of the incident wave. because of the weaker scouring action of the lower
The top of this high-pressure region, the triple point, velocity gases. If an explosive is buried at a depth
travels away from the reflecting surface. As pressure exceeding the radius of rupture, the compression effect
and impulse appear to have their maximum values just downward and horizontally and the lifting with
above and below the triple point, respectively, the region subsequent subsidence cause a depression on the
of maximum blast effect is approximately that of the surface known as a camouflet.
triple point. The region of maximum blast effect is
determined by the height above the ground at which the c. Blast Effects Under Water. The detonation of
blast occurs. At distances that are large compared to high explosive under water results in shock waves of
the height of the burst, the incident and reflected waves extremely high pressure which decay rapidly with
have fused and proceed outward as a single shock. distance from the charge. Since the total damage is
After the point of complete fusion of the waves, the due to both the shock wave and the subsequent bubble
shock wave is the same as one produced by a double pulses, these effects must be separately evaluated.
charge detonated on the ground. As the distance from One measurement to make is that of the periods of
point of the blast increases, the Mach stem becomes oscillation of the bubble, that is, the time intervals
normal to the ground. between successive minima in the bubble radius. The
length of the bubble period is related to the energy left
(7) Blast effects are enhanced by after passage of the shock wave. In general, the longer
confinement due to the reflection of blast waves by the the bubble period the greater the energy. A second
confining surfaces. A blast wave traveling through a measure of the energy may be obtained from a study of
tunnel, corridor, trench, or even a street decreases in the maximum and minimum radii of the bubble. By a
intensity much more slowly than in the open. combination of radius and period measurements, energy
calculations can be made.
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4-7. Shaped Charge Effect. A shaped charge (figure Very little effect is produced by explosives having rates
4-11) is a cylindrical explosive charge with a lined of detonation less than 5,000 meters per second. The
conical cavity in one end. The explosive is generally liner focuses the energy of detonation, thus enabling
pressed or cast. The higher the detonation velocity and penetration of very thick and very hard targets such as
CJ pressure the more effective the shaped charge is. armor.
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a. As the charge explodes, the detonation wave Penetration occurs as the target material flows out of the
passes over the liner. The liner material is accelerated hole. The material dislodged in the deeper parts of the
somewhat normal to the explosive-liner interface (figure hole flows out along the walls. Penetration is affected
4-12). Nearer the apex of the cone, the liner mass to greatly by the distance of the base of the shaped charge
charge ratio is lower so the velocity the liner material to the target. This is called stand-off and is usually
attains is higher. Also, nearer the apex of the cone, the expressed in charge diameters. There is an optimum
metal liner does not have to distort as much as further stand-off distance for maximum penetration. At closer
down. This also causes the velocity to be higher toward distances, the jet has not fully formed and at further
the apex. When the liner material converges at the distances the jet is breaking up, causing the particles to
center line, or axis, of the charge, the surface material is hit off center such that they do not contribute to
squeezed out at high velocity. This material forms the penetration. Generally the optimum stand-off is
jet. Since the material closest to the apex is at a higher between two and six charge diameters. Penetration is
velocity, the portion of the jet which comes from that normally around four to six diameters but could go as
area is also highest in velocity. Therefore, the jet has a high as 11 to 12 diameters. The optimum liner
velocity gradient. The material in the leading tip is thickness is about three percent of the charge diameter
moving faster than the material toward the rear. The for soft copper. If a different material is used, the
remaining material, which is the bulk of the liner, forms thickness should be determined by measuring the
a heavy slug which follows the jet at a much lower weight of soft copper that would be used for the
velocity. After traveling a distance of about five or six particular charge diameter. This amount of material is
diameters of the original charge, the jet begins to break then used. Liners made of less dense material will be
up because of the velocity gradient and inhomogenieties thicker than the copper counterpart and liners made of
in the charge and liner. Inhomogenieties in the charge more dense material will be thinner. Materials which are
and liner cause the jet particles to have slightly different commonly used include copper, steel, glass, and
directions of flight. aluminum. The angle of the cone apex varies from 42
degrees to 60 degrees in American ammunition and 18
b. The pressure applied by a shaped charge to a degrees to 90 degrees in foreign ammunition. Forty-two
target is to the order of several megabars. This is well degrees is the optimum angle for maximum penetration.
into the plastic range for almost all materials. Figure 4-
13 illustrates the response of the target material to a
shaped charge jet.
4-15
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c. When used in projectiles that rotate, shaped d. The United States uses one other geometry of
charge penetration is considerably reduced. Projectiles shaped charge liner, hemispherical. A hemispherical
that have conical liners may lose as much as 50 percent liner produces comparable jet energies to a coneshaped
of their effectiveness due to rotation. In general, liner. However, the velocity and mass distribution in the
penetration is reduced as spin increases from about jet are different. Hemispherical liners turn inside out
zero to 200 revolutions per second, after which further with almost all of the material projected in the jet. As
increases have little effect. Rotating shaped charges much as 70 to 80 percent of the material in conical liner
produces holes of greater diameter than static charges, stays behind to form the slug. In hemispherical shaped
but rotation does not affect the volume of the hole charges, however, jet velocity is only about half of that
produced. Changing the apex angle of the cone does obtained in a conical shaped charge. Hemispherical
not eliminate the reduction in penetration caused by shaped charges are less sensitive to rotation than
rotation of the charge. conical shaped charges.
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CHAPTER 5
PROPERTIES AND TESTS OF EXPLOSIVES
5-1. General Requirements of Explosives for This is not true, however, for some of the metalloorganic
Military Applications. primary explosives. The high density of these
compounds is caused by the presence of mercury or
a. General. Numerous compounds are explosive, lead which does not add to energy content.
however the number of compounds that can be used
militarily is relatively small. This chapter describes the g. Hygroscopicity. Hygroscopicity, the property of
tests used to cull the usable explosives from the many absorbing moisture, can have an adverse effect on the
that are unusable. Many explosive items are designed sensitivity, stability, or reactivity of some explosives.
for a minimum lifespan of ten years. These tests are Explosives which are hygroscopic must be loaded in
designed to characterize the explosive as much as moisture-proof containers. This extra precaution is
possible before deployment to avoid problems during generally undesirable, so explosives which are
the user phase. The types of tests performed on each nonhygroscopic are used. Ammonium nitrate is an
explosive depend, to a large degree, on the intended exception. Although very hygroscopi, the compound is
use of the explosive. Most of the tests yield data which extremely cheap and readily available.
are used to rank explosives relative to a standard h. Volatility. Volatility can cause loss by
explosive. The relative rank is then used to determine evaporation, development of pressure in rounds of
possible applications. Few tests have absolute ranges ammunition, and separation of ingredients in composite
that explosives must fall into before use in military items explosives. These undesirable characteristics must be
is permitted. minimized in military explosives.
b. Availability and Cost. In view of the enormous i. Reactivity. A military explosive must be as
quantity demands of modern warfare, explosives must nonreactive as possible with the materials used in
be produced from cheap raw materials that are construction of munitions. Compatibility of specific
nonstrategic and available in great quantity. In addition, explosives with these materials is discussed in Chapter
manufacturing operations must be reasonably simple, 8. The reactions, which are accelerated by moisture in
cheap, and safe. many cases, can cause liberation of gaseous products,
loss of power, and loss of sensitivity. In some cases,
c. Sensitivity. A military explosive must be such as with an azide and copper, the metallic salt
capable of being detonated and yet be as insensitive as formed can be dangerously sensitive. When the
possible. Military requirements for sensitivity are strict. explosive is to be loaded in contact with or mixed with
Many compounds that detonate are not used as military another explosive or binder, reactivity between the
explosives because of unfavorable sensitivity ingredients must be minimized.
characteristics. j. Toxicity. Minimum toxicity is a desirable quality
d. Brisance and Power. The brisance and power for any military explosive. A discussion of the toxicity of
of an explosive determine applicability for specific the explosives of military interest is presented in
purposes. A bursting charge must be brisant, but a Chapter 12.
ditching charge needs to be powerful and less brisant. k. Environmental Impact. The impact of
e. Stability. Military explosives must be able to manufacturing and loading operations on the
withstand long periods of storage under unfavorable environment must be as small as possible.
conditions. Storage conditions range from extreme heat I. Demilitarization. A military explosive should
and humidity in the tropics to the cold of arctic regions. have favorable demilitarization characteristics. An
f. Density. The fixed volume available in a round example is plastic bonded explosives in which a
of ammunition necessitates using explosives of thermally sensitive binder is used. Upon heating, the
maximum energy density. In general, the greater the binder decomposes and the explosive may be totally
density of the explosive the greater the energy recovered for reloading.
available.
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Results are reported in millimeters. 5-13. Jumble. In this test an end item containing
c. LANL Large Scale Gap Test (LSGT). explosives is placed in a wood lined steel box. The box
is then rotated about two diagonal corners at a speed of
Donor 41.3 millimeters diameter x102 30 revolutions per minute. The rotation is continued for
millimeters long (1.625 x4 inches) PBX- 3,600 revolutions.
9205 pellet.
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When explosives contain liquids as impurities, they 5-17. SUSAN Test. The SUSAN Sensitivity Test is a
often undergo irreversible dimensional changes when projectile impact test. The projectile head contains
subjected to many temperature cycles between 54°C about 0.45 kilograms of explosive and the target is
and + 71°C. In explosives containing TNT, the armor-plate steel. Figure 5-7 shows the projectile used
dinitrotoluenes form low-melting liquid eutectics which in this test. The results of the tests are expressed as a
cause problems. Mononitrotoluenes added as anti- sensitivity curve in which the relative point-source
cracking agents give large irreversible growth in TNT detonation energy released by the explosive on impact
explosives. In the use of pure TNT explosives, one is plotted as a function of the projectile velocity. The
solution to the cracking problem is the use of pure TNT relative point-source detonation energy can be derived
with addition of high melting point eutectic formers from a transit-time measurement of the air shock from
which reduce cracking without introducing objectionable the point of impact to a pressure gauge three meters (10
irreversible dimensional change during the normal feet) from the point of impact. The results determined in
temperature variations encountered. Another cause for this manner are somewhat subjective, particularly when
irreversible dimensional change is the solid polymorphic the reaction level shows a large but relatively slow
transition such as occurs with ammonium nitrate. (Refer increase with time. The currently preferred way to
to ammonium nitrate in Chapter 8.) Procedures for determine the point-source detonation energy is to relate
solids include measuring any cylindrical sample at least it to the overpressure measured by the pressure gauge.
1.27 centimeters in diameter by 1.27 centimeters in This method gives much more reproducible data and is
height, temperature cycled between -54°C and +60°C not subject to many of the errors of the transit-time
for 30 cycles or more. If no exudation or excessive measurements. On the figures in Chapter 8, the energy
growth is noted, an additional test can be made for scale ranges from zero (no chemical reaction) to about
exudation by placing two cylinders together inside a 100 for the most violent detonation-like reactions (all
sealed can. These should be held together by parallel explosive consumed). Less violent burning reactions
steel face plates and clamped together at an initial that appear to consume all of the explosive can give
pressure of 413.7 kilopascals. The sealed unit is values as low as 40, whereas the energy equivalent of
subjected to 30 cycles from ambient to 140°F, TNT fully reacted as a point source would be 70. In the
maintaining each temperature long enough for the entire test material of Chapter 8 details of the impact process
sample to reach the temperature of the oven. The pertinent to the impact safety of an explosive are given.
sample is then observed for exudation. Any exudate is Remarks about probabilities of large reactions are
removed and weighed. relevant to unconfined charges in the 11 kilogram (25
pound) class. Smaller unconfined charges show a trend
5-16. Rifle Bullet Impact Test. Rifle bullet impact of decreasing reaction level as the charge size
tests may use a .30 or .50 caliber bullet. Results decreases. References to the "pinch" stage of impact
reported in this manual use a .30 caliber bullet. In refer to the terminal stage of the test when the nose cap
the.30 caliber test a bomb is prepared by screwing a has completely split open longitudinally and has peeled
closing cap to one end of a piece of cast iron pipe 7.62 back to the steel projectile body, which is rapidly brought
centimeters long, 5.08 centimeters in diameter, and to a halt.
threaded at
5-8
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Figure 5-7. Scaled drawing of the SUSAN projectile. The high explosive head
is 4 in. long and 2 in. in diameter (102 m x0.051 m).
5-18. Skid Tests. A combination of friction and impact 5-21. Cylinder Expansion Test.
is a frequent cause of accidents where large pieces of
an explosive can be dropped a few feet. The skid test a. An important problem faced by the designer of
measures the sensitivity of an explosive material hitting fragmentation warheads is that he must maximize the
a rigid surface at glancing angle. In one testing energy which is transferred from explosive to metal
configuration a sample of the explosive is dropped during the detonation. The most frequently encountered
vertically onto a hard surface inclined at 45 degrees. In configuration is that of an explosive-filled metal cylinder
another testing configuration the explosive sample is detonated by a wave moving axially. The best scaling
attached to the end of a pendulum. The pendulum is law that has been devised for this condition is that of
allowed to swing from a predetermined height. Gurney, who disregarded detonation conditions and
shock effects in the metal and assumed implicitly that all
5-19. Adiabatic Sensitivity Test. In the adiabatic the energy of the explosive is conserved. His equation
sensitivity test a sample of the explosive is placed in an for the cylinders is
airtight holder. The top of the holder has an air
compressing piston that decreases the volume and thus
increases the pressure in the test chamber when struck
by a falling weight. The results of the test are reported
as the height the weight must fall, thus the degree of
where v is the velocity to which the metal is accelerated
compression, to produce detonation in 50 percent of the
by the explosive, E is unit energy content of the
cases.
explosive, C is the weight of the explosive, and M is the
metal weight. This expression of velocity in terms of
5-20. Fragmentation Test. In the fragmentation test a
C/M implies that weight-ratio scaling of explosive and
charge of the explosive under test is loaded into a
metal is of prime importance and that dimensional
cylinder or artillery shell and detonated in a pit filled with
scaling need not be considered at all. The term 2 E has
sand or sawdust. The fragments are separated
the dimensions of a velocity as was pointed out by
magnetically and categorized by weight. This test also
Gurney in his original report.
gives an indication of the brisance of the explosive.
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b. Determination of the Gurney constant of a d. The method for observing the wall's expansion
warhead explosive is made in the cylinder expansion varies. It has been recorded through the use of
test where the explosive contained in a metal cylinder is electronic pin probes and raster oscilloscope recording
end-detonated and the maximum lateral velocity of the systems as well as with flash X-ray techniques. It has
metal is measured. The geometry resembles that of also been accomplished by the use of streak cameras
most fragmentation warheads, particularly as to lateral and framing cameras. The Lawrence Radiation
confinement of the explosive. The dimensions of the Laboratory method uses a streak camera for the
cylinder can be chosen so as to give the full run-up to recording of the wall velocity and a pin probe method for
detonation velocity before reaching the location of determining the detonation velocity of the explosive
fragment velocity measurements, and the end-release while it is expanding the walls of the test cylinder. The
effects can be kept far enough downstream so as not to Atomic Weapons Research Establishment, UK, uses
affect fragment velocities. Other techniques for both electronic pin probe and streak camera methods to
evaluating explosives, while of full value in their own record the wall expansion, and pin probes for the
contexts, are all less applicable to the prediction of detonation velocity. There is some reason to believe
effects in the fragmentation warhead. The plate-push that, perhaps in the early stages of the expansion, the
test transfers only about one-fourth as much of the pin probe method may be more accurate, but the data
energy of the explosive to the metal as does the cylinder reduction is also a bit more difficult in some respects
expansion; also, the air cushion between explosive and than with the streak camera record.
plate is highly unrepresentative of the warhead e. When various explosives are rated in the
configuration. Other rating tests such as the plate dent, standard geometry, the relative performance of these
ballistic mortar, and the Trauzl lead block are even more explosives becomes readily apparent. This permits the
unrepresentative geometrically. warhead design engineer to select an explosive
c. The cylinder expansion test is any test compound for a specific feature of its performance.
performed where a metal cylinder (relatively thin walled) f. It has been demonstrated that cylinder
is loaded with an explosive and this explosive charge is expansion test results scale up or down over a wide
detonated. As the detonation occurs, the expansion of range of sizes.
the cylinder wall is observed and recorded in such a way
that the rate at which the wall moves outward can be
followed up to the point where the expanding cylinder
wall is obscured by the reaction products as they break
through the wall.
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CHAPTER 6
PROPERTIES AND TESTS OF PROPELLANTS
6-1. Introduction. The tests performed on propellants 6-5. Heat Tests. Heat tests are performed at 1
can be divided into three classes: mandatory, 34.5°C for single-base propellants and 1 20°C for
prescribed, and optional. The mandatory tests, covered double-and triple-base propellants. These tests
in paragraphs 6-2 through 6-13, are safety tests. These measure the stability of the propellant Specimens
tests must be run on each propellant formulation. The of the propellant are placed into the bottom five
prescribed tests, covered in paragraphs 6-14 through 6- centimeters (two inches) of a glass test tube. A
17, provide useful information about a propellant piece of methyl violet indicator paper is placed
formulation. These tests are generally run on propellant vertically in the tube so that the lower end of the
formulations after the mandatory tests. The optional paper is 25 millimeters from the specimen. The
tests, covered in paragraphs 6-18 through 6-23, are only tube is corked and set into a constant
run if warranted by the intended application of the temperature block or a constant temperature
propellant formulation. Tests in which a propellant reflux bath. The temperature must be
formulation is heated are called accelerated aging tests. maintained to within 0.5°C. The result of the test
is reported as the time required for the test paper
6-2. Compatibility. Compatibility can be measured by to change color to salmon pink. For the
any of three methods: Taliani test, vacuum stability propellant to pass the test, the color change
test, and differential thermal analysis. The propellant cannot occur in less than 40 minutes or 60
and the inert material being tested for compatibility are minutes, depending on the propellant
mixed together in some ratio which may vary from equal formulation, and the sample may not explode in
parts of propellant and test material to 10 parts less than five hours.
propellant and 1 part inert material. In the vacuum
stability test, increased reactivity is indicated by the 6-6. Vacuum Stability. Vacuum stability tests are
mixture evolving more than five milliliters of gas over performed at 100°C for single-base propellants and
the sum of the amount of gas produced by the 90°C for double-and triple-base propellants. This test
ingredients tested separately. In a differential thermal determines propellant stability on the basis of the
analysis, increased reactivity is indicated by an upward volume of gas liberated on heating the propellant under
displacement of the curve. In the Taliani test, increased vacuum. The propellant specimen is placed in a heating
gas production also indicates more reactivity. Increased tube which is then connected to a capillary tube.
reactivity is considered evidence of incompatibility. Mercury is placed in a cup on the other end of the
capillary tube. The system is then evacuated to
6-3. External Heat. In this test, also called the bonfire approximately five millimeters. The mercury is then
test, the propellant formulation is loaded into a standard allowed to enter the capillary. The heating tube is then
cartridge assembly or storage container. The sample is placed in a constant temperature reflux bath. The
mounted 30.5 centimeters (one foot) above a fire which volume of gas liberated during the test is determined by
is allowed to burn for 30 minutes. The test is recorded observing the mercury level. If rate data is desired, the
using a 16 millimeter movie camera. The film record of volume of gas is observed at regular intervals. If the
the test is examined to determine if any detonation volume of condensable gases is desired, the volume of
occurred. No detonation reaction is considered the gas is calculated based on measurements before the
acceptable criteria for a propellant formulation. tube is removed from the constant temperature bath.
Although there is no specific pass-fail criteria
6-4. Deflagration to Detonation Transition. In this established for this test, the test is stopped when the gas
test, an igniter is placed in the bottom of a tall test volume reaches 11 +mil.
container which is then filled with the sample material.
Propellants must not undergo detonation when ignited in 6-7. Closed Bomb. The standard closed bomb is a
this manner. thick-walled cylindrical vessel capable of withstanding
gun pressures. The bomb is equipped with firing
electrodes to affect ignition, a pressure transducer, a
gas release valve, a thermocouple, and temperature
controlled water jacket. The result of the test is a
pressure time plot. There is no pass-fail criteria for this
test.
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6-8. Surveillance. In the surveillance test, a 45 gram High sensitivity material yields results in the range of
sample of the propellant is placed in a 237 milliliter 0.001 to 0.00875 joules, medium sensitivity material in
(eight ounce) glass, stoppered bottle which provides an the range of 0.00875 to 0.0125 joules, and low
essentially airtight seal. The bottle consists of a special sensitivity material in the range of 0.0125 to 12.5 joules.
colorless resistance glass which has no more than 0.02
percent alkalinity calculated as potassium hydroxide. 6-12. Friction Sensitivity. This test is performed on
The test is performed at 65.5°C. The bottle and an apparatus which consists of a metal sliding block, a
contents are placed in a chamber and the temperature is stationary metal wheel that is attached to a hydraulic
regulated to within one degree centigrade. After 24 ram, and a weighted pendulum. The sample, amounting
hours of heating, the stopper is reseated. Daily to no more than 50 milligrams, is placed on the block
observations are then made to check for the appearance under the wheel. Pressure is applied using the hydraulic
of reddish fumes which indicate the presence of oxides ram. The pendulum is raised to a 90 degree position
of nitrogen. Single-base propellants, when new, should and dropped. Results are reported as the maximum
last for fifteen hundred days before fuming. Double- force which can be applied to the wheel without causing
base propellants should last at least 400 days. This test the sample to decompose. Normally, 20 consecutive
does not yield reliable data for triple-base propellants. negative results must be obtained. The results of this
For these propellants, the stabilizer content is analyzed test are compared to those obtained for other
at regular time intervals. The rate of stabilizer depletion propellants. Most standard propellants have values of
gives an indication of the maximum storage life of the about 4,360 Newtons.
propellant. A stabilizer depletion test can also be
performed on single-and double-base propellants. 6-13. Impact Sensitivity. This test may be performed
on any of the standard impact sensitivity devices. The
6-9. Card Gap. The card gap test measures the results of the test are compared with data obtained for
sensitivity of a propellant formulation to detonation by a other standard propellants.
shock wave. A sample of the propellant is placed in a
cardboard tube with a booster explosive. The explosive 6-14. High Loading Rate Compression. In this test,
and sample are separated by a series of 0.254 propellant grains are subject to compressive loading at
millimeter (0.01 inch) cellulose acetate cards. The test about the same rate and in the same time frame as
results are reported as the number of cards necessary to occurs in the chamber during firing. The propellant
prevent detonation of the sample. Three successive grains are machined to give flat parallel ends with a
trials with no detonation are required. Seventy cards length to diameter ratio of approximately one. The
represent the dividing line between an explosive and fire machined samples are compressed perpendicular to the
hazard material. flat ends using a high rate hydraulic servo. The servo is
computer controlled. The results of the test are the
6-10. Cap. This test determines whether a propellant maximum compressive strength, the strain at the
formulation can be detonated by a shortened number maximum compressive strength, stress-strain curves,
eight blasting cap. The sample and blasting cap are the time to maximum compressive strength, and
placed on top of a lead cylinder. Whether a detonation whether the mode of failure was brittle or ductile. A
occurs is determined by the degree of compression of drop tower apparatus may also be used to obtain higher
the cylinder. The test results are reported as either a strain rates.
detonation, sample burned, sample fragmented but no
reaction, or no reaction. To pass this test, the propellant 6-15. Low Loading Rate Compression. For this test,
must not detonate. propellant grains are machined to give flat parallel ends
usually with a length to diameter ratio of one. Solid
6-11. Electrostatic Discharge Sensitivity. This test grains are usually extruded to yield a diameter of
determines the sensitivity of a propellant formulation to approximately 1.27 centimeters (0.5 inches). The
energy from an electrostatic discharge. A test sample of device used for this test is a mechanically driven,
not more than 50 milligrams is placed on a test plate. A electronically controlled tester capable of continuously
capacitor is charged to the desired energy level with a recording the load exerted on a test specimen. The
5,000 volt power source and discharged into the sample compressive effect on the sample is also measured.
through a steel needle. Results are reported as the The result of the test is a load-displacement curve.
maximum energy which can be applied without From this curve the strain at maximum compressive
decomposing the sample. Twenty consecutive negative strength and maximum stress are computed.
results are required at the specified energy level.
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6-16. Taliani. The Taliani test is used to determine the 6-18. Strand Burner. In this test a strand of propellant
stability of a propellant. A dry sample of the propellant that is 17.8 centimeters (seven inches) long and 3.2
is placed in a tube, heated to a specified temperature millimeters (one-eighth of an inch) in diameter is placed
(usually 110°C), and the tube is evacuated. The in a bomb in which the temperature and pressure can be
composition of the atmosphere above the sample is regulated. The strand is placed vertically in a jig and
controlled by alternately filling with nitrogen or another ignited at the top. Vertical burning is ensured by coating
gas and evacuating a specified number of times. The the strand with a compound that does not interfere with
pressure is then reduced and heating is continued. The the burning of the propellant. Two wires are inserted
pressure in the tube is measured with a manometer. through the jig, one 6.4 millimeters (one-quarter of an
The increase in pressure as the test progresses is a inch) from the top of the strand and the other 12.7
measure of the rate of decomposition of the sample. centimeters (five inches) below the first. As the
The test result is a graph of the time versus the pressure propellant burns, an electronic circuit through the two
in the tube. The following data is usually reported: the wires is broken and an automatic timer is used to
time in minutes required for the pressure to reach 100 determine the burning time. The rate is calculated from
millimeters of mercury, the slope of the line at 100 the strand length and burning time. The effect of initial
millimeters of mercury, and the slope of the line at 100 temperature and pressure on the burning rate is
minutes. measured.
6-17. Explosion Temperature. In this test, a sample 6-19. 90°C Dutch Weight Loss Test. In this test, a
of the propellant formulation is loaded into a gilding four gram sample of a propellant is placed in a
metal tube and then immersed in a woods metal bath stoppered tube and inserted in a heating block which is
which has been raised to a specified temperature. The maintained at 90°C. Every second day the stoppered
time to ignition is recorded. Ignition is detected by tube is removed and cooled to room temperature for 30
noise, flash, or smoke. The ignition time is obtained at minutes. The stopper is then briefly lifted and closed
several temperatures. A time-temperature plot is made. again. The tube is weighed to the nearest milligram and
The result that is reported, the temperature required to reinserted in the heating block. The test results are then
ignite the propellant in five seconds, is obtained by plotted as weight loss percentage versus the time in
extrapolation of the time-temperature plot. days, as shown in figure 6-1. The initial bump in the
curve, which results from loss of volatiles, is ignored.
The results reported are the number of days coinciding
with the kink in the curve, which indicates the onset of
instability.
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6-20. Shaped Charge Jet Impact. This is a 6-22. Single Fragment Impact. This is a vulnerability
vulnerability test. The propellant is loaded into a test. The propellant is loaded into a standard cartridge.
standard cartridge. The cartridge is placed behind a Standard .50 caliber 208 grain fragments are fired into
1.27 centimeter (one-half inch) steel plate. A shaped the cartridge at a velocity of about 1,585 meters per
charge jet is fired through the steel plate directly at the second (5,200 feet per second). The velocity of the
cartridge. Video tape and film are used to record the fragments before impact is recorded and video tape and
reaction of the propellant in the cartridge. The results film are used to record the reaction of the propellant in
are compared to the results for other propellants. the cartridge.
6-21. Shaped Charge Jet Spall. This is a vulnerability 6-23. Multiple Fragment Impact. This is a
test. The propellant is loaded into a standard cartridge. vulnerability test. The propellant is loaded into a
The cartridge is placed behind a 1.27 centimeter (one- standard cartridge. Fragments are explosively launched
half inch) steel plate. A shaped charge is aligned so at a velocity of about 2,286 meters per second (7,500
that the jet does not impact the cartridge shell when feet per second) in a pattern such that each cartridge is
fired through the plate, but the spall from the plate does. impacted by at least two fragments. The velocity of the
Video tape and film are used to record the reaction of fragments before impact is recorded and video tape and
the propellant in the cartridge. film are used to record the reaction of the propellant in
the cartridge.
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CHAPTER 7
UNITED STATES PRIMARY EXPLOSIVES
7-1
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Table 7-1. Various Types of Lead Azide (Continued).
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(1) Dextrinated Lead Azide (DLA) is also (5) RD-1333 lead azide is an insensitive form
known as type I lead azide. Dextrin is used as a of lead azide. The method of manufacture as well as
colloiding agent which prevents the formation of large, some properties of RD-1333 are confidential.
sensitive crystals and regulates crystal shape during
manufacture. (6) Dextrinated Colloidal Lead Azide (DCLA)
is essentially DLA with a very small particle size. The
(2) Service Lead Azide (SLA) consists of lead particle size is in the range of one to two microns.
azide crystals each containing a nucleus of lead
carbonate. This form of lead azide is used extensively c. In the manufacture of DLA two stock solutions
in the United Kingdom. The method of manufacture of must be prepared. Solution A is prepared by dissolving
this compound is confidential. SLA is practically about 73.9 kilograms (169 pounds) of lead nitrate in
nonhygroscopic and is superior to DLA in functioning about 750 liters of water treated by the permutit
characteristics. Storage under water is considered demineralization process. Care must be taken to
hazardous due to the possibility of growth of the crystals remove all grit and insoluble matter. The pH of this
and formation of agglomerates which detonate solution is in the range of 4.2 to 4.6. To neutralize this
spontaneously. Other long term storage tests dispute acidity 25 to 30 grams of sodium hydroxide in dilute
this result. solution are added. The sodium hydroxide will
neutralize the occluded acid and the acid formed by the
(3) Colloidal Lead Azide (CLA) is also known hydrolysis of the lead nitrate. An excess of sodium
as type II lead azide. CLA is nondextrinated lead azide nitrate must be avoided to prevent the production of
of very small particle size. The size of the particles is in elongated crystals which are very sensitive. About 4.08
the range of three to four microns. CLA is not suited for kilograms of potato dextrin that was previously dissolved
uses requiring good flow characteristics, but, because of in about 100 liters of water is then added and the
the very fine particle size, is ideal as a spot charge and solution is brought to 7.325-0.07 percent lead nitrate
a priming charge in low energy, electric initiators. CLA content. Solution B is prepared by diluting a refined
successfully replaced the milled DLA formerly used for solution of 27 percent sodium azide to 3.175-+0.02
this purpose, thus eliminating the milling operation percent sodium azide content. Then 794 grams of
which was always considered dangerous, even under sodium hydroxide in the form of pellets are added. The
carefully controlled conditions. In preparing a spot sodium hydroxide is added to neutralize most of the free
charge for a low energy, electric detonator, dry CLA is acid formed during the interaction of solutions A and B.
mixed with a concentrated solution of nitrocellulose in This quantity of sodium hydroxide is also just sufficient
ether, alcohol, or other organic solvent, and a small to control the purity of the finished lead azide by
quantity of the resulting paste is placed on the precipitating a small quantity of lead as Pb(OH)2 or
bridgewire to form a droplet called a spot. For a type of Pb(OH)N3. The solution is then adjusted to 3.175 ±
detonator in which the bridgewire is located inside a 0.025 percent sodium azide content. Solution A is then
cavity, the charge of CLA can be made in the form of a heated to between 57.5°C and 60°C with agitation and
pellet by pressing wet CLA into the cavity. 50 liters of solution B are added at the rate of two liters
per minute. The slow rate of mixing these two very
(4) Polyvinylalcohol Lead Azide (PVA-LA) dilute solutions inhibits the formation of the
consists of lead azide crystals coated with orthorhombic crystalline polymorph. After solution B
polyvinylalcohol. PVA-LA possesses practically the has been added, the temperature is lowered to 90°C or
same sensitivity to impact as DLA, but is much more lower with continued agitation. When agitation stops the
efficient in detonators and is practically nonhygroscopic. lead azide settles out. The precipitate is caught on filter
The ignitability is about the same as for straight lead cloths under vacuum and washed with four changes of
azide and better than for DLA. The normal lead azide
content is 93 to 96 percent. Other substances, such as
polyethylene glycols and ureaformaldehyde polymer,
can be used to produce mixtures with properties very
similar to PVA-LA.
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water to remove the acidity. To manufacture colloidal A needle shaped crystal is defined as a crystal having a
lead azide, a solution of four percent sodium azide is length to diameter ratio of 7 to 1 or greater. Needle
maintained at 25°C. Then a solution of lead acetate or shaped crystals are more sensitive than crystals of
lead nitrate is added with agitation. The lead nitrate or normal shape and tend to detonate under pressure. RD-
acetate is in slight excess of the amount required by the 1333 lead azide must be precipitated from a solution of
equation: sodium carboxymethyl cellulose which is used as the
crystal growth agent. The color shall be white to buff.
2NaH3 + Pb(NO3)2 → Pb(N3)2 +2NaNO3 The aggregates shall contain no well defined translucent
The resulting slurry is then filtered and the precipitate crystals when examined microscopically. The particles
washed with several changes of water and dried. shall be opaque and irregular in size and shape and the
powder shall be free flowing. RD-1333 lead azide must
d. The specifications for dextrinated lead azide, have a minimum bulk density of 1.1 grams per milliliter,
type I, and collodiol lead azide, type II, are: be 98.5 percent pure, have a pH in the range of 7.5 to 5,
and have a maximum solubility of one percent in water.
In nitric acid, the insoluble material shall be no more
Type
Properties I II
than 0.05 percent and none of the material shall be
retained on a US standard sieve 230. In addition there
shall be no more than trace quantities of iron, copper,
Color White to buff White to buff
chlorides, nitrates, and acetates. Carboxymethyl
Form,
cellulose may be present in concentrations of 0.6 to 1.20
dimension Free from
percent. Another specification for special use lead azide
maximum needle shaped
has the same requirements as stated for RD-1333,
crystal
except there is no limitation for trace quantities of iron,
Purity,
copper, chlorides, nitrates, and acetates.
minimum 91.5% 99.0%
Acidity None None
Solubility in e. Dextrinated lead azide is less sensitive to
water, 1.0% impact than mercury fulminate, lead styphnate,
maximum diazodinitrophenol, tetracene, or crystalline lead azide.
Particle size The small aggregates that pass through a No. 325 sieve
geometric are slightly less sensitive than those that pass through a
mean, No. 230 sieve and are retained on a No. 270 sieve.
micron When wet with water or 95 percent ethanol, lead azide
maximum - 5 has the comparative sensitivity values shown by table 7-
Largest 2. The impact test results are from the Picatinny
micron Arsenal apparatus with a two kilogram weight.
maximum - 10
100 - - 4 1 1 - -
80 20 - 9 10 0 4 1
80 - 20 4 1 1 - -
75 25 - 9 10 0 12 0
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hydroxide, aqueous potassium cyanide, and pyridine utes after the acidic solution of mercury nitrate is added
dissolve mercury fulminate. The compound can be to the ethanol, a violent reaction starts and the liquid
recovered by treating the ammonium or potassium boils with the evolution of white fumes. Most of these
solution with acid and the pyridine solution with water. fumes are recovered by the condenser. As the reaction
The heat of formation is 221 to 226 calories per gram, approaches the end point, the fumes change color to
heat of combustion is 938 calories per gram, and the brownish-red because of the decomposition of nitric acid
heat of explosion is 427 calories per gram. Mercury by heat. A small quantity of dilute alcohol is added at
fulminate was used extensively as an initiator, however, this point to moderate the reaction and prevent the
poor stability has prompted replacement of this decomposition of the mercury fulminate by the heat of
compound by such initiators as lead azide. reaction. The reaction normally takes about an hour
and a half. The reaction mix is then allowed to cool to
b. Mercury fulminate reacts with concentrated room temperature, at which time all the mercury
hydrochloric acid to produce hydroxylamine, H2N,OH, fulminate has settled out. The mercury fulminate
and formic acid, HCOOH. The reaction with sodium crystals are then caught on a screen and washed with
thiosulfate in aqueous solution forms mercury cold water until free of acid and five impurities known as
tetrathionate according to the equation: fulminate mud. The washed mercury fulminate is then
drained and packed into cloth bags which are stored in
Hg(ONC)2 + 2Na2 S203 + H20 → tanks of water until required for use. The acid mother
HgS4O6 + 2NaOH + NaCN +NaNCO liquor and the water washings are neutralized with alkali,
evaporated to recover the alcohol, and treated to
If allowed to stand, a secondary reaction occurs with the recover any mercury or mercury salts. The yield of the
formation of sulfate and thiocyanate according to the process is 120 to 130 parts per 100 parts of mercury.
equation:
HgS4O6 +2NaOH + NaCN + NaNCO→ d. In the manufacturing process ethyl nitrate
HgSO4 +Na2SO4 + 2NaNCS +H2O (C2H5.ONO2), ethyl nitrite (C2H5.ONO), and nitroethane
(C2H5NO2) also are produced. The intermediate
The first reaction can be used for the determination of products of oxidation and nitration involved in the
the purity of mercury fulminate. Even in the presence of preparation of mercury fulminate are as follows:
0.5 percent moisture, pure mercury fulminate does not
react with any of the common metals. However, the CH3.CH2OH → CH3.CHO →
standard grade of the compound may contain as much Ethanol Acetaldehyde
as one percent free mercury, formed by exposure to
light or elevated temperatures. The free mercury readily CH2(NO).CHC→ - CH(:NOH).CHO→
forms amalgams with copper, brass, or bronze, so Nitrosoace- Isonitrosoace-
components containing these metals must be taldehyde taldehyde
protectively coated if used with mercury fulminate.
CH(:NOH).COOH →
Isonitrosoacetic acid
c. Mercury fulminate is manufactured in relatively
small quantities. About one pound of redistilled mercury C(NO2)(:NOH).COOH →
is added to an open, earthenware vessel or five liter Nitroisonitrosoacetic acid
flask that contains eight to ten pounds of nitric acid with
a specific gravity of 1.4. The nitric acid is in excess of O2H.CH:NOH → C:NOH → Hg(ONC)2
the amount required by the equation: Formoni- Fulminic Mercury
trolic acid acid fulminate
3Hg + 8HN03 → 3Hg(NO3)2 + 2NO +4H20
A large number of such charges are usually prepared The product so obtained is not more than 99 percent
and allowed to stand overnight until the mercury is pure. The material can be purified so as to have a
completely dissolved. The charges are then poured into fulminate content of 99.75 percent or more by dissolving
a large balloon flask which contains eight to ten pounds the impure material in concentrated ammonium
of 95 percent ethanol. The flask rests in a bath of hydroxide, filtering the solution, cooling the filtrate, and
running, cold water. This installation has to be either reprecipitating slowly adding concentrated nitric acid
outside or in a building provided with an exhaust with rapid agitation while keeping the temperature below
system. The flask is fitted with a reflux condenser. 35°C. Conditions can be established so that the
About two to three min-
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precipitated fulminate is of essentially the same The sensitivity of mercury fulminate to percussion is one
granulation as the impure material. The precipitated of the compound's most advantageous characteristics.
pure fulminate is washed with distilled water until free of Mercury fulminate is highly sensitive to electric spark. A
acid. The yield is 80 to 87 percent. spark from a person charged to less than 5,000 volts
causes ignition. This condition is possible in plant
e. Mercury fulminate for military use consists of operations. The sensitivity to electrostatic discharge is
one grade. The requirements applying are: reported to be 0.025 to 0.07 joules.
Appearance: Crystals of sparkling appearance g. The sand test indicates mercury fulminate is
that are white, gray, or light gray 27.3 to 59 percent as brisant as TNT. The rate of
with a yellowish tint. detonation of a charge with a density of 2.0, 3.0, and 4.0
Granulation: A maximum of 15 percent retained grams per cubic centimeter is 3,500, 4,200, and 5,000
on a No. 100 and a maximum of 75 meters per second. When ignited, a single crystal will
percent passing through a No. 200 burn rapidly with a flash, but detonation does not take
sieve. place. When a layer of crystals is ignited, high order
detonation takes place. The Trauzl test indicates a
Sand test: 0.400 gram shall crush a minimum power of 37 to 50 percent of TNT. Mercury fulminate is
of 44 grams of sand. distinctly more powerful than lead azide.
Mercury
fulminate: Minimum, 98.0 percent.
h. Although mercury fulminate is not as efficient an
Acidity: None. initiator of detonation as lead azide and
Insoluble diazodinitrophenol, satisfactory results are obtained
matter: Maximum, 2.0 percent. when used in conjunction with tetryl, RDX, or PETN, the
Free mercury: Maximum, 1.0 percent. most generally used booster explosives. The number of
Chlorine: Maximum, 0.05 percent. grams of mercury fulminate required for complete
detonation of TNT is 0.25 to 0.36, for tetryl is 0.20 to
The chlorine content requirement is due to the 0.29, for RDX is 0.19, for PETN is 0.17, and for
occasional use of a small quantity of cupric chloride, explosive D is 0.85.
CuCI2, for the purpose of improving the color of the
product. The chloride is added to the solution of i. Mercury fulminate is no longer used by the
mercury in nitric acid. While this improves the color, United States military because of poor stability. The
there is also a decrease in the purity of the product. The usual stability tests are not applicable to mercury
insoluble matter represents decomposition products, fulminate, due to explosion in a relatively short time at
which are formed as the result of side reactions. temperatures above 85°C. The products of deterioration
are nonexplosive solids rather than gases. When the
f. The impact sensitivity on the Bureau of Mines purity of mercury fulminate is reduced to about 92
apparatus with a 20 milligram sample is five millimeters percent, the initiating efficiency is destroyed although
and on the Picatinny Arsenal apparatus with a the material will explode when ignited. When purity has
nonstandard 2.2 kilogram weight is four inches. This been reduced to 95 percent, the stability of mercury
indicates mercury fulminate is more sensitive to impact fulminate must be considered seriously impaired. Table
than lead azide and lead styphnate. Being of the same 7-4 gives a summary of the approximate times of
sensitivity to impact as diazodinitrophenol and storage required to cause deterioration to 92 percent
tetracene, these three compounds are the most and 95 percent. Mercury fulminate gains 0.02 percent
sensitive initiating explosives used in military when exposed to 90 percent relative humidity at 30°C.
ammunition. Mercury fulminate is more sensitive to When dry, mercury fulminate reacts rapidly with
friction than lead azide and lead styphnate, exploding aluminum and magnesium and reacts slowly with
with both the steel and fiber shoe. The five second copper, zinc, brass, and bronze. When wet, mercury
explosion temperature is 210°C which indicates mercury fulminate reacts immediately with aluminum and
fulminate is more sensitive to heat than lead azide or magnesium and rapidly with copper, zinc, brass, or
lead styphnate, but less sensitive than bronze. Dry or wet, the compound does not effect iron
diazodinitrophenol and tetracene. or steel.
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is caught on a filter and washed with ice water until the fulminate. The five second explosion temperature is
washings give no indication of hydrochloric acid or 195°C. A mixture of DDNP and water is desensitized to
sodium chloride. If this material is dissolved in hot the extent that a number eight blasting cap cannot
acetone and a large volume of ice water added to the cause detonation. DDNP detonates when struck with a
agitated solution, the DDNP is precipitated as a bright sharp blow. An unconfined sample burns with a flash if
yellow, amorphous powder. Recrystallization from a ignited but even the slightest confinement causes a
solvent is used to produce the tabular crystals that transition from burning to detonation. A charge of
comprise specification grade material. After DDNP undergoes detonation when ignited if pressed
manufacture, the DDNP is kept wet with water until into a blasting cap shell with a reinforcing cap and a
used. piece of black powder safety fuse crimped in the shell.
A spark falling into the open end of such a blasting cap
d. Only one grade of DDNP is used for military causes only ignition and flashing of the DDNP. The
purposes. This complies with the following maximum energy of a static discharge that does not
requirements: cause ignition is 0.25 joules.
Color: Greenish yellow to brown. f. The sand test indicates DDNP is 94 to 105
Form: Tabular crystals having a maximum percent as brisant as TNT. DDNP is considerably more
length of 0.2 millimeter. brisant than mercury fulminate, lead azide, lead
Granulation: 100 percent shall pass through a styphnate, and tetrazene. At a density of 1.58 grams
No. 100 US standard sieve. per cubic centimeter DDNP and TNT have the same
Bulk density: Minimum, 0.4 grams per milliliter. velocity of detonation, 6,900 meters per second. At
densities of 0.9 and 1.63 grams per cubic centimeter the
Acidity: Maximum, 0.01 percent as detonation velocities are 4,100 and 7,100 meters per
hydrochloric acid. second, respectively. The Trauzl test and ballistic
Sand test: 0.40 gram shall crush not less than mortar test indicate that DDNP is 110 percent and 95
33 grams of sand. percent as powerful as TNT, respectively. The gas
volume produced on detonation is 856 liters per
e. DDNP is less sensitive to impact than lead kilograms.
azide or mercury fulminate. The friction sensitivity is
approximately the same as lead azide but less than
mercury
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g. The sand test indicates DDNP is a better the detonation of ammonium picate and cast TNT. For
initiator of detonation than mercury fulminate or lead initiation of the more sensitive high explosives, DDNP is
azide for less sensitive high explosives. The most not superior to lead azide. Comparative values showing
marked evidence of this is the ability of DDNP to initiate relative initiating efficiencies are given in table 7-6.
h. In the vacuum stability test at 100°C, 7.6 cubic The compound has yellow orange or reddish brown,
centimeters of gas are evolved from a five gram sample rhombic, needle like crystals with a density of 3.02
in 40 hours. In the 100°C heat test, 2.10 percent is lost grams per cubic centimeter at 30°C. The anhydrous salt
in the first 48 hours, 2.20 percent in the second 48 has a density of 2.9 grams per cubic centimeter. Both
hours, and no explosions occur in 100 hours. These forms of lead styphnate are soluble in aqueous
results indicate DDNP is not as stabile as lead azide, but ammonium acetate. Basic lead styphnate is practically
is markedly more stabile than mercury fulminate. insoluble in water; normal lead styphnate is only soluble
Storage tests have shown dry DDNP to withstand to the extent of 0.04 percent at room temperature.
storage at 50°C for at least 30 months, as compared Normal lead styphnate is even less soluble in methanol
with nine months for mercury fulminate. When stored and ethanol than in water. Both forms of lead styphnate
under water, DDNP is of unimpaired brisance for 24 are insoluble in ether, chloroform, carbon tetrachloride,
months at ordinary temperature and for 12 months at carbon disulfide, benzene, toluene, concentrated
50°C. The stability of DDNP, therefore, is considered hydrochloric acid, and glacial acetic acid. Normal lead
satisfactory for commercial and military use, and DDNP styphnate has a heat of formation of 92.3 calories per
and lead azide have replaced mercury fulminate in gram, a heat of combustion of 1,251 calories per gram,
blasting caps to a large extent. DDNP is hygroscopic to and a heat of detonation of 460 calories per gram. Both
the extent of 0.04 percent in an atmosphere of 90 forms of lead styphnate are used as ingredients in
percent relative humidity at 30°C. priming compositions. When used alone, despite a
favorable rate of detonation and good power
7-5. Lead Styphnate. characteristics, lead styphnate is a relatively poor
a. Two forms of lead styphnate are used as initiator of detonation. Detonation of 60 percent
primary explosives: basic (figure 7-5) and normal dynamite and sometimes gelatin dynamite is possible.
(figure 7-6). Basic lead styphnate has a nitrogen However, of the military high explosives, only unpressed
content of six percent and a molecular weight of 705.53. PETN can be detonated. The minimum detonating
The compound has two crystal forms: yellow needles charge for unpressed PETN is 0.55 gram, as compared
with a density of 3.878 grams per cubic centimeter and to 0.30 gram of mercury fulminate or 0.40 gram of lead
red prisms with a density of 4.059 grams per cubic azide. The ease of ignition of the compound has led not
centimeter. The apparent density is 1.4 to 1.6 grams only to use in priming compositions, but also use as a
per cubic centimeter. Normal lead styphnate has a cover charge for igniting lead azide.
nitrogen content of nine percent and the monohydrate
has a molecular weight of 468.38.
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d. For military use normal lead styphnate must azide. The five second explosion temperature is 282°C,
comply with the following requirements: less than that for lead azide but much greater than those
of mercury fulminate and diazodinitrophenol. Normal
Appearance: The material shall be free from visi- lead styphnate is much more easily ignited by flame or
ble impurities and aggregates of electric spark than mercury fulminate, lead azide, and
crystals and be yellow brown to diazodinitrophenol. The sensitivity to electrostatic static
brown in color. discharge is 0.001 joules. When ignited, the rate of
detonation is less than the maximum rate. The
Crystal form: The material shall consist of the dis- calculated activation energy for the decomposition of
crete crystals of the monoclinic lead styphnate is 61.5 kilogram-calories per gram
system and the longest dimension molecule as compared with a value to 25.2 kilogram-
of any crystal shall not be greater calories for mercury fulminate.
than three times the next longest
axis. Hexagonal plates are accept-
f. When subjected to the sand test with ignition by
able.
a black powder fuse, the brisance of normal lead
Crystal The largest dimension of any crystal styphnate (10.5 grams of sand crushed) is much less
dimension: shall not exceed 0.5 millimeter. than that of lead azide (16.7 grams of sand crushed).
Granulation: 100 percent of the material shall However, when initiated with a small charge of mercury
pass through a US standard number fulminate or lead azide, the brisance (24 grams of sand
100 sieve. crushed) is greater than that of lead azide or mercury
Apparent 1.30 to 1.60 grams per cubic cen- fulminate. The range of brisance reported is from 27 to
density: timeter. 53 percent of TNT. When initiated with blasting caps,
lead styphnate pressed to a density of 2.9 has a rate of
Acidity: The pH shall be between 5.0 and 6.0 detonation of 5,200 meters per second, which is greater
in a one percent solution. than the rate of detonation of either lead azide or
Material 0.3 percent, maximum mercury fulminate at the same density. Trauzl lead
insoluble block tests, with large and small blocks, show lead
in ammonium styphnate to be more powerful than lead azide and 42
acetate: percent as powerful as TNT.
Material soluble 0.1 percent, maximum g. Normal lead styphnate is of a high order of
in ether: stability as indicated by vacuum stability tests at 100°C
Lead content: 43.2 to 44.3 percent and 120°C. In both tests 0.4 cubic centimeters of gas
are evolved in 40 hours. The loss of 1.5 percent in the
Nitrogen content: 8.87 to 9.07 percent
100°C heat test may be attributable to the removal of
Instantaneous 310°C to 330°C the water of crystallization, which is present to the extent
flash point: of 3.84 percent. Storage at 80°C caused no change in
the 120°C vacuum stability test value, although the
e. Normal lead styphnate is slightly less sensitive explosion temperature and sand test values were
to impact than mercury fulminate or diazodinitrophenol, increased slightly. These changes also may be
but is more sensitive than lead azide. The friction attributable to loss of the water of crystallization. The
sensitivity is less than that for mercury fulminate or lead stability of lead styphnate is the same as lead azide and
better than that of mercury fulminate or
diazodinitrophenol. Figure 7-7 shows the DTA curve for
lead styphnate and figure 7-8 shows the TGA curve.
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TEMPERATURE IN °C
7-6. Tetracene.
a. Tetracene is also known as guanyldiazoguanyl
tetrazene and 4-guanyl-1 -(nitrosoaminoguanyl)-1 Figure 7-9. Structural formula for tetracene.
tetrazene. The compound (figure 7-9) is a colorless to
pale yellow, fluffy material with needle crystals, an
oxygen balance to CO2 of-57.6 percent, an oxygen b. Boiling water decomposes tetracene liberating
balance to CO of-43 percent, a nitrogen content of 74.4 two molecules of nitrogen per molecule of tetracene.
percent, and a molecular weight of 188.15. Tetracene Hydrolysis with sodium hydroxide yields ammonia,
forms a hydrate with three molecules of water. The cyanamide, and triazonitrosoaminoguanidine
melting point of the pure compound is between 140°C (N3C(:NH).NH.NH.NO). Tetracene reacts with an
and 160°C accompanied by decomposition and excess of silver nitrate to form the double salt
explosion. The apparent density is only 0.45 grams per C2H7N10OAg.AgNO3.3H2O and forms explosive salts
cubic centimeter. When compressed at 20,685 such as the perchlorate.
kilopascals (3,000 pounds per square inch), the density c. To prepare tetracene, 34 grams of
is 1.05 grams per cubic centimeter. The crystal density aminoguanidine carbonate are dissolved, with warming,
is 1.7 grams per cubic centimeter. The compound can in a mixture of 2.5 liters of water and 15.7 grams of
be easily dead pressed. Tetracene is practically glacial acetic acid. After the solution has been filtered
insoluble in water and ethanol and so can be stored wet and cooled to 30°C, 27.6 grams of solid sodium nitrite
with water or a mixture of water and ethanol. The are added. The sodium nitrite is dissolved by stirring.
compound is also insoluble in ether, benzene, acetone, After standing for three or four hours, the solution is
carbon tetrachloride, and ethylene dichloride. Tetracene shaken to start precipitation and the mixture is allowed
is soluble in dilute nitric acid or strong hydrochloric acid. to stand for about 20 hours longer. The precipitate of
In a solution with hydrochloric acid, the hydrochloride is tetracene is separated and washed with water until free
precipitated by the addition of ether. Tetracene may from acid. An alternate method is to dissolve five
then be recovered by treatment with sodium acetate or grams of aminoguanidine dinitrate in 30 milliliters of
ammonium hydroxide. The heat of formation is 270 distilled water, cooling to 0°C, and mixing with a solution
calories per gram and the heat of detonation is 658
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of 2.5 grams of sodium nitrite in 15 milliliters of water. The range of brisance values reported are 40 percent to
While maintaining the temperature at 10°C, 0.5 grams 70 percent of TNT. The volume of gas developed on
of glacial acetic acid is added to precipitate the explosion is 1,190 cubic centimeters per gram. The
tetracene. After allowing the slurry to stand, at least Trauzl test indicates tetracene has a power of 51 to 63
overnight, the precipitate is washed by decantation with percent of TNT.
several portions of water and then transferred to a filter
to be washed more thoroughly with water using suction. g. Unpressed tetracene, when ignited by a flame,
Then the product is air dried at room temperature. can cause the detonation of loose or pressed PETN, but
Another method for the preparation of tetracene uses pressed tetracene does not detonate PETN. Unpressed
aminoguanidine sulfate and sodium nitrite in distilled tetracene can cause low order detonation of tetryl. The
water. unpressed material, however, cannot detonate TNT
even when primed with mercury fulminate. Tetracene,
d. Tetracene must meet the following requirements therefore, does not have sufficient initiating efficiency to
for military use: be used with military high explosives.
Color and Tetracene shall be white to light h. Tetracene is relatively stable at temperatures
appearance: yellow and under the microscope not greater than 75°C. However, in the 100°C heat test,
shall appear as needle shaped extreme decomposition occurs in the first 48 hours. The
crystals. reactivity with water and the slightly high 75°C
international test value (0.5 percent) indicate an order of
Melting and 130±2°C.
stability approximating that of mercury fulminate.
explosion point:
Tetracene gains only 0.77 percent in an atmosphere
Granulation: 100 percent shall pass through a US with 90 percent relative humidity at 30°C.
number 45 standard sieve.
Specific gravity: 1.65±0.05. 7-7. Potassium Dinitrobenzofuroxane (KDNBF).
Heavy metals: There shall be no heavy metals a. KDNBF (figure 7-10) is a red crystalline solid
present. with a nitrogen content of 21.21 percent and molecular
weight of 264.20. The oxygen balance of the compound
Nitrogen content: 74.5+1 percent.
to CO2, H2O, and K2O is -42.4 percent. The anhydrous
e. Tetracene is of the same order of sensitivity as salt has a density of 2.21 grams per cubic centimeter
mercury fulminate and diazodinitrophenol. Using the and a melting point, with explosive decomposition, of
Bureau of Mines apparatus with a two kilogram weight, 210°C. KDNBF is soluble to the extent of 0.245 grams
the result obtained is seven centimeters as compared to per 100 grams of water at 30°C. Between the
five centimeters for mercury fulminate. Using the temperatures of 50C to 50°C the specific heat is 0.217
Picatinny Arsenal apparatus with a 226.8 gram (eight calories per gram per degree centigrade. KDNBF is
ounce) weight, the result obtained is eight inches, as used in primary compositions.
compared to nine to ten inches for mercury fulminate.
b. Using a .45 kilogram (one pound) weight in the
The five second explosion temperature (160°C) is
Picatinny Arsenal impact apparatus, the drop height is
relatively low as compared with the other initial
only six inches. In the pendulum friction test, KDNBF
detonating agents. This ease of ignition along with a
explodes with both the steel and fiber shoes. The
relatively high heat of explosion and large gas volume
minimum charge required for initiation is 0.30 grams of
produced makes tetracene useful in priming
mercury fulminate or 0.10 grams of lead azide. The
compositions and with lead azide in explosive rivets.
sensitivity of KDNBF is between that of mercury
When exposed to contact with a flame, tetracene
fulminate and lead azide.
undergoes mild explosion with the production of much
black smoke. The minimum detonating charge of c. In the sand test, 44.8 grams of sand are
mercury fulminate is 0.40 grams. crushed, which indicates a brisance of 93 percent of
TNT. The volume of gas developed on explosion is 604
f. In the sand test, loose tetracene crushes 13.1
cubic centimeters per gram.
grams of sand, but when loaded under a pressure of
20,685 kilopascals (3,000 pounds per square inch), only d. In the 100°C heat test, the weight loss in the first
two grams of sand are crushed. However, tetracene 48 hours is 0.03 percent and in the second 48 hours
pressed at 20,685 kilopascals crushes 21.1 grams of 0.05 percent with no explosions in 100 hours. At 30°C
sand when initiated with mercury fulminate. This and 90 percent relative humidity KDNBF is hygroscopic
maximum brisance is equal to that of mercury fulminate. to the extent of 0.27 percent.
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e. The specifications for KDNBF are: thirty percent of the peak at 8.63
ppm. In addition, there shall be no
Color: Light orange to dark red. peak at 9.22 ppm greater than five
Bulk density: 0.2 grams per milliliter, minimum. percent of the peak at 8.63 ppm.
Forms: KDNBF shall be in the form of
plate-like crystals. In addition, the 7-8. Lead Mononitroresorcinate (LMNR).
dried KDNBF powder shall be easily
dispersible. a. LMNR (figure 7-11) has a nitrogen content of 3.89
percent, an NO2 content of 12.77 percent, a lead content
Granulation: Through a No. 50 US standard of 57.51 percent, and a molecular weight of 360.30. The
sieve, 98 percent minimum. compound forms microscopic reddish brown crystals.
Retained on a No. 100 US standard LMNR has slow burning properties and a low combustion
sieve, 4 percent maximum. temperature. The compound is used in electric detonators
Retained on a No. 200 US standard with DLA as the spot charge to initiate a PETN base
sieve, 10 to 75 percent. charge, as an upper charge, and as an ingredient in
Retained on a No. 270 US standard primary compositions.
sieve, 85.0 to 100 percent.
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b. LMNR is prepared by mononitrating recorcinol sulfide, and calcium silicide. The last two also serve to
then allowing the slurry of mononitrorecorcinol to react sensitize the composition to friction or percussion.
with Pb(OH)2 at elevated temperatures. The LMNR is Oxidizing agents include potassium chlorate and barium
stored and transported under water with not less than 10 nitrate. Other ingredients include primary explosives
percent denatured alcohol. and binders. The major determining factor in ingredient
c. LMNR must meet the following requirements for selection is the impetus which is to detonate the priming
military use: composition. The types of impetus commonly used are
percussion and electrical.
Color and LMNR shall be light brown in color.
appearance: b. Percussion type primers are used extensively
for the ignition of propellants. In the early 1900's this
Apparent 0.20 to 0.35 grams per milliliter. type of priming composition contained mercury
density: fulminates. At the present time, however, mercury
fulminate has been replaced by more stable
Acidity: The pH shall be between 5.0 and 6.5 compounds. Potassium chlorate was used in this type
for a solution of one gram of the of priming composition from about 1917 through World
material in 150 milliliters of water. War II. Except for special applications, the use of this
compound has been discontinued because of the
Lead content: 70.5 to 72.5 percent. corrosive action of potassium chloride, a decomposition
product of potassium chlorate, on gun barrels.
Nitro group 7.2 to 7.6 percent. Potassium chlorate is still used in high temperature
content: priming compositions. Table 7-7 lists the composition of
two such mixtures. The percentages listed are by
Vacuum stability 0.4 milliliters of gas in 40 hours with weight. Table 7-8 lists several commonly used
at 120°C: a 2.3 gram sample, maximum. percussion priming compositions.
Composition
FA959 FA982 FA956
Normal lead styphnate, % 35 36 37
Tetracene, % 3.1 12 4
Barium nitrate, % 31 22 32
Antimony sulfide, % 10.3 7 15
Powdered zirconium, % 10.3 9
Lead dioxide, % 10.3 9
PETN - 5 5
Aluminum, - - 7
Gum arabic - - 0.2 (added)
Autoignition temperature 199°C 240°C 184°C
Decomposition temperature 209°C 262°C 193°C
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Composition
FA959 FA982 FA956
Density in grams per
cubic centimeter 1.3-2.3(bulk) 1.4-2.4 1.3-2.4
Fuel to oxidizer ratio 0.5 to 1 0.52 to 1 0.69 to 1
Gas volume produced 5-10 milliliters 5-10 milliliters 5-10 milliliters
per gram per gram per gram
Electrical spark sensitivity < 0.05 joules
Friction sensitivity yes
The output of percussion type primers includes hot table 7-9. The intermediate charge is an energetic
gases, hot particles, thermal radiation, and a pressure material such as lead azide or black powder. The base
pulse. In some cases the pressure pulse may be a charge may be lead azide, black powder, or a more
shock wave. brisant explosive such as RDX or PETN. The base
charge initiates the secondary explosive.
c. Stab detonators are used to directly initiate
secondary explosives. As the name implies, a stab d. Electrical primers are of several types:
detonator is initiated by penetration of a firing pin. The
mechanical energy of the firing pin is converted to heat, (1) exploding bridge wire
which causes detonation. Rather than using one (2) hot wire bridge
homogenous priming mixture as percussion type (3) film bridge
primers do, stab detonators contain three layers of (4) conductive mixture
charges; primary, intermediate, and base. Priming (5) spark gap
compositions used in the primary charge are shown in
Table 7-9. Stab Detonator Priming Compositions
Composition
NOL 130 PA101 NOL 60
Lead azide, % 20
Basic lead styphnate, % 40 53 60
Tetracene, % 5 5 5
Barium nitrate, % 20 22 25
Antimony sulfide, % 15 10 10
Powdered aluminum, % - 10 -
Autoignition temperature 274°C 196°C 210°C
Decomposition temperature 280°C 215°C 227°C
Density in grams per cubic 1.85 (loading) 1.3-2.0 1.3-2.0
centimeter
Fuel to oxidizer ratio 0.75 to 1 0.91 to 1 0.4 to 1
Gas volume produced 10-25 milliliters 5-10 milliliters 5-10 milliliters
per gram per gram per gram
Electrical spark sensitivity 0.0022 joules <0.05 joules 0.0022 joules
Friction sensitivity yes yes yes
Hygroscopic yes yes yes
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In an exploding bridge wire detonator, a large current is Examples are listed in table 7-10. In these detonators
passed through a wire which causes the wire to burst. the wire or film is heated by an electric current. The
The bursting of the wire causes a shock wave that is of heat causes ignition of the charge which may then
sufficient strength to cause detonation. With this type of undergo a deflagration to detonation transfer. The
primer no priming composition is used; the wire is functioning of a conductive mixture or spark gap primer
placed directly in a charge of RDX or PETN. Hot wire is readily apparent from the name. These two types of
bridges and film bridges use priming compositions. primers are not commonly used.
Composition
I II III IV V VI
Potassium chlorate, % 8.5 55 25 60 66.7 66.7
Lead mononitroresorcinate, % 76.5 - - - - -
Nitrocellulose, % 15.0 - - - - -
Lead thiocynate, % - 45 - - - -
DDNP, % - - 75 20 - -
Charcoal, % - - - 15 - -
Nitrostarch, % - - - 5 - -
Titanium, % - - - - - 33.3
Aluminum, % - - - - - 33.3
Autoignition temperature 244°C 203°C 396°C 396°C 475°C 446°C
Decomposition temperature 296°C 240°C 451°C 442°C 486°C 465°C
Density in grams per cubic
centimeter 1.9-2.6 1.6-2.2 1.6-2.2 1.6-2.4 2.16-2.36 0.6
Fuel to oxidizer ratio 0.9 to 1 0.82 to 1 0.3 to 1 0.25 to 1 0.5 to 1 0.5 to 1
Gas volume produced - - 148 96 286 150
milliliters milliliters milliliters milliliters
per gram per gram per gram per gram
7-20
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CHAPTER 8
UNITED STATES BOOSTER AND SECONDARY EXPLOSIVES
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(2) DEGN can be manufactured with a yield of the cellulose for nitrocellulose preparation is obtained
of approximately 85 percent of the theoretical by adding from coniferous wood, which is 50 to 60 percent
diethylene glycol to mixed acid containing cellulose. Another source is straw, which is 30 to 40
approximately 50.3 percent nitric acid, 44.7 percent percent cellulose. The nitration of cellulose involves
sulfuric acid, and 5.0 percent water. The temperature of replacement of the hydrogen in the three hydroxyl (OH)
the mixture is kept at 10° to 15°C. The spent acid is groups in the anhydroglucose units with NO2 groups. A
very unstable and fumes off if heated or allowed to representative formula for the nitrated cellulose may be
stand for a few hours. The separated DEGN is purified written as C6H7(OH)x (ONO2) y where x+ y=3. The
by washing with successive portions of water, dilute mononitrate, x =2 and y =1, has a nitrogen content of
sodium carbonate solution, and water until neutral. The 6.76 percent; the dinitrate, x=1 and y =2, has a nitrogen
purity of the product is dependent mainly on the purity of content of 11.11 percent; the trinitrate, x =0 and y =3,
the diethylene glycol used in the manufacturing process. has a nitrogen content of 14.14 percent. As a practical
matter, however, any desired degree of nitration up to
(3) DEGN is so insensitive that mixing with 14.14 percent may be obtained by adjusting the
another nitrated compound is required to produce a composition of the mixed acid used for nitration, the
useful explosive. DEGN alone, however, does explode acid to cellulose ratio, the time of nitration, or the
in the pendulum friction test. The explosion temperature of nitration. In nitrocellulose with less than
temperature test value for DEGN is 237°C. 14.14 percent nitrogen, the NO2 groups are distributed
(4) As indicated by the vacuum stability tests, randomly along the entire length of the cellulose
DEGN is much more stable than nitroglycerin at 100°C polymer, so x and y should be regarded as average
and will, when free from acidity, withstand long term values over the entire length of the chain. The nitrogen
storage at ordinary temperatures. content determines the chemical and physical properties
of any particular nitrocellulose. The five grades of
(5) The brisance of DEGN, as judged by the nitrocellulose listed below are recognized and used.
modified sand test, is equal to that of TNT and 81
percent that of nitroglycerin. At a density of 1.38 grams (a) Pyroxylin or collodion, which
per cubic centimeter, DEGN's rate of detonation is 6,760 contains from about 8 to 12.3 percent nitrogen, is light
meters per second, slightly less than TNT's. The Trauzl yellow, matted filaments. The theoretical maximum
lead block test indicates DEGN to be 144 to 150 percent density is 1.653 grams per cubic centimeter, the melting
as powerful as TNT and 77 percent as powerful as point with decomposition is greater than 135°C, and the
nitroglycerin. The ballistic pendulum test indicates heat of formation is -216 kilocalories per mole for
DEGN to be 127 percent as powerful as TNT and 90 pyroxylin with a nitrogen content of 12 percent. When
percent as powerful as nitroglycerin. dissolved in 3 parts ether and 1 part alcohol, the solution
is pale yellow and viscous. Pyroxylin is also soluble in
c. Nitrocellulose (NC). acetone or glacial acetic acid, and is precipitated from
(1) Nitrocellulose or cellulose nitrate is a solution by water. When thin layers of solutions are
mixture of nitrates obtained by nitrating cellulose. permitted to evaporate, the pyroxylin forms a tough,
Cellulose (figure 8-3) is a long chain polymer of colorless film. Pyroxylin is very flammable and is
anhydroglucose units (C5H10O5). The number of decomposed by light. The pyroxylin used for the
anhydroglucose units or degree of polymerization (DP) manufacture of celluloid contains 11.0 to 11.2 percent
is variable. Cellulose used for preparation of military nitrogen, while that used in the manufacture of blasting
grades of nitrocellulose have a DP of approximately explosives has a nitrogen content of 11.5 to 12.0
1,000 to 1,500. Cellulose threads possess micellar percent. The pyroxylin used for military purposes
structure and consist of numerous rod-like crystallites contains 12.20 ±0.10 percent of nitrogen. Pyroxylin with
oriented with their long axis parallel to the thread axis, 11.13 percent nitrogen is hydrolyzed to the extent of
thus forming a fiber. Almost pure cellulose is found in 1.71 percent of the available nitrogen after 240 hours of
the pith of certain plants, in absorbent cotton, and in boiling in water. The heat of detonation of pyroxylin with
some filter papers. Pure cellulose is most readily a nitrogen content of 12 percent is 1.16 kilocalories per
obtained from cotton by treating with a dilute acid or gram for liquid water and 1.02 kilocalories per gram for
base solution then thoroughly washing with water. At gaseous water.
the present time most
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(e) Blended nitrocellulose is a mixture drowned in a large amount of ice water. If, on the other
of 60 to 65 percent guncotton and 35 to 40 percent hand, drowning is done into a small amount of water and
pyrocellulose. The guncotton should have a nitrogen the temperature is allowed to rise, a certain amount of
content of 13.4 percent and the pyrocellulose nitrogen denitration takes place. During the wringing operation,
content should be 12.6 percent. Straight guncotton has which removes the spent mixed acid, if the
a higher ballistic potential than blended nitrocellulose nitrocellulose is left in contact with a humid atmosphere
but is only slightly soluble in an ether-alcohol solution, longer than usual, considerable denitration takes place,
the mixture most commonly used in the United States to especially in the outer layers of the wrung nitrocellulose.
colloid nitrocellulose. Blended nitrocellulose of the
(3) A point should be made here regarding
proportions given above is soluble to the extent of about
the mechanism of solubility of nitrocellulose. As a
37 ± 2 percent in a mixture of 2 parts ether and 1 part
general rule, solvents for polymers like nitrocellulose act
alcohol. This property makes blended nitrocellulose
at first as swelling agents and only afterwards as
suitable as a single-base propellant. Two grades of
dispersing reactants. The fibrous structure of
nitrocellulose are commonly used: one with a nitrogen
nitrocellulose is not lost when swelling compounds such
content of 13.15-±0.05 percent and one with a nitrogen
as cyclohexanone, fenchone, and meta-xylene are used.
content of 13.25±0.05 percent.
When nitrocellulose is treated with a solvent a gel is
(2) X-ray diffraction studies have yielded the obtained and the phenomena known as gelatinization
following information regarding the nitration of cellulose. occurs. A volatile solvent can be evaporated in order to
In the first stage of nitration, nitric acid penetrates the obtain a plasticlike colloided material. A smokeless
entire cellulose structure. The amorphous part of the nitrocellulose propellant processed with the aid of an
cellulose is more reactive than the crystalline part, so ether-alcohol mixture is an example. If the solvent is
the second stage involves nitration of the amorphous nonvolatile or only slightly volatile, the nitrocellulose
part. At the same time the micellar arrangement is forms a gel, but usually heat is required for completion
being broken down. The third stage of nitration involves of the operation. A double-base, solventless, smokeless
the swelling and breakdown of the micellar propellant is an example. If heating is undesirable
arrangement. Swelling takes place as shown in figure 8- because of danger, gelatinization can be achieved by
4. The nitrating agent, as is the case with any blending nitrocellulose at room temperature with a
esterifying reagent, attacks one end of the micelle and gelatinizer dissolved or suspended in a liquid, such as
causes a gradual sliding apart of the chain as nitration alcohol, which is not necessarily a solvent for
proceeds. When 12.2 percent nitrogen content is nitrocellulose. If a solid solvent such as camphor is
reached, an orderly arrangement of the chains becomes used in the preparation of celluloid, the water-wet
possible and there is a sudden appearance of the nitrocellulose is mixed with powdered camphor, some
trinitrate crystalline structure. The nitration of cellulose alcohol is added, and the mass is kneaded at room
is a reversible reaction, proceeding as: temperature for several hours. The process is usually
called plasticization. Both gelatinization and
(C6HO2)(OH)3 +xHNO3(C6H7O2) plasticization yield similar materials which are flexible
(OH)3-y (ONO2) y +xH2O and crack resistant. The difference is a gelatinizer tends
to draw the molecules together and a plasticizer spreads
where y varies between 0 and 3 over the length of the them out. The solubility of nitrocellulose in organic
polymer. Therefore, an equilibrium exists for each solvents and the formation of gels is attributed to
concentration of nitrating acid, which corresponds to a formation of molecular addition compounds between
definite degree of nitration, provided all other conditions, nitrocellulose and the solvent.
such as temperature and pressure, remain the same.
This means that if the concentration of nitrating bath (4) In the manufacture of nitrocellulose, the
containing nitrocellulose nitrated to a certain nitrogen first step is the pretreatment of the cellulose. Short
content, is slightly weakened by the addition of water, fibered cotton or cotton linters that have been suitably
the reaction will go from right to left and nitrocellulose purified by washing with water are dried at 105° to
will be partly hydrolyzed to the nitrogen content 110°C until the moisture content is reduced from 6 to 7
corresponding to the concentration of the new nitrating percent to about 0.5 percent. If the starting material is
bath. This reaction is known as denitration. The rate of wood pulp, the pulp sheets are fed into a drier
denitration is insignificant if the acid is rapidly diluted to maintained at 110° to 115°C. During a drying time of
a very low concentration and cooled at the same time about 15 minutes, the moisture content is reduced from
as, for example, when nitrocellulose wet with acid is 4 to 5 percent to about 0.5
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percent. The dried pulp sheets pass from the drier into type of cellulose nitrated, the degree of nitration desired,
a shredder where they are reduced to pieces about five and the season of the year. Higher temperatures cause
millimeters in length. In storage, the cellulose should be denitration of the mixed acid, so the nitric acid content
kept in airtight containers to prevent moisture from must be greater during the summer than during the
being absorbed. The cellulose is nitrated by the winter. Table 8-1 lists typical compositions of mixed
mechanical dipper process which has displaced other, acid.
more hazardous processes. The composition of the
mixed acid used in this process varies depending on the
8-5
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About 1,500 pounds of mixed acid are placed in a step in the process is pulping. Because cellulose fibers
stainless steel nitrator at a temperature of 30°C. The are tubular, having capillary channels running through
nitrator is equipped with two vertical agitators revolving them, part of the impurities present in guncotton are
in opposite directions that impart motion toward the included in these channels and cannot be removed
center. Approximately 32 pounds of cellulose are unless the fibers are cut into very short fragments. This
added. The paddles of the agitator are designed to operation is done in an apparatus called a beater, or
immediately draw the cellulose below the surface of the Jordan engine similar to that employed in the paper
acid, away from the fume exhaust line. The addition of industry. The beating operation is carried out with a
the cellulose requires about four minutes; agitation is large volume of water with just enough sodium
then continued for twenty minutes. Nitration is carbonate solution added to preserve a slightly alkaline
exothermic, so provisions must be made to prevent the reaction to phenolphthalein. Beating is continued until
temperature from rising above 300C. When nitration the nitrocellulose has been reduced to the desired
has been completed, the slurry is discharged through a degree of fineness, as determined by a settling test.
valve in the bottom to a centrifuge, called a wringer, After the slurry from the beater has been settled and
where most of the mixed acid is removed. The decanted, the nitrocellulose is subjected to poaching.
composition of the spent acid can be adjusted if the acid Poaching consists of one four-hour, one two-hour, and
is to be reused in nitration. The acid-wet, crude two one-hour boiling treatments with settling,
nitrocellulose is then forked through an opening in the decantation, and the addition of fresh water after each
bottom of the wringer into a drowning basin where rapid treatment. In the four-hour boiling treatment, sodium
submersion in cold water takes place. The nitrocellulose carbonate equaling 0.5 percent of the weight of dry
must then be stabilized and purified. High nitrogen nitrocellulose is added. The poaching treatment is
nitrocellulose can be prepared in the following additional followed by not less than two washes with cold water,
ways. Guncotton wetted with 25 percent water can be each wash consisting of agitation of the nitrocellulose
nitrated to 14 percent nitrogen content by a mixed acid with fresh water for at least half an hour. The next step
containing either 60 percent nitric acid, 20 percent in the process is called screening. Uniformity of
acetic acid, and 20 percent acetic anhydride or 50 characteristics is difficult to obtain in the various batches
percent nitric acid, 25 percent acetic acid, and 25 of nitrocellulose. To ensure uniform characteristics in
percent acetic anhydride. This process yields the final product, portions of batches having high
nitrocellulose with 14 percent nitrogen of low viscosity nitrogen content and high viscosity are mixed with
which is suitable for military use. Other nitrating agents portions having low nitrogen content and viscosity. The
may be used to produce different percentages of resulting mixtures possess properties intermediate
nitrogen. Another method of nitration is to heat between those of the individual batches. The mixed
concentrated nitric acid to form N2O5 vapors which are slurry is fed through a distributor which spreads the
passed over cellulose in the shape of paper rolls. This nitrocellulose uniformly on packer screens. The screen,
process yields a 14 percent nitrogen content. with 0.02 inch slots, is vibrated mechanically and the
(5) Removal of the impurities in the raw properly pulped nitrocellulose passes through the screen
nitrocellulose is critical to obtain a product with suitable into collecting boxes. If a blended nitrocellulose is
stability. Acids and other impurities are absorbed on the desired, blending is the next step in the manufacturing
fibers of the nitrocellulose and are hard to remove. The process. Each blending unit consists of two tubs,
first step in the process, called the sour boil, is carried equipped with propeller type agitators, interconnected so
out in large cypress wood tubs equipped with ducts for that the contents are kept in constant circulation. The
heating and circulating water at approximately 100°C. receiving tub, or high tub, is filled with slurry from the
During the first two hours, the acidity of the water is screening operation so that the overflow discharges into
adjusted to 0.05 to 0.50 percent, calculated to H2SO4. the low tub. When the low tub is partially full, a
Pyrocellulose and pyroxylin are subjected to 40 hours of circulating pump is started and part of the slurry is
boiling treatment with three changes of water during this returned from the low tub to the high tub. This process
period. Guncotton is subjected to 60 hours of boiling is continued for 6 to 7 1/2 hours after which time a
treatment followed by two five-hour boiling treatments sample is tested for nitrogen content and solubility in a
with a change of water after each treatment. The next solution of 2 parts ether and 1 part alcohol. The last
step in the
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manufacture of nitrocellulose is wringing. Nitrocellulose test values and deteriorate more rapidly. The nitrates of
from the screening or blending process is placed in a oxidized cellulose are also objectionable and cause
centrifugal wringer with a perforated brass basket lined increased instability of nitrocellulose if not removed
with a 24 mesh copper screen. The basket revolves at during the purification process. Elevated temperature
950 rpm for about seven minutes. The wrung tests show that even nitrocellulose of high purity is much
nitrocellulose, with a moisture content of about 31 less stable than most of the noninitiating military high
percent is stored in rustproof metal cans with tight fitting explosives. The stability of pyrocellulose and blended
covers. nitrocellulose is 35 minutes, minimum, by the 65.5° KI
(6) Dry nitrocellulose is very sensitive to test and 30 minutes, minimum, by the 134.5°C heat test.
impact, friction, heat, and spark and is never handled in Figure 8-5 shows the DTA and pyrolysis curves for
quantity in the United States. The results of impact nitrocellulose. Vacuum stability tests indicate the
sensitivity tests for all types of nitrocellulose are stability of nitrocellulose decreases with increasing
approximately 8 centimeters, which indicates nitrogen content. For nitrocellulose with a nitrogen
nitrocellulose is 460 percent as sensitive as TNT or content of 12 percent, 5.0 cubic centimeters of gas are
about the same as mercury fulminate and lead azide. evolved in 48 hours at 120°C. In the LLNL reactivity
Rifle bullet impact tests indicate nitrocellulose to be very test, 1.0 to 12 cubic centimeters of gas are evolved per
sensitive with 100 percent of the trials yielding complete .25 grams of sample. Nitrocellulose appears to undergo
detonations. While the five second explosion very slow decomposition even at ordinary temperatures.
temperature test value for pyrocellulose (170°C), The rate of decomposition increases 3.71 times with
blended nitrocellulose (200°C), and guncotton (230°C) each 10°C increase in temperature. The presence of
are not particularly low, the rapid rate of decomposition moisture increases the rate of decomposition
of the material at temperatures greater than 100°C and considerably and the presence of free acid or alkali has
the exothermicity of such decomposition make the an even more pronounced effect. Rates of
material very sensitive to ignition by a spark. decomposition of pyrocellulose under various conditions
Nitrocellulose can be detonated even when wet. A are shown in table 8-2.
mixture of 60 percent nitrocellulose and 40 percent
water confined in a steel barrel sometimes is detonated
Table 8-2. Decomposition of Nitrocellulose
by a stick of dynamite. The frequency of detonation is
greater when the water is frozen. Tests have shown that
Percent available nitric
nitrocellulose uniformly wetted with 35 percent ethanol
Decomposition medium acid liberated per hour at -
will also detonate, on occasion, when initiated with
dynamite. 50°C. 97.5°C.
Heat 0.0000045 0.0028
(7) The brisance of nitrocellulose, as Water 0.0000111 0.0051
determined by the sand test, is directly comparable with 0.06 Percent nitric acid 0.0000325
TNT but less than tetryl. The brisance of nitrocellulose solution
increases with increases in the nitrogen content. The 0.035 Percent nitric acid - 0.0088
rate of detonation of guncotton with a nitrogen content solution
of 13.45 percent and density of 1.2 grams per cubic 0.035 Percent sodium 0.0006870 0.1358
centimeter is 7,300 meters per second; greater than that carbonate solution
of TNT. As nitrocellulose propellants can be detonated 95 Percent ethanol 0.0000290 -
as well as burned, their brisance values are high. Trauzl
lead block tests show guncotton (13.2 to 13.4 percent From these data, it is apparent that alkali is more
nitrogen) to be 136 to 147 percent as powerful as TNT effective than acid in causing the deterioration of
and the ballistic mortar test indicates guncotton is 118 nitrocellulose. Pyrocellulose is hygroscopic to the extent
percent as powerful as TNT. of 3 percent at 30°C and 90 percent relative humidity.
Under the same conditions blended nitrocellulose, 13.15
(8) The great care taken in the purification of
percent nitrogen, is hygroscopic to the extent of 2.5
nitrocellulose is due to the necessity for removing
percent, guncotton, 13.45 percent nitrogen, to 2 percent,
impurities that are much less stable than the
and high nitrogen nitrocellulose, 14 percent nitrogen, to
nitrocellulose. Cellulose sulfate is unstable with respect
1 percent.
to heat and moisture. Propellants made from
nitrocellulose containing even comparatively small
amounts of such esters give decreased 134.5°C heat
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(9) Military grades of nitrocellulose are: 20°C. Viscosity values are 0.36, 0.21, 0.094, and 0.068
poise at 20°, 30°, 50°, and 60°C, respectively. The
vapor pressure values for nitroglycerin in torr are 0.0013
Class Nitrogen, percent at 1 5°C, 0.0015 at 20°C, 0.00177 at 25°C, 0.00459 at
35°C, 0.0075 at 40°C, 0.01294 at 45°C, 0.03587 at
Grade A Pyrocellulose 55°C, and 0.06 at 60°C. Decomposition begins at 50°to
Type I 12.60±0.10 60°C. Nitroglycerin is volatile to the extent of 0.11
Type II 12.60±0.15 milligram per square centimeter per hour at 60°C. The
Grade B Guncotton 13.35 minimum specific heat of nitroglycerin is 0.356 calories per gram
Grade C Blended per degree centigrade between 35°C and 200°C.
Type I 13.15±0.05
Type II 13.25±0.05 (4) The heat of detonation is 1,486 calories
Grade D Pyroxylin 12.20 ±0.10 per gram for gaseous water and 1,590 for liquid water.
Grade E 12.00±0.10 One gram/mole of nitroglycerin produces 715 millititers/
163.5 liters. The heat of formation is-90.8 kilocalories
The maximum allowable ash left after ignition of the per mole.
nitrocellulose in any grade is 0.4 percent. The minimum
percentage that is insoluble in ether alcohol in grades A, (5) Nitroglycerin is soluble in one liter of
D, and E is 99 percent. The solubility limit for grade C water to the extent of only 0.173, 0.191, 0.228, and
in ether alcohol is left to discretion of the contractor 0.246 gram at 20°, 30°, 50° and 60°C, respectively and
manufacturing propellants from the nitrocellulose. is essentially nonhygroscopic when exposed to
atmospheric humidity. Absolute ethanol dissolves 37.5
and 54 grams of nitroglycerin per 100 grams of solvent
d. Nitroglycerin (NG).
at 0° and 20°C, respectively. 96 percent alcohol
(1) Nitroglycerin, glycerol trinitrate, or 1,2,3- dissolves 40 grams per 100 grams of solvent at 20°C.
propanetriol trinitrate, shown in figure 8-6, is a clear, Carbon tetrachloride dissolves 20 milliliters per liter and
colorless, odorless, oily liquid with a theoretical trichloroethylene dissolves 20 parts per 100 parts of
maximum density of 1.596 grams per cubic centimeter. solution. Carbon disulfide at room temperature
Nitroglycerin has a sweet, burning taste and a molecular dissolves only 12.5 grams per liter of solvent. Hot
weight of 227.1. ethanol and nitroglycerin are miscible in all proportions.
Nitroglycerin is miscible in all proportions with ether,
acetone, glacial acetic acid, ethyl acetate, benzene,
toluene, phenol, nitrobenzene, chloroform, ethylene
chloride, and nitric esters such as glycol dinitrate.
Nitroglycerin can be used as a solvent for other
explosives; 35 grams of dinitrotoluene dissolve in 100
Figure 8-6. Structural formula for nitroglycerin. grams of nitroglycerin at 20°C and 30 grams of
trinitrotoluene dissolve per 100 grams at 20°C.
(2) Pure nitroglycerin freezes to form Nitroglycerin is used extensively in propellant
dipyramidal rhombic crystals with a heat of compositions as a gelatinizing agent for nitrocellulose as
crystallization of 33.2 calories per gram. This is a well as in dynamites and for the shooting of oil wells.
stabile form with a freezing point of 13.2°C and melting
point of 13.5°C. Under some conditions, glassy triclinic (6) Concentrated sulfuric acid decomposes
crystals with a heat of crystallization of 5.2 calories per nitroglycerin resulting in the formation of nitric acid. In
gram are formed. This is a labile form with a freezing the presence of metallic mercury, nitric oxide is formed
point of 2.1°C and a melting point of 2.8°C. The labile quantitatively, and this reaction is the basis for
form gradually changes into the stabile form after a determination of the purity of nitroglycerin by the
week or two with a heat of conversion of 28 calories per nitrometer method. The reaction between nitroglycerin
gram. Nitroglycerin has an apparent boiling point of and aqueous sodium hydroxide is slow because of their
145°C, but this is merely the temperature at which immiscibility, but if ethanol is added the reaction is
nonexplosive decomposition becomes vigorous enough rapid. Sodium nitrate, nitrite, formate, and acetate are
to resemble boiling. True boiling takes place at reduced produced in this reaction and resinous material, oxalic
pressure; at 2 torr the boiling point is 125°C and at 50 acid, and ammonia are produced as byproducts.
torr the boiling point is 180°C. Even under high vacuum Nitroglycerin is hydrolysed to a very slight extent by
boiling, however, some decomposition takes place. water; producing less than 0.002 percent of acidity in 10
days
(3) Nitroglycerin has a specific gravity value
of 1.596 20/15 and a refractive index value of 1.4732 at
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at 22°C or 0.005 percent of acidity in 5 days at 60°C. sodium chloride solution to remove any nitroglycerin
An aqueous solution of sodium sulfide decomposes water emulsion. Moisture content gives the product a
nitroglycerin producing great heat. This reaction can be milky appearance, but on storage in a heated building,
used for the destruction of waste material. the material becomes clear and the moisture content
decreases to 0.4 percent or less. The yield of
(7) Nitroglycerin is manufactured by nitrating nitroglycerin is 230 ±5 parts by weight per 100 parts of
glycerin with a mixed acid. Several processes are glycerin.
currently used in the United States and Europe. The
(b) The chemistry involved in the
processes can be generally classified according to
continuous manufacture of nitroglycerin is basically the
whether they are continuous or batch production.
same as that described for batch processing except the
(a) In batch production, high grade equipment is designed to allow nonstop production. The
glycerol is added to mixed acid that consists of 45 to 50 advantages of continuous processes are: faster
percent nitric acid and 50 to 55 percent sulfuric acid. production, better process control, lower labor costs,
The mixed acid is prepared well in advance to allow and, perhaps most important, safety, as a result of the
metallic sulfates to settle out. The metallic sulfates smaller accumulations of nitroglycerin at any given plant
might otherwise interfere with separation of the location. In the United States the common practice is to
nitroglycerin. Two important factors determine the nitrate mixtures of glycol and glycerol. The nitration
proportions in the mixed acid. First, that the ratio of the proceeds in the same manner as with pure glycerol.
sulfuric acid to water at the end of the reaction, the
dehydrating value of the sulfuric acid or DVS, is 1 The Schmid-Meissner process
maintained between 4.35 and 4.5. The water includes (figure 8-7) involves continuous nitration of glycerin or
both the water in the original reactants and that other liquids, such as ethyleneglycol or diethyleneglycol,
produced during the reaction. This ensures that the separation of the nitrated product from spent acid, and
nitric acid is maintained at a sufficient concentration to purification by neutralization and washing. The stainless
ensure completion of the reaction so that completely steel nitrator is equipped with a motor driven, steel
nitrated products that are subject to exothermic propeller, vertical cooling coils, and an overflow tube to
oxidation reactions are not formed. Second, that separator. A two way valve, which may be connected to
enough nitric acid is present to drive nitration, which is a the mixed nitric-sulfuric acid line or may be opened to
reversible reaction, to completion. A slight excess of the drowning tank, is fitted centrally to the bottom of the
nitric acid will accomplish this. The reaction between nitrator. Brine at about-5°C is circulated at a controlled
the glycerol and mixed acid is carried out in a nitrator rate around the cooling tubes in the annular space
equipped with a mechanical agitator and cooling coils outside the nitrator. As a measured amount, per unit
that carry a brine solution of calcium chloride at-20°C. time, of mixed acid is fed in from the bottom, a
A 6,800 pound charge of mixed acid is placed in the calculated amount of glycerin is fed in from the top at a
nitrator and the glycerol is added in a small stream. The level below that of the overflow pipe. The flow of
mixed acid to glycerol ratio, by weight, is between 5.5 materials into the nitrator is by means of automatically
and 6.5. If too much glycerol is added, exothermic controlled air pressure. The propeller mixes the two
decomposition and oxidation reactions occur and liquids and glycerin is nitrated to nitroglycerin. The
temperature control becomes difficult. The temperature temperature in the nitrator is not allowed to exceed
is maintained at 2° to 3°C by cutting off the flow of 18°C. The emulsion of nitroglycerin and spent acid
glycerol as necessary. If the temperature does rise flows off continuously through the overflow to the
above 3°C, the contents are drowned in a water tank separator, which is a stainless steel, inclined,
beneath the nitrator. Stirring must be adequate to rectangular tank provided with a number of vanes,
prevent freezing on the cooling coils. Stirring is equipped with a bottom draw off valve for spent acid, a
continued for a few minutes after the 50 to 60 minutes sight glass near the top, and a steel neck with overflow
required to add the glycerol. Then the nitroglycerin is pipe for the nitroglycerin. Because of difference in
allowed to separate completely. The lower layer of density, the spent acid settles to the bottom of the
spent acid is drained off to be recycled or otherwise separator and the nitrated product rises. The withdrawal
disposed of, and the nitroglycerin is run off into a of acid from the bottom is regulated to keep the
neutralizer. An initial 40°C water wash removes most of separated nitrated product in the top of the separator at
the acid. Then a wash with a 2 to 3 percent sodium a predetermined level. The spent acid is discharged to
carbonate solution neutralizes the residual acid. the acid recovery plant and the nitroglycerin flows by
Washing with water is continued until the water is free of gravity to the base of the first of the washing columns.
alkali and the nitroglycerin is neutral to litmus. The final
step in this manufacturing process is to wash with a
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Each column consists of superimposed cylindrical glass solution of soda and ammonia and then emulsified with
sections (rings) separated by perforated stainless steel air. The emulsion flows from the top of the column to
plates and rubber ring gaskets. The nitrated product another intermediate separator where the nitrated
from the separator enters the bottom of the first washing product settles to the bottom and is separated from the
column, is mixed with cold water and emulsified by soda ash water, which is conducted to waste via settling
means of air injected into the liquid. This also forces the tanks. Any nitroglycerin held in the tanks is drawn off
material to rise to the top of the column, where the periodically and rewashed. The nitrated product is
emulsion overflows into a tank which serves as an subsequently passed through additional wash columns
intermediate separator. Here the nitrated product and separators until the desired stability is attained.
rapidly settles to the bottom, and flows to the base of the Finally the purified product is passed through a flannel
second wash column. In the second column the filter bag before being caught in a lead tank for storage
separated nitroglycerin is mixed with a hot dilute and use.
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2 The Biazzi process (figure 8-8) storage tank. In cases of overheating, the nitrator and
is similar to the Schmid-Meissner, but is considered to the first separator can be emptied quickly into a
be safer because of the smaller amount of nitroglycerin drowning tank which is generally filled with water but can
in the system at a given time. The nitrator is a small, be filled with sulfuric acid. The Biazzi process is also
cylindrical, stainless steel vessel provided with a bank of used in the manufacture of DEGN and other aromatic
helical cooling coils. A high speed, shrouded, impeller- and alphatic nitrocompounds. Only one nitrator is
type agitator forces the nitrating acid up through the required for mononitration but for higher degrees of
bank of coils and down through the cylindrical space in nitration more nitrators are added in series. Such
the center of the coils. The fresh, mixed acid and the nitrations usually employ the spent fortified acid from
material to be nitrated stored in large scale tanks or bins the higher nitration as the mixed acid for the next lower
enter, in controlled ratio, at the top of the nitrator, nitration.
striking the liquid at such a point in the vortex that the 3 The Swedish Nobel
feed is immediately thrust beneath the surface and Aktiebolaget process for nitrating glycerin consists of an
carried down through the central space formed by the injector nitrator and a centrifugal separator for
coils. The mixture then spirals back, up and out, separating nitroglycerin from spent acid. The mixed
through the banks of cooling coils and a portion is acid used in this process is a mixture of about 1.7 parts
carried off by the overflow pipe which leads to the spent acid and one part conventional, 50 percent nitric
separator. The flow of mixture past the coils is counter and 50 percent sulfuric acids, mixed acid. This mixture
to the flow of cooling brine circulating through the coils. contains about 27 percent nitric acid and 10 percent
Because of this arrangement which permits rapid water. Glycerin flow into the injector is controlled by the
reaction through rapid heat absorption, the mixed acid acid flow through the injector in the same manner that
can be stronger than that used in the Schmid-Meissner suction is produced by a water aspirator. Thus, if the
process. The cooling coils, agitator, and cover of the acid flow is reduced by some equipment malfunctioning,
nitrator are mounted as a unit separate from the the glycerin flow is automatically decreased. This
cylindrical body, which can be lowered hydraulically for process, unlike most of the others, operates at a high
inspection. The Biazzi acid separator is a stainless steel temperature, about 45° to 50°C. The glycerin or
vessel of the shape shown in the figure. The emulsified glycerin-glycol mixture is heated to 45° to 50°C before
mixture of nitrated product and spent acid enters entering the injector. The mixed acid is cooled to 0°C.
tangentially through the side about midway up and In the injector the heat of reaction maintains the fluid
imparts a slight centrifugal action to the upper layer of temperature at 45° to 50°C. Automatic controls give
liquid in the separator. This action helps to break the warning or shut down the operation if the temperature
emulsion and to prevent local overheating. The spent rises a few degrees above the normal range. The
acid flows continuously from the bottom of the separator nitroglycerin acid emulsion enters a cooling system
through a draw off valve, controlled by an adjustable immediately after leaving the injector. The temperature
collar, which can be raised or lowered by means of a of 45°to 50°is maintained for only about half a second.
micro screw attachment. After leaving the first During the next 80 to 90 seconds the mixture is cooled
separator, the acid is passed through an after-separator to 15°C. In the following 30 seconds the nitroglycerin is
from which some of the nitrated product is recovered. separated from the spent acid. A continuous centrifugal
The spent acid leaving the after-separator is usually separator separates nitroglycerin from the spent acid.
diluted with water to dissolve traces of dissolved nitrated The centrifuge operates at 3,200 rpm. For a unit with a
product. The separated, nitrated product is continuously capacity of 25,000 liters per hour the quantity of
drawn off from the first separator into a stainless steel nitroglycerin in the separator bowl during operation is
wash tank equipped with a cylindrical baffle and an only 3.5 kilograms. The separated acid free
impeller-type agitator. Water is continuously added to nitroglycerin is emulsified immediately by a wash jet to
the washer and the mixture overflows into a second form a nonexplosive mixture and is removed
separator. The nitrated product is drawn from the continuously from the separator house to the
bottom of the separator and is conducted to the second nitroglycerin wash-and-weigh house.
washer where some soda wash solution is added with
agitation. If a high purity nitrated product is required, 4 Another proposed method is
such as for nitroglycerin used in propellants, the very similar to the Nobel Aktiebolaget process where the
emulsion from the second washer, together with some reaction is carried out in a tube. The significant
soda ash solution, is conducted through a battery of difference is that the mixed acid and glycerin are
three or four washers in which wash waters are running pumped and turbulent flow is maintained in the tube to
countercurrent to the movement of nitroglycerin. From ensure a complete, rapid reaction. The reactants are
there the emulsion passes through a series of then cooled, separated, and washed.
separators arranged in cascade and is collected in a
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diammonium carbonate, chalk, or talc did not transmit per second, 0 meters per second, and 1,165 meters per
the detonation even at zero gap. The particle size of the second were obtained for the stabile, labile, and liquid
salts is important. For NaCI the optimum size is 0.10 to forms, respectively. Use of a 20 gram tetryl booster
0.12 millimeter in greatest dimension. Nitroglycerin is gave 9,100 meters per second for the labile form. Use
initiated to detonation by a black powder squib, but not of 10 to 15 grams of the stabile form as a booster gave
uniformly so. No data are available in connection with 8,750 meters per second for the liquid form. Tests
the sensitivity of nitroglycerin to initiation by initial indicate that the brisance of the stabile form is much
detonating agents. However, the fact that 40 percent higher than either the labile or liquid form. The Trauzl
straight dynamite can be detonated by lead styphnate lead block compression test indicates nitroglycerin is
indicates a high degree of sensitivity, since lead 115 percent as brisant as TNT while the sand test
styphnate will not detonate pressed PETN and this is indicates a value of 120 percent. The temperature of
very sensitive to initiation. explosion is given as 4,577°C for the decomposition as
shown:
(10) Pure nitroglycerin is too sensitive to be
transported by common carrier. A mixture of 70 parts of NG 3CO2 +2.5H2O + 1.52N +0.5O2
nitroglycerin and 30 parts of acetone by weight is
relatively insensitive and sometimes is transported by and a resultant pressure of 10,000 atmospheres. Trauzl
wagon or truck. Such a mixture can be detonated by a lead block test results of 390 cubic centimeters, 518
No. 8 blasting cap. Modified Bureau of Mines impact cubic centimeters, and 560 cubic centimeters were
tests of various mixtures gave the sensitivity values obtained for the stabile, liquid, and labile forms,
shown by table 8-3. respectively. The Trauzl lead block test value for
nitroglycerin is greater than that for any other military
explosive. This is in agreement with the
Table 8-3. Impact Sensitivity of correspondingly high heat of explosion value. The
Nitroglycerin-Acetone Mixtures ballistic pendulum test values indicate RDX and PETN
Composition, percent Impact test to be more powerful than nitroglycerin. This can be
Nitroglycerin Acetone centimeters explained by the fact that nitroglycerin has a ratio of
100 0 16 combined oxygen to oxygen required for complete
90 10 23 combustion of 105.9 percent, while RDX and PETN
80 20 41 have corresponding ratios of 66.7 and 85.7 percent,
75 25 60 respectively. In the Trauzl test, the samples are not in
73 27 64 contact with air, while in the ballistic pendulum test, air
70 30 100 + surrounds the sample when placed in the explosion
chamber. This would tend to increase the test value for
The nitroglycerin in such a mixture can be separated explosives that are less than oxygen-balanced but have
from the acetone by precipitating the nitroglycerin by no effect on the test value for nitroglycerin.
addition of an excess of water or by evaporating the
acetone with a current of air. An emulsion of 87 percent (12) Nitroglycerin is quite stable at
nitroglycerin and 13 percent water that has been temperatures less than 50°C, as shown by storage tests
stabilized with methyl cellulose also has been found to over a period of years. At higher temperatures, the rate
be sufficiently insensitive to permit safe handling. This of decomposition increases rapidly, and 100°C vacuum
mixture is not detonated by a blasting cap. stability test data show that at that temperature
nitroglycerin is the least stable of the standard military
(11) The detonation velocity of nitroglycerin explosives of the noninitiating type. Nitroglycerin does
varies according to the method of initiation. When not cause significant corrosion of metals. This is
properly initiated, the normal rate of detonation at a attributed to the low solubility in water, the stability, and
density of 1.60 grams per cubic centimeter is given as the neutrality of nitroglycerin. Rust markedly increases
7,700 meters per second. When improperly initiated, the decomposition of nitroglycerin, as indicated by
the rate can be as low as 1,500 to 2,000 meters per 100°C vacuum stability tests. The presence of more
second. The rate of detonation also varies according to than a trace of free acid renders nitroglycerin quite
the state of the nitroglycerin. In a 22 millimeter inner unstable; decomposition with the appearance of red
diameter glass tube with a 7,000 meters per second fumes takes place within a few days.
picric acid fuse, detonation velocities of 9,150 meters
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PETN forms eutectic mixtures with a number of enhances the hydrolysis. The main product of
compounds as shown in table 8-6. hydrolysis is pentaerythritol dinitrate. At temperatures
up to about 50°C, dry PETN does not react with copper,
Table 8-6. PETN Eutectics brass, aluminum, magnesium, magnesium-aluminum
Melting alloys, stainless steel, mild steel, mild steel coated with
Composition point (C°) acid-proof black paint, and mild steel plated with copper,
1.5 percent PETN with 98.5 percent 12.3 cadmium, nickel or zinc. Wet PETN does not react with
nitroglycerin stainless steel, and aluminum is affected only slightly
20 percent PETN with 80 percent 82.4 after long periods of storage. However copper, brass,
m-dinitrobenzene magnesium, magnesium-aluminum alloys, mild steel,
10 percent PETN with 90 percent 67.3 mild steel coated with acid-proof black paint, and mild
2,4-dinitrotoluene steel plated with cadmium, copper, nickel or zinc are
13 percent PETN with 87 percent 76.1 affected. PETN is used in the explosive core of
trinitrotoluene industrial detonating fuses, in the charge of commercial
30 percent PETN with 70 percent tetryl 111.3 blasting caps, and as the entire explosive charge in
20 percent PETN with 80 percent 101.3 exploding bridge wire detonators. PETN is also used in
mannitol hexanitrate certain plastic bound explosives and in a mixture with
TNT called pentolite.
(2) PETN is decomposed much more slowly
by a boiling 2.5 percent solution of sodium hydroxide (3) While PETN can be manufactured by
than nitrocellulose. Several hours are required for treating pentaerythritol with nitric acid and adding
complete decomposition. At 50°C a solution of sodium concentrated sulfuric acid to complete the separation of
sulfide decomposes PETN slowly, but decomposition the PETN, manufacture in the United States has been
proceeds rapidly in a boiling solution of ferrous chloride. with nitric acid alone:
PETN does not reduce Fehling's solution even on C(CH2OH)4 +4HNO3- C(CH2NO3)4 +4H2O
boiling. Hydrolysis of PETN takes place in water about
100°C; at 125°C under pressure the reaction proceeds
quite quickly. Addition of 0.1 percent nitric acid
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Class A PETN is used in detonating fuses and boosters; is going from a region of 90 percent crystal density to
class B is used in priming compositions; class C is used one of 80 percent crystal density. Initiation by friction
in the manufacture of pentolite; and class D is used in and electrical spark proceeds like initiation by impact
blasting caps and detonators. Pure PETN has a after the formation of the hot spots. The maximum
nitrogen content of 17.72 percent and a melting point of nonignition spark voltage and nonignition energy for
141.3°C. The military grade is approximately 99 PETN with a particle size of 2.6 microns is 12000 volts
percent pure. The insoluble particles requirement is and 0.036 joules, respectively, at 500 micro farads
important because of the sensitivity of PETN and the capacitance and a spark gap of 0.005 inches. The
known effect of gritty material in increasing sensitivity. energy required to detonate PETN 50 percent of the
The acidity or alkalinity requirement is important since time is 0.19 and 0.36 joules for brass electrodes with
the presence of as little as 0.01 percent of either has lead foil coatings of 3 and 10 mils, respectively. For a
been found to accelerate the deterioration of PETN steel electrode, the energy required is 0.1 and 0.41
markedly. The granulation requirements are those joules with lead foil coatings of 1 and 10 mils,
found optimum for specific uses of PETN. respectively. The physical condition of the explosive
appears to have some influence on the amount of
(5) PETN is not as sensitive to impact as energy required for initiation. The discharge energy
nitroglycerin or nitrocellulose, but is slightly more required increases with PETN particle size, packing
sensitive than RDX and distinctly more so than tetryl. density, water content, circuit inductance, and a
Experiments using a five kilogram weight dropped one decrease in ambient temperature. PETN is not
meter onto a 15 milligram sample of polycrystallin PETN particularly sensitive to electrostatic spark. The
show the physical changes that occur before initiation. electrostatic sensitivity parameters should not be
The layer of PETN compresses to about 0.1 millimeter confused with the initiation of PETN by an exploding
thick. After about 10 microseconds, lateral spreading bridge. The exploding bridge is a wire through which a
stops and jetting occurs at 150 meters per second. The large current is passed, causing the wire to burst. There
initially opaque layer of PETN becomes gradually is an optimum length for each wire material and a
translucent in an additional 10 to 15 microseconds and minimum critical volume of explosive that must be
completely transparent in 15 to 20 microseconds. The detonated to cause initiation. Other factors that
transparency and rapid mobility of the PETN is enhance the ability of the bridge to detonate PETN are:
associated with surface fusion and then melting of the high power input to increase temperature and pressure,
entire sample. About 25 microseconds after the lateral a sustained electrical energy input just after the wire
spreading has stopped, the jetting velocity has bursts to provide simultaneous electrical and chemical
increased to 300 meters per second and five energy contributions during the critical growth to
microseconds after that several hot spots develop detonation period, and use of wire materials with low
simultaneously. The exact mechanism of how the hot boiling points and heats of vaporization for greater heat
spots form is controversial and no generally satisfactory transfer. Attempts to initiate PETN by normal light have
explanation has been put forward. The hot spots are been generally unsuccessful although a few instances of
points where deflagration has started. Initially, the some deflagration have occurred with very intense light.
deflagration proceeds at several tenths of a meter per Lasers can be used to initiate PETN. The energy
second. The products of gaseous combustion raise the required for initiation increases with increased packing
pressure of the reaction region and accelerate the rate density. PETN five millimeters thick with a density of
of deflagration. At the same time, the products of hot one gram per cubic centimeter can be detonated by a
combustion penetrate into unreacted regions to produce neodymium glass laser with an output at 10600
new ignition sites and a further pressure increase, Angstroms when the beam is focused to produce a
accelerating deflagration even more. At about 5 to 15 power density in excess of 0.08 megawatts per square
millimeters from the point of initiation, the velocity of the millimeter. The delay in producing a steady detonation
flame front has increased to several hundred meters per under these conditions is 1.5 to 2.0 microseconds. The
second. The flame front drives a compression wave delay can be reduced to under 0.5 microseconds if the
into the unreacted material. When this compression PETN is coated with a 1000 Angstrom thick layer of
wave attains a velocity of about 700 to 800 meters per aluminum which has been deposited on the sample, and
second, there is a sharp increase in the propagation the laser radiation is from 0.5 to 4.2 joules for 25
velocity to about 1000 meters per second. Depending nanoseconds. Initiation appears to be a thermal
on the condition of the explosive, this low velocity process. The laser energy is absorbed rapidly in a thin
detonation can propagate over considerable distances layer of explosive which produces a shock wave that
or can go over into a normal detonation whose causes the initiation of the entire sample.
propagation velocity is determined by the density and
dimensions of the PETN layer. One condition that can
cause acceleration of the detonation velocity to normal
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(6) Gap tests indicate the shock sensitivity of particle size increases. Gap test results are shown in
PETN increases as packing density increases and as table 8-8.
Table 8-8. Gap Test Results for PETN
Percent Sensitivity in
Density voids millimeters
NSWC small scale gap test 1.775 0.3 6.03
1.576 11.5 14.38
1.355 27.9 13.56
LANL small scale gap test 1.757 0.7 5.21
(pressed)
LANL large scale gap test 0.81 (raw) 54.2 69.4
Increasing the pressure of an inert gas such as carbon 8-9 lists the detonation velocity of PETN at various
dioxide, nitrogen, or a Nobel gas in the interstices of a packing densities determined experimentally with the
PETN pressing decreases shock sensitivity. Increasing confinement indicated.
the pressure of oxygen increases shock sensitivity. In
Table 8-9. Detonation Velocity Versus Density
cast PETN and PETN that has been pressed to 90
Detonation Detonation
percent of the crystal density, substantial reactions take
place well behind the shock front that enters the charge Density velocity Density velocity
and proceeds through the explosive. Stable detonation (g/cc) (m/sec) (g/cc) (m/sec)
occurs when the compression waves produced by this 1.773 8,300* 1.27 6,660†
reaction catch up with the initial shock front. PETN is 1.765 8,280† 1.26 6,760†
less sensitive to friction than RDX and more sensitive 1.765 8,240* 1.09 5,830†
than nitroglycerin, as judged by the pendulum friction 1.763 8,270* 0.55 3,850*
test. Explosion temperature test values indicate PETN 1.762 8,250* 0.436 3,400*
to be as sensitive to heat as nitroglycerin or 1.762 8,260* 0.241 2,810*
nitrocellulose. However, the minimum temperature 1.51 7,440† 0.201 2,730*
required for the explosion of PETN, 215°C, is greater 1.51 7,490† 0.185 2,670*
than that required for the explosion of nitroglycerin,
210°C, and nitrocellulose, 175°C. PETN is more *Unconfined rate stick
sensitive to initiation than nitrocellulose, RDX, or tetryl, †Cylinder test
as judged by the sand test. This is shown, also, by the
fact that PETN with 35 percent of water present can be The following equations, which are in agreement with
detonated by a No. 6 electric blasting cap, whereas the data in the table, specify the detonation velocity in
RDX fails to explode if more than 14 percent of water is kilometers per second as a function of density, p, for the
present. PETN is one of the most sensitive of the range indicated.
standardized military explosives.
D=2.14+2.84p p < 0.37
(7) As measured by the sand test, PETN is D=3.19+3.7(p-0.37) 0.37 < p < 1.65
between 129 and 141 percent as brisant as TNT. Plate D=7.92+3.05(p -1.65) p > 1.65
dent tests indicate PETN is 127 percent as brisant as
TNT and the lead block compression test indicates a
brisance of between 130 and 137 percent of TNT. Table
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The diameter of a PETN charge has little effect on the confinement effects parallel the diameter effects, the
velocity of detonation. The charge diameter below detonation velocity of PETN is not greatly affected by
which no detonation can take place (the critical confinement for any particular charge size. This is also
diameter) is only 0.9 millimeters for PETN at a density indicated by table 8-9. Detonation, or Chapman-
of one gram per cubic centimeter with 0.025 to 0.1 Jouguet, pressure is shown as a function of packing
millimeter particles. The critical diameter becomes density in table 8-10.
smaller as the density of the charge is increased. Since
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The ballistic mortar test indicates PETN is 137 to 145 evolved per .25 grams of sample. Figure 8-10 shows
percent as powerful as TNT. The Trauzl test indicates the percentage of PETN decomposition as a function of
PETN is 161 to 189 percent as powerful as TNT. PETN is time and temperature for temperatures over 140°C.
ranked with RDX and nitroglycerin as the most potent of The curves were obtained by heating a sample to the
military explosives. indicated temperature for the indicated time then
analyzing the remaining PETN. The following six
(8) The products obtained upon detonation of reactions, which take place simultaneously, show the
PETN depend on the density of the explosive. The four mechanism of thermal decomposition:
equations listed in subparagraphs (a) through (d) are valid
at the density given. The subscript s refers to soot. The
soot is produced in the Chapman-Jouguet region by the
reactions:
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(2) TEGN is prepared by the nitration of a 1 percent sodium bicarbonate solution until the
triethylene glycol. The laboratory procedure for the washings are colorless. The ether solution is then water
production of TEGN is given here. The actual washed until the pH is seven. The solution is then
manufacturing procedure is by the Biazzi process, carefully separated from the excess water, treated with
discussed under nitroglycerin. The triethylene glycol is chemically pure calcium chloride to remove the
purified by fractional distillation under vacuum in an 18 dissolved water, and filtered. The ether is removed by
inch Vigeaux fractionating column. The assembly as a bubbling with dry air. The yield is 1.34 grams of TEGN
whole is equivalent to 4.5 theoretical plates. The per gram of triethylene glycol, 84 percent of theoretical.
distillation is conducted using a 5 to 1 reflux ratio, at a The nitrogen content of different batches can vary from
pot temperature of approximately 180°C and a take-off 11.60 to 11.69 percent with 11.67 percent the calculated
temperature of approximately 120°C. The purified value. A modification that allows continuous rather than
triethylene glycol is carefully stirred into a mixed acid batch nitration is to dissolve the triethylene glycol and
that consists of 65 percent nitric acid, 30 percent sulfuric mixed acid separately in dichloromonofluoromethane,
acid, and 5 percent water that is maintained at 0 ± 5°C. CHFCI2 or freon 21, and then mix the two solutions. A
The mixture is stirred and held at 0 ± 5°C for 30 sufficient quantity of CHFCI2 must be used to maintain
additional minutes and then drowned by pouring over a the temperature at 11°C and to ensure a safe degree of
large quantity of ice. The TEGN is extracted three times dilution of the solution. The dispersant is evaporated
with ether and the combined extract is water washed and the TEGN is recovered. The yield of this process is
until the pH is about four, then shaken with an excess 74 percent.
solution of sodium bicarbonate, and further washed with
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(3) TEGN is unaffected in the pendulum friction liquid. In an acid bath, TMETN is hydrolyzed to the
test with the metal and fiber shoe. The Bureau of Mines extent of 0.018 percent in 10 days at 220°C and 0.115
impact test indicates a sensitivity of over 100 centimeters percent in 5 days at 60°C. TMETN can be used as a
and the Picatinny Arsenal impact test indicates 109 flash and erosion reducing additive in propellants and an
centimeters. The five second explosion temperature test ingredient of commercial explosives. TMETN alone
value is 225°C. does not gelatinize nitrocellulose unless the temperature
is raised to 100°C, which would be dangerous. But if
(4) The 1 00°C heat test, with losses of 1.8 mixed with only 8 percent of metriol triacetate,
percent and 1.6 percent for the first and second 48 hour gelatinization takes place at 80°C. When TMETN is
periods, respectively, indicates TEGN is much more mixed with nitroglycerin, the mechanical properties of
stable than nitroglycerin but considerably less stable than double-base cast propellants are improved.
all other standard explosives. No explosions occur in the Combinations with triethylene glycol dinitrate are used
100 hour observation period. The vacuum stability test as plasticizers for nitrocellulose.
results, 45 milliliters of gas in 40 hours at 100°C and 0.80
to 0.99 milliliters of gas in eight hours at 120°C, indicate
that TEGN is more stable than PETN, slightly less stable
than RDX, and much less stable than TNT.
(5) TEGN is insensitive to detonation. No
detonation occurs in samples placed in relatively light
steel tubing with a diameter of 3.175 centimeters at a
density of 1.33 grams per cubic centimeter. When heavily
confined, the detonation velocity is less than 2,000 meters
per second, or 30 percent of TNT. The 200 gram sand
test indicates a brisance of 30.6 percent of TNT, with 14.7
grams of sand crushed. TEGN's deflagration point is
195°C.
(6) TEGN is extremely toxic and should be Figure 8-14. Structural formula for TMETN.
considered a potent poison when absorbed through the
skin or ingested. Tests with rabbits indicate 21 millimoles (2) One method for the manufacture of
per kilogram of body weight causes death in two to three TMETN is to feed 50 kilograms of finely powdered
weeks when absorbed through the skin. A level of metriol into a nitrator provided with cooling coils and an
intraperitonal exposure of 995 milligrams per kilogram of agitator. The nitrator contains 175 kilograms of mixed
body weight causes death within 24 hours to 50 percent of acid that consists of 65 percent nitric acid and 35
the rats treated. TEGN, when selectively applied, can percent sulfuric acid. The nitration time is about 20
also inhibit the nerve functions in rats. minutes at 20°C after which the contents of the nitrator
are allowed to set for 15 minutes. The TMETN
h. 1,1,1 Trimethylolethane Trinitrate (TMETN). separates from the spent acid and is decanted and then
washed at 40°C with an aqueous solution of soda and
(1) This explosive is also known as metriol
then with water. The yield is almost 100 kilograms of
trinitrate and is sometimes referred to as MTN. The
TM ETN with a nitrogen content of 16.32 to 16.36
compound (figure 8-14) is a slightly turbid, viscous oil with
percent.
a nitrogen content of 16.41 percent and a molecular
weight of 255.15. TMETN has a melting point of -3°C and (3) The Bureau of Mines impact apparatus
an apparent boiling point of 182°C, but this is merely the indicates TMETN is as sensitive as nitroglycerin, with a
temperature at which decomposition becomes vigorous drop height of four centimeters for a two kilogram
enough to resemble boiling. Other properties of the liquid weight. The five second explosion temperature test
are a density of 1.47 grams per cubic centimeter at 22°C value is 235°C and TMETN detonates with both the
and a refractive index of 1.4752 at 25°C. TMETN is metal and fiber shoe in the pendulum friction test.
practically insoluble in water. Less than 0.015 grams
dissolved per 100 grams of water at up to 60°C. TMETN (4) TMETN is 91 percent as brisant as TNT
is soluble in alcohol and many other organic solvents. At with 43.7 grams of sand crushed in the sand test. The
60°C TMETN's volatility is 24 milligrams per square Trauzl test and ballistic mortar test indicate TMETN to
centimeter. The heat of formation is 422 calories per be 140 percent and 136 percent, respectively, as
gram at constant volume and 446 calories per gram at powerful as TNT.
constant pressure. The heat of combustion is 2,642
calories per gram at constant volume with the water being
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(5) The stability of TMETN is not very acetone, nitric acid, or nitrometrane with very slow
satisfactory as indicated by the vacuum stability and cooling. The alpha form is precipitated from the same
heat tests. In the 100°C heat test, a 2.5 percent weight solution with more rapid cooling and the gamma form is
loss is reported in the first 48 hours and 1.8 percent in precipitated with even more rapid cooling. The delta form
the second 48 hours. No explosions occur in the first is crystallized from solution such as acetic acid or
100 hours. In the 100°C vacuum stability test, 1.9 cubic betachloroethyl phosphate, in which HMX is only slightly
centimeters of gas are evolved in the first 40 hours. At soluble. Very rapid chilling of the solution is required.
25°C TMETN is hygroscopic to the extent of 0.07 This is usually accomplished by pouring small quantities of
percent with 90 percent relative humidity and 0.14 the solution over ice. Military grade HMX consists only of
percent at 100 percent relative humidity. the beta polymorph. HMX is insoluble in water, but is
soluble in the solvents listed in table 8-11 to the degree
8-3. Nitramines. Compounds in this class are prepared shown.
by N-type nitration in which a nitro group is attached to a
nitrogen atom of the compound being nitrated.
a. Cyclotetramethylenetetranitramine (HMX).
(1) HMX is also known as: octahydro-1,3,5,7-
tetranitro-1 ,3,5,7-tetrazocine; 1,3,5,7-tetranitro-1 ,3,5,7-
tetrazacyclooctane; cyclotetramethylene tetranitramine;
or octogen. HMX (figure 8-15) is a white, crystalline
solid with a nitrogen content of 37.84 percent, a
theoretical maximum density of 1.905 grams per cubic
centimeter, a nominal density of 1.89 grams per cubic
centimeter, a melting point of 285°C, and a molecular
weight of 296.17. There are four polymorphs of HMX:
an alpha, beta, gamma, and delta form. Each
polymorph has a range of stability and there are Figure 8-15. Structural formula for HMX.
differences among them in physical properties such as
density, solubility, and refractive index. The most Table 8-11. Solubility of HMX
common polymorph is the beta form. The term HMX
without an alpha, gamma or delta qualifier refers to the
Solvent Grams of Temperature
beta form throughout the rest of this text. The
HMX dissolved °C
crystalline structure of beta HMX is monoclinic with a
density of 1.903 grams per cubic centimeter. The unit per 100 grams
cell dimensions are a=6.54 Angstroms, b=11.05 of solution
Angstroms, and c=8.70 Angstroms. Beta HMX is stable
to about 102°C to 104.5°C, when the crystalline Dimethylformamide 4.4 25
structure is converted to the alpha form. The crystals of Nitrobenzene 0.129 25
the alpha form are orthorhombic with a density of 1.82 1,2-Dichlorethane 0.125 70
grams per cubic centimeter. The unit cell dimensions Acetic acid 0.0375 25
are a=15.14 Angstroms, b =23.89 Angstroms, c = 5.91 Acetone 0.96 25
Angstroms. At approximately 160°C to 164°C the meta Acetonitrile 1.98 25
stable gamma form exists. The crystals of the gamma Cyclohexanone 2.11 25
form are monoclinic with a density of 1.76 grams per Ethylacetate 0.02 25
cubic centimeter. The unit cell dimensions are a=10.95 Ethylbromide 0.02 25
Angstroms, b =7.93 Angstroms, and c = 14.61 Methylethylketone 0.46 25
Angstroms. Above the 160°C to 164°C range to the Nitroethane 0.172 25
melting point, the delta form exists. The crystals of the Nitromethane 0.778 25
delta form are hexagonal with a density of 1.80 grams Triethylphosphate 1.75 25
per cubic centimeter. The unit cell dimensions are
a=7.71 Angstroms and b=32.55 Angstroms. The Table 8-12 lists the solubility of HMX by volume for
polymorphs may also be prepared by precipitation from various solvents.
solution under various conditions. The beta form is
precipitated from a solution of HMX in acetic acid,
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8 100
12 99 min 85 min 99 min
35 25 ± 15
50 90 ± 6 100 40 ± 15 90 min
100 50 ± 10 20 ± 10 15 max 65 ± 15
120 90 min
200 20 ± 6 10 + 10 30 ± 15
325 8 ±5 75 min 98 min 15 ± 10
(3) To manufacture HMX, a solution of 785 parts hot water are added and the solution is refluxed for
parts glacial acetic acid, 13 parts acetic anhydride, and 30 minutes. After cooling to 20°C by adding ice, the
17 parts paraformaldehyde is maintained at a water insoluble precipitate is collected and washed with
temperature of 44°C ± 1°C. All part measurements in three portions of cold water. The yield of 200 parts HMX
this discussion are by weight. The solution is held at is 95 percent of the theoretical and the purity is higher
that temperature throughout the subsequent steps of the than 90 percent. The product is alpha HMX which is
process. Two more solutions are prepared. One converted to beta HMX by crystallization from boiling
consists of 101 parts hexamine and 165 parts acetic acetone, acetonitrile, or cyclohexanone, using
acid. The other is prepared by dissolving 840 parts equivalent parts of solid and solvent. The recrystallized
ammonium nitrate in 900 parts of 99 percent or stronger HMX has a melting point of 278° to 279°C. The
nitric acid. Over a 15 minute period with constant recrystallization process also removes any RDX that
stirring, the hexamine-acetic acid solution, 180 parts of was formed during manufacturing.
the nitric acidammonium nitrate solution, and 320 parts
(4) HMX has similar sensitivity to impact and
acetic anhydride are added simultaneously,
friction as RDX. The Bureau of Mines impact apparatus
continuously, and equivalently. The mixture is aged for
with two kilogram weight measures 32 centimeters for a
15 minutes. In the second stage of the reaction, 320
20 milligram sample. In the pendulum friction test, HMX
parts of acetic anhydride and 271 parts of the nitric acid-
explodes with the steel shoe but is unaffected by the
ammonium nitrate solution are added proportionately,
fiber shoe. Table 8-14 shows the gap test results for
then 160 parts of acetic anhydride are added in bulk.
HMX.
The mixture is allowed to age for 60 minutes. Then 350
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The minimum charge of lead azide required for DTA curve is shown in figure 8-16 and the TGA curve is
detonation to obtain maximum brisance is 0.30 grams. shown in figure 8-17.
Explosion temperature test values are 306°C in 10
seconds, 327°C in five seconds, and 380°C in 0.1 b. Cyclotrimethylenetrinitramine (RDX).
second. When HMX is under a compression of 93,082 (1) This explosive is also known as:
kilopascals (13,500 pounds per square inch), the hexahydro-1,3,5-trinitro-1,3,5-triazine; 1,3,5-trinitro1,3,5-
explosive can be reliably detonated by a Q-switched triazacyclohexane; cyclotrimethylene trinitramine;
laser operating at 6,943 Angstroms. As measured in a hexogen; cyclonite; or 1,3,5-trinitrotrimethylene-triamine.
differential thermalgraph analysis study, the auto ignition The compound (figure 8-18) is a white solid with a density
temperature of HMX is 234°C. In the spark sensitivity of 1.806 grams per cubic centimeter, a nitrogen content of
test with a brass electrode and a sample size of 66.9 37.84 percent, and a molecular weight of 222.13. RDX
milligrams, the energy required for a 50 percent has orthorhombic crystals with a wide variety of habits;
probability of explosion for lead foil thicknesses of 3 and from needles when precipitated from HNO3, to plates
10 mils is 0.2 joules and 1.03 joules respectively. For a when precipitated from acetic acid, to a massive form
steel electrode, the energy required is 0.12 joules and when precipitated from nitroethane or acetone. The unit
0.87 joules for lead foil thicknesses of 1 and 10 mils, cell dimensions are a=13.18 Angstroms, b = 1 1.57
respectively. Angstroms, and c = 10.71 Angstroms, and there are eight
(5) The sand test indicates HMX is 125 molecules per cell unit. On the Moh's scale RDX has a
percent as brisant as TNT or about 96 percent as brisant scratch hardness of 2.5. Other properties of pure RDX
as RDX. The ballistic pendulum test indicates 170 include a specific heat as shown in table 8-15 and a heat
percent of TNT, the ballistic mortar test indicates 150 of combustion at constant pressure of 2,307.2 calories per
percent, and the Trauzl test indicates a power of 159 to gram. The heat of formation value is + 14.71 kilocalories
165 percent of TNT. The detonation velocity of HMX at per mole. RDX has an extremely low volatility.
a density of 1.89 grams per cubic centimeter is 9,110
meters per second. The following critical diameters Table 8-15. Specific Heat of RDX
were measured for HMX:
Temperature Calories per
Density °C gram per
HMX/Wax, grams per cubic Critical degree
percent centimeter diameters 20 0.298
40 0.331
90/10 1.10 6.0 < dc < 7.0 60 0.360
78/22 1.28 7.0 < dc < 8.0 88 0.384
70/30 1.42 8.0 < dc < 9.0 100 0.406
120 0.427
The diameters are given in millimeters. A gelled 140 0.446
aqueous slurry of 30 percent HMX will detonate high
order. At 25 percent HMX concentration detonation Packing density as a function of pressure is shown in table
would be partially propagated and at 20 percent 8-16.
concentration the detonation would not propagate.
Settled slurries propagate high order detonation at and Table 8-16. RDX Packing Density
above 10 percent HMX concentration. At the five
percent level, the settled slurry will detonate about one Pressure Density
third of the time. Pressure pounds per grams per
kilopascals square inch cubic centimeter
(6) The 150°C vacuum stability test indicates
34,475 5,000 1.52
HMX is comparable to TNT in stability, with test values
68,950 10,000 1.60
of 0.6 and 2.5 milliliters of gas evolved. The 100°C heat
137,900 20,000 1.68
test loss in the first 48 hours is 0.05 percent and in the
172,375 25,000 1.70
second 48 hours 0.03 percent. No explosions occur in
206,850 30,000 1.72
100 hours. At 30°C and 95 percent relative humidity,
HMX is nonhygroscopic. In the LLNL reactivity test, less
than 0.01 cubic centimeters of gas are evolved. The
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RDX does not blend with or gelatinize nitrocellulose. detonation is 1.62 kilocalories per gram with liquid water
With nitroglycerin, RDX forms an explosive plastic and 1.48 kilocalories per gram with gaseous water.
mass. Table 8-17 lists the solubility characteristics with RDX detonates according to the empirically determined
TNT. equation:
Table 8-17. RDX-TNT Solubility
(CH2.NNO2)3 - 2CO +CO2 +2H2O+H2+3N2
Temperature Grams of RDX dissolved
°C per 100 grams of TNT The temperature developed on explosion is 3380°C.
81 4.5 There are two grades specified for RDX: types A and
85 4.7 type B. Type A contains no HMX and type B has a
90 5.0 constant impurity of from 8 to 12 percent HMX. Types A
95 5.8 and B are produced by different manufacturing
100 6.5 processes. Type A RDX melts between 202°C and
105 7.3 203°C; type B RDX melts between 192°C and 193°C.
110 8.2 The vapor pressure of RDX is given by the equation:
The eutectic mixture is 4.16 percent RDX at 79°C. log p= 11.87 - 5850/T(K)
Table 8-18 lists the solubility of RDX in various solvents. for 55.7°C < T < 97.7°C
There is considerable divergence in the solubility data
for RDX taken from different sources in the literature, Pure RDX is used in press loaded projectiles but not in
probably due to the different methods and conditions cast loaded projectiles because of extensive
used in making the determinations, the difference in decomposition at the melting point. Cast loading is
purity, and the difference in physical state of the RDX accomplished by blending RDX with a relatively low
tested. melting point substance. Compositions in which the
RDX particles are coated with wax are called
Therefore, the values given in table 8-18 are only Composition A, in mixtures with TNT, Composition B,
approximate. The coefficient of cubical expansion and blends with a nonexplosive plasticizer, Composition
between 20°C and 100°C is 0.00025 cubic centimeters C. Straight RDX is used as a base charge in detonators
per gram per degree centigrade. RDX has a heat and in some blasting caps, and as an oxidizer in
combustion of 501.8 to 507.3 kilocalories per mole at specialized gun propellant.
constant volume with liquid water. The heat of
formation is 14.7 kilocalories per mole. The heat of
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cent nitric acid and may be recovered from solution by presence of the acetic anhydride, (CH3CO)2O, to form
dilution with water. Hot or cold hydrochloric acid does hexamethylenetetramine, which is nitrated by the nitric
not attack RDX. Complete decomposition can be acid to form the second mole of RDX. The HMX
obtained by heating RDX with equal parts of Ca(OH)2 for impurity is not shown. The yield of the type B reaction is
four hours at 60°C. RDX decomposes slowly when greater than for the reaction using nitric acid alone.
heated at 60°C with a one tenth normal solution of Other methods for producing RDX include a process of
sodium hydroxide for five hours, but rapidly when nitrating hexamethylenetetramine by nitric acid in the
heated with a normal solution of sodium hydroxide. presence of phosphorous pentoxide with a yield of 90
When RDX is placed in an alkaline solution, percent of theoretical. Nitration by some processes in
decomposition occurs. The products of that the presence of ammonium salts such as (NH4)2SO4 can
decomposition which have been isolated are: nitrogen increase yields. Yields of 65 percent, 80 percent and 91
gas, ammonia, nitrates, nitrites, formaldehyde, percent were obtained using no ammonium salt,
heramine, and organic acids such as formic. When ammonium nitrate, and ammonium sulfate, respectively.
mixed with oxides of heavy metals, such as iron or Another possible method of manufacture uses nitrogen
copper, RDX forms unstable compounds which may pentoxide dissolved in inert, nonaqueous solvents such
undergo decomposition and cause ignition of mixtures at as hydrocarbons or chlorinated hydrocarbons to nitrate
temperatures as low as 100°C. hexamethylenetetramine. The equation for the reaction
(3) Type A RDX is manufactured by the would be:
nitration of hexamethylenetetramine which is obtained
by the reaction of formaldehyde and ammonia. The C6H12N4 +3N2O5
process is accomplished by slowly adding one part by (CH2NNO2)3 +3HCHO +2N2O3
weight of hexamethylenetetramine to 11 parts of 100
percent nitric acid, the temperature of which is The yield for this method is claimed to be 89 percent. A
maintained at 30°C or less while being stirred proposed method for the production of type A RDX
vigorously. The reaction proceeds according to the consists of oxidizing the compound 1,3,5-trinitroso1,3,5-
equation: triazacyclohexane, which is obtained from
hexamethylenetetramine, HCL, and NaNO2. Oxidization
C6H12N4 +3HNO3 3HCHO + NH3 +(CH2NNO2)3 with hydrogen peroxide and nitric acid yields as an
intermediate 1-nitroso-3,5 dinitroso-1,3,5
The formaldehyde, HCHO, liberated by the reaction is triazacyclohexane which is converted on further
oxidized by the nitric acid if the mixture is allowed to treatment with hydrogen peroxide and nitric acid into
stand or is warmed. After being cooled to 0°C, the RDX having a melting point of 205°C.
mixture is stirred for 20 minutes more and then drowned
in ice water. As a result of the rupture and degradation
(4) Type A and type B RDX are equally
of the hexamethylenetetramine molecule, numerous
sensitive to impact, friction, heat, and initiation. This is
aliphatic and cyclic nitrocompounds are formed that are
due to the fact that HMX, the chief impurity in type B
present in crude RDX. The crude RDX is caught on a
RDX, has sensitivity characteristics that are very similar
filter and washed with water to remove most of the acid.
to those of RDX. Impact tests indicate RDX is 300
Removal of all but a trace of acid is important and
percent as sensitive as TNT. Temperature has a
purification is accomplished by grinding the wet material
marked effect on the sensitivity of RDX. Impact tests of
then treating with boiling water or by recrystallizing from
a sample of type A RDX at 20°, 88°, and 105°C gave
cyclohexanone or acetone. Production of type B RDX is
values of 9, 8, and 5 inches, respectively. Granulation
based on the following reaction:
also affects sensitivity; the height of fall increases with
decreasing particle size. In pendulum friction tests,
C6H12N4 +4HNO3 +2NH4NO3 +6(CH3CO)2O
RDX explodes with the steel shoe but is unaffected by
2(CH2NNO2)3 + 12CH3COOH
the fiber shoe. When rubbed in an unglazed porcelain
mortar, partial deflagration occurs. RDX displays great
The hexamethylenetetramine is nitrated to RDX by the
sensitivity in the rifle bullet impact test, but the test
nitric acid and, as indicated for the production of type A
samples partially deflagrate rather than detonate. RDX
RDX, three moles of formaldehyde are produced. The
can be initiated by lead azide or mercury fulminate.
formaldehyde reacts with the ammonium nitrate in the
Gap test results for RDX are shown in table 8-19.
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(7) In the United States and England, RDX is Table 8-20. Types of RDX
stored wetted with water. In Germany and Japan it is
stored dry. RDX does not cause corrosion of aluminum Properties Type A Type B
or stainless steel, even in the presence of moisture. Dry Melting point, °C (min) 200.0 190.0
RDX causes no corrosion of and RDX with 0.5 percent Acetone insoluble (max) 0.05 0.05
moisture causes only slight corrosion of nickel or zinc. Inorganic insoluble (max) 0.03 0.03
Dry or damp RDX causes very slight corrosion of Insoluble particles 5 5
copper, brass, mild steel, or cadmium. retained on US standard
(8) Table 8-20 lists the requirements for sieve No. 60, particles (max)
military grade RDX for the United States government. Acidity, percent (max) 0.05 0.02
Through US Class
standard (% of material passing sieve)
sieve No. A B C D E F G H
8 - - - 100 - - - -
12 - - 99* - - - - -
20 98 - - - - - - -
35 - 99 - 20 - - - 100
50 90 95 40 - - - 98 98*
60 - - - - - 99 - -
80 - - - - - 97 - -
100 60 65 20 - - - 90 90*
120 - - - - - 83 - -
170 - - - - - 65 - -
200 25 33 10 - - - 46 70
230 - - - - - 36 - -
325 - - - - 97* 22 - 50
*Minimum Percent
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(9) The suggested uses of RDX based on This is followed by the concentration and crystallization
class and granulation are as follows: of the salt formed.
(a) Class A, for use in Composition A3, (3) EDDN is more sensitive to shock than
Composition B, Composition C4, and cyclotol TNT, having impact test values of nine inches and 75
(b) Class B, for use in Composition A3 centimeters, respectively, with the Picatinny and Bureau
and Composition C4 of Mines apparatuses. In rifle bullet impact tests with a
(c) Class C, for use in the preparation charge of specific gravity 1.0 no detonations occurred
of RDX booster and detonator pellets on the impact of bullets with velocities below 960 meters
per second and incomplete detonations occurred with
(d) Class D, for use in cyclotols bullet velocities around 1,000 meters per second.
(e) Class E, for use in Composition C4 EDDN is less sensitive to initiation than TNT, requiring a
and plastic bonded explosives (PBX's) minimum detonating charge of 0.10 gram of tetryl
(f) Class F, for use in Composition B3 according to the sand test. Two grams of mercury
(g) Class G, for use in PBX's fulminate are required for the initiation of a 50 gram
(h) Class H, for use in Composition C4 sample pressed to a specific gravity of 1.23 in a paper
cylinder 30 millimeters in diameter. In a gap test a
minimum separation of 3.75 centimeters was found with
c. Ethylenediamine Dinitrate (EDDN). paper cartridges each containing a 50 gram sample
(1) This explosive is also designated EDD or pressed to a density of 0.75. The explosion temperature
EDAD. The compound (figure 8-21) is composed of test value of EDD is 445°C, as compared with 475°C for
white crystals with a specific gravity of 1.595 at 25/40, a TNT. A small sample placed in a test tube ignites in six
nitrogen content of 30.10 percent, an oxygen balance to seconds when plunged into a bath preheated to 370°C,
C02 of-25.8 percent, a melting point of 185° to 187°C, and in one second when the temperature of the bath is
and a molecular weight of 186.13. The compound is increased to 430°C. EDDN is ignited by open flame
soluble in water, but insoluble in alcohol or ether. EDDN after one minute and continues to burn at the rate of 1.5
has a heat of combustion of 374.7 kilocalories per mole centimeters per minute.
at constant pressure, a heat of formation of 156.1 (4) The sand test indicates EDDN is 96
kilocalories per mole, and a heat of explosion of 127.9 percent as brisant as TNT, and plate dent test values
to 159.3 kilocalories per mole. Eutectics are formed are practically the same for the two explosives. The
with ammonium nitrate, but EDDN is immiscible with detonation velocity for a sample of EDDN with a specific
molten TNT. An aqueous solution of EDDN is distinctly gravity of 1.00 is 4,650 meters per second, 6,270 meters
acidic. EDDN has been used to a limited extent as a per second at a specific gravity of 1.33, and 6,915
bursting charge pressed in shells and as a cast charge meters per second at a specific gravity of 1.50. EDDN
in eutectic mixtures with ammonium nitrate. Mixtures is indicated to be 114 percent and between 120 and 125
with wax were used in boosters during World War II by percent as powerful as TNT by the ballistic pendulum
the Germans. and Trauzl lead block tests, respectively.
(5) When heated in vacuum EDDN vaporizes
and condenses without noticeable decomposition.
When heated at 10 millimeters of pressure in an
atmosphere of nitrogen or air, autocatalytic
decomposition occurs between 230°C and 360°C.
EDDN is hygroscopic to the extent of 1.24 percent at 90
percent relative humidity and 25°C. In the 120°C
vacuum stability test, five milliliters of gas are evolved.
Because of poor solubility, hygroscopicity, and acidity
Figure 8-21. Structural formula for EDDN. characteristics, EDDN is not very satisfactory for use as
a military explosive and is an inferior substitute for TNT.
(2) EDDN is produced by neutralization of
ethylenediamine dihydrate with concentrated nitric acid.
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washed with ice water until the washings are almost Grit: None.
neutral. Additional dinitroethyleneurea is recovered by 120°C vacuum stability test: Maximum, 5.0 milliters of
drowning the spent acid in ice water. A total yield of 97 gas in 40 hours.
percent of the theoretical is obtainable. One part Granulation:
dinitroethyleneurea, by weight, is suspended in seven Percent
parts water and boiled until the evolution of carbon Through US No. 10 sieve, minimum 100
dioxide ceases. The reaction is shown in figure 8-24. Through US No. 100 sieve, maximum 20
Haleite separates as shining crystals when the solution
is cooled to room temperature. This is caught on a (5) Impact tests show Haleite to be slightly
filter, washed with cold water, and dried. The total yield more than twice as sensitive as TNT, with a 48
of Haleite from ethyleneurea is approximately 92 centimeter drop height versus 100 centimeters for TNT.
percent of the theoretical. Another method of producing In the rifle bullet impact test for 100 trials, there were 60
Haleite is by treating dinitroethylenediurethane with an partial detonations, 20 burnings, and 20 unaffected.
alcoholic solution of ammonia followed by acidifying Haleite is unaffected by either the fiber or steel shoe in
with hydrochloric acid. This reaction is shown in figure the pendulum friction test. A minimum initiating charge
8-25. of 0.21 grams of mercury fulminate or 0.13 grams of
(4) One grade of Haleite is specified for lead azide are required for initiation. In the gap test, a
military purposes. This complies with the following minimum separation of 14 centimeters was found for
requirements: two paper cartridges, each containing 50 grams of
Haleite at a density of 0.80. This value is 64 percent of
Color: White to buff. that for tetryl at a density of 0.94. The explosion
Moisture: Maximum, 0.10 percent. temperature test value is 190°C. The 0.1 second
Melting point: Minimum, 174.0°C. explosion temperature test value is 265°C. Haleite
Purity: Minimum, 99.0 percent. flammability index is 138 seconds.
Water insoluble matter: Maximum, 0.10 percent.
8-40
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(6) As measured by the sand test, Haleite has temperatures are 170°C in 20 seconds, 1730C in 15
a brisance of 109 to 1 19 percent of that for TNT. The seconds, 178°C in 10 seconds, 1890C in 5 seconds. At
plate dent test indicates a brisance value of 113 to 122 higher temperatures, Haleite darkens to a red brown
percent of TNT. The plate cutting test indicates a with the evolution of NO2. Haleite is hygroscopic to the
brisance equal to that of PETN. A fragmentation test extent of 0.01 percent at 90 percent relative humidity.
using a three inch, high explosive, M42A shell with a In the vacuum stability test at 1 00°C with a five gram
charge of 95 percent Haleite and 5 percent wax at a sample, 0.5 cubic centimeters of gas are evolved in 48
density of 1.56 was found to produce 117 percent as hours. At 120°C, 1.5 to 2.4 cubic centimeters of gas are
many fragments as TNT. Other fragmentation test evolved, and at 135°C more than 11 cubic centimeters
values varied from 136 to 147 percent of TNT. The are evolved. Tests have shown Haleite to be volatilized
detonation velocity for a sample at a density of 1.55 at the rate of 0.05 percent per hour when heated at
grams per cubic centimeter is reported as 7,883 meters 100°C in an open dish. Storage tests have shown dry
per second. For a sample of density 1.50, a detonation Haleite to be of unimpaired stability after storage at
velocity of 7,580 meters per second was reported and a 65°C for five months or 50°C for 30 months. Therefore,
velocity of 5,650 meters per second for a sample of Haleite is considered to be of satisfactory stability at the
density 1.0. The ballistic mortar tests indicate Haleite is normal exposure temperatures for storage and handling.
136 to 140 percent as powerful as TNT. The Trauzl test Dry Haleite does not cause corrosion of aluminum,
indicates a power of 122 to 143 percent of TNT. brass, copper, mild steel, stainless steel, cadmium,
(7) In the 100°C heat test, a 0.2 percent nickel, or zinc. Magnesium and magnesium alloys are
weight loss was reported in the first 48 hours, and 0.3 slightly affected by dry Haleite. Stainless steel is not
percent was lost in the second 48 hours. No explosions corroded by wet Haleite, but copper, brass, mild steel,
occurred. The 135°C heat test results are satisfactory. cadmium, nickel, and zinc are heavily corroded in the
The 75°C international heat test result is that a 0.01 presence of as little as 0.5 percent moisture.
percent loss occurs in 48 hours. Decomposition
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8-44
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Density Sensitivity
grams per cubic Percent in
centimeter voids millimeters
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8-46
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FRACTION OF
ORIGINAL SAMPLE
AS PERCENT OF
WEIGHT
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8-49
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This can be nitrated to tetryl with relative ease. A methylaniline which is nitrated to 2,3,4,6-
considerable amount of tetryl was prepared by this tetranitrophenylnitramine (also called m-nitroethyl)
method in the United States during World War II. A which in turn is readily hydrolyzed to 2,4,6-trinitro-3-
variation on this method is used at the present time in hydroxyphenylmethylnitramine. The nitration and
Germany. The reaction between the 2,4or 2,6- hydrolysis are shown in figure 8-34. The compound
dinitrochlorobenzene and methylamine is carried out in formed is readily soluble in water and easily removed. If
the presence of sodium hydroxide. The the water content of the mixed acid is too high, benzene
dinitrophenylmethylamine is then dissolved in sulfuric insoluble impurities are formed which are benzidine
acid, which is made up from spent acid and contains derivatives. The derivatives are shown in figure 8-35.
some nitric acid, oxides of nitrogen and 16 percent After the reaction is completed in the reactor, the liquid
water. This solution is then added to mixed acid which contains partially crystallized tetryl is allowed to
containing 78 percent nitric acid, 6 percent sulfuric acid, run into a crystallizer which is maintained at 20°C. The
and 16 percent water. The second method uses crystallized product is discharged to a vacuum filter
dimethylaniline as the starting material. The use of where the tetryl is collected and the spent acid is passed
dimethylaniline has the disadvantage of requiring nitric on to be renitrated. Tetryl must then be purified
acid for the removal of one methyl group by oxidation carefully to remove any tetranitrocompound and
according to the equation: occluded acidity, which have adverse effects on the
stability of tetryl. Most of the acidity is removed by
C6HN(CH3)2+10HNO3 washing with cold water. Treatment with boiling water
(NO2)3C6H2N (NO2)CH3+6NO2+CO2+8H2O decomposes any tetranitrocompound present and
removes any products. If benzene is used as a solvent,
This disadvantage is not shared by the first process the crude tetryl is dissolved, the solution is washed with
described above. Direct nitration of dimethylaniline water to remove residual acidity, and filtered to remove
proceeds so violently that the reaction can be carried insoluble matter. Upon cooling the solution, the tetryl is
out only under specialized conditions. The precipitated, separated, and dried. If acetone is used as
dimethylaniline is converted to dimethylaniline sulfate by the solvent, the solution is neutralized and filtered and
dissolving one part of the chemical in 14.4 parts of 96 to the tetryl is precipitated by mixing the solution with
99 percent sulfuric acid at 20°C to 30°C. Many years water. The acetone purification process is carried out
experience in tetryl manufacture has shown that the on a continuous basis, while that with benzene is
ratio of sulfuric acid to dimethylaniline should not be operated as a batch process. In the lab, high purity
lower than 3: 1, since a smaller amount of sulfuric acid tetryl can be obtained by nitrating dimethylaniline with
may be detrimental to the nitration process. However, nitric acid, not mixed acid, in the presence of inert
the ratio of sulfuric acid to dimethylaniline must not be solvents such as dichloromethane, chloroform, or
too high, otherwise tetryl yield is decreased. Sulfonation carbon tetrachloride.
of the benzene ring will occur if the temperature is not
maintained between 20°C and 40°C. A quantity of 15.4
parts of the solution of dimethylaniline sulfate is added
in a nitrator to 9.2 parts of mixed acid which contains
66.7 percent nitric acid. 15.8 percent sulfuric acid, and
17.5 percent water. The contents of the nitrator are
heated to 68°C then heating is discontinued. This step
involves a reaction that oxidizes a methyl group and is
highly exothermic. The temperature of the reaction
must be maintained at 60°C to 72°C by external means,
if necessary. For safe and efficient nitration, very
vigorous stirring is essential to ensure that the reacting
liquids are mixed almost instantaneously. The mixture
is kept in this nitrator for a very short period, so the
reaction may be incomplete. The contents of the
nitrator are discharged via an overfall to a larger reactor
that is also equipped with a stirrer. In this reactor, which Figure 8-34. Nitration and hydroylsis of
is maintained at 70°C, the reaction is completed. methylaniline.
Commercial dimethylaniline contains some
Change 4 8-50
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Time to explosion
Temperature in °C in seconds
302 0.4
280 1.1
260 2.0
236 6.2
Figure 8-35. Benzidine derivatives during tetryl
manufacture. Slightly different results were obtained with confined
samples of tetryl. The explosion times for 25 milligrams
(8) One grade of tetryl is specified for military of tetryl in copper shells of 0.635 millimeter diameter
purposes. This complies with the following submerged in a hot woods metal bath are shown in table
requirements: 8-29.
No. 12, minimum 100 When a 0.5 gram sample of tetryl is heated at a rate of
No. 16, minimum 95 20°C per minute, ignition occurs between 190°C and
No. 30, minimum - 194°C. If the temperature of a sample is held at 180°C
No. 40, maximum - ignition occurs in 40 seconds. The minimum primary
No. 60, maximum 30 charges necessary for reliable detonation of tetryl with
No. 100, maximum 5 mercury fulminate is 0.20 to 0.29 grams and with lead
azide is 0.025 to 0.10 grams. Tetryl containing 60
A requirement also exists for an infrared spectrum with percent water cannot be detonated by a commercial
only certain specified peaks and no extraneous peaks. detonator. Shock sensitivity as measured by the gap
The requirement with respect to insoluble matter is tests are summarized in table 8-30.
included because of the marked desensitizing effect of
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Density Sensitivity
grams per cubic Percent in
centimeter voids millimeters
The shock sensitivity of a lightly confined sample there is a transition to normal detonation velocity. Table
decreases as temperature decreases, but confined 8-31 summarizes the dependence of transition diameter,
samples show only a slight tendency toward reduced minimum diameter for low velocity detonation, minimum
shock sensitivity. Particle size has an effect on shock diameter for normal detonation, and the approximate
sensitivity. As the particle size decreases, the shock speed for low velocity detonation on particle size for 0.9
sensitivity increases. Deflagration can also be initiated grams per cubic centimeter tetryl. Low velocity
by shock. For coarse tetryl with a density of 1.65 grams detonation is not affected by the initiating power of the
per cubic centimeter in a 21 millimeter diameter detonator, provided the detonator is weak enough not to
plexiglas tube, the deflagration threshold pressure is initiate normal detonation. For charge diameters
12.1 to 14 kilobar, as compared to 18 kilobar for between the minimum diameter for low velocity
detonation. Tetryl's sensitivity to shock initiation by an detonation and minimum diameter for normal
explosive bridge wire is dependent on particle size and detonation, even powerful initiators will produce only
crystal habit. The sensitivity decreases as packing steady, low velocity detonation, provided the charge is
density increases. In studies of tetryl's sensitivity to of sufficient strength. Low velocity detonation is
initiation by laser beams, no initiation occurred upon maximum at the transition diameter. This velocity is
direct exposure to the beam. But if the tetryl sample virtually independent of particle size and even type of
was coated with a thin metal film, initiation was explosive. TNT, PETN, RDX, and tetryl all have the
observed at a density of 1.08 grams per cubic same maximum low velocity detonation. Experiments
centimeter. With higher density tetryl no initiation with oil coated or crushed particles suggest that the
occurred. main reaction in low velocity detonation is surface
(10) At a density of about 1.60 grams per cubic combustion. The power of tetryl by the ballistic
centimeter, the sand test indicates a brisance of 113 to pendulum test is 145 percent that of TNT, by the ballistic
123 percent of TNT, the copper cylinder compression mortar test 126 to 132 percent of TNT, and by the
test indicates 117 to 125 percent, the lead block Trauzl test 125 to 145 percent of TNT. The heat of
compression test indicates 112 percent, the plate dent detonation as a function of density is given by the
test indicates 115 percent, and the fragmentation effect equation:
test indicates 121 percent. The ideal detonation velocity
as a function of density is given by the equation: Q=680+282p
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detonation transfer in tetryl. After ignition, the length of the ignition region. Both of these effects are attributed
the column before detonation occurs is determined by to the low temperature of decomposition of tetryl. The
the markings on the tube fragments recovered. This addition of 3 percent wax to a sample changes the initial
result is checked with the ionization probe and strain low temperature decomposition to behavior typical of
gage records for consistency. The results for coarse other explosives, with accelerated burning starting
tetryl with a particle size of 470 microns and fine tetryl sooner. The burning rate of tetryl is not greatly affected
with a particle size of 20 microns are plotted in figure 8- by the initial temperature of the sample; the rate
37. According to the graph, both fine and coarse tetryl increasing by less than a factor of two for a temperature
show the same effects of compaction on predetonation difference of 100°C. The burning rate decreases with
column length, which is nearly constant at low density, additions of small amounts of water, and increases with
with increasing values at 75 percent density. At a given increasing ambient pressure.
density, the fine tetryl has a greater predetonation (11) Figure 8-38 shows the amount of gas
column length than the coarse, as well as longer relative evolved by tetryl as a function of temperature and time.
time to detonation. In the experiments with tetryl, the The presence of picric acid tends to accelerate the
ionization probes frequently failed to respond because evolution of gas, while trinitroanisole or trinitroaniline
the decomposition products formed shortly after ignition tend to slow the evolution of gas. Table 8-32 shows the
have such a high electrical resistance. Another unique composition of the gaseous products of tetryl
characteristic of tetryl is that the onset of accelerated decomposition.
burning is located nearer to the onset of detonation than
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Figure 8-37. Effect of compaction on predetonation Figure 8-38. Kinetic gas-evolution curves in the
column length in tetryl. decomposition of tetryl.
Moles of
gas per Composition of dry gas Composition of gas, moles per
Time mole of volume % mole of tetryl
mins tetryl CO2 CO NO N2 CO2 CO NO2 NO N2
221 0.650 23.6 10.6 4.3 61.5 0.134 0.060 0.016 0.024 0.348
1530 2.208 25.9 12.0 5.3 56.8 0.493 0.229 0.000 0.101 1.080
40 0.450 25.1 10.9 5.0 59.0 0.087 0.035 0.021 0.017 0.204
50 0.667 24.5 11.3 6.3 57.9 0.124 0.057 0.018 0.032 0.282
80 1.338 23.9 11.1 8.2 56.8 0.243 0.113 0.031 0.084 0.578
110 1.808 24.3 10.8 8.1 56.8 0.358 0.158 - 0.118 0.838
140 2.010 25.2 11.5 8.5 54.8 0.420 0.193 0.016 0.143 0.925
200 2.149 25.1 11.8 8.6 54.5 0.448 0.210 0.004 0.153 0.972
422 2.304 25.7 12.1 8.2 54.0 0.491 0.231 0.001 0.156 1.030
1440 2.674 27.8 13.4 8.4 50.4 0.624 0.302 0 0.190 0.130
40 1.950 24.5 11.6 8.8 55.1 0.397 0.188 0.023 0.142 0.892
382 2.572 27.7 12.7 9.6 50.0 0.584 0.268 0.003 0.202 1.060
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The heat of reaction for the slow decomposition of tetryl monoclinic crystals and a meta stable form as red,
is 328 to 341 calories per gram. Vacuum stability tests orthorhombic crystals. The unit cell dimensions are a
show tetryl to be less stable than TNT. The DTA curve =13.45 Angstroms, b =19.74 Angstroms, and c =7.12
for tetryl is shown in figure 8-39 and the TGA curve is Angstroms. The compound manufactured for military
shown in figure 8-40. Ammunition that has been loaded use is yellow to orange in color. Table 8-34 lists the
with tetryl cannot be stored at temperatures greater than density of ammonium picrate as a function of loading
125°. This is specifically why the United States has pressure.
discontinued the use of this explosive. Tetryl corrodes
steel heavily. Slight corrosion is reported for iron, zinc, Table 8-34. Density of Ammonium Picrate
zinc plated steel, tin plated steel, parkerized steel,
brass, and monel metal. Tetryl does not react with Pressure in Density in
copper, tin, nickel, lead, copper plated steel, bronze, Pressure in pounds per grams per
stainless steel, cadmium, aluminum, silver, and kilopascals square inch cubic
titanium. Tetryl frequently is used with one to two centimeter
percent of a binding agent or lubricant, such as graphite,
stearic acid, or magnesium stearate; and has been 20,685 3,000 1.33
found to be compatible with such materials as well as 34,475 5,000 1.41
black powder. 68,950 10,000 1.47
82,740 12,000 1.49
8-4. Nitroaromatics. Compounds in this class are 103,425 15,000 1.51
prepared by C-type nitration in which a nitrogroup is 137,900 20,000 1.53
attached to a carbon atom of the compound being 344,750 50,000 1.59
nitrated. 689,500 100,000 1.64
a. Ammonium Picrate. The refractive index at 20°C is: alpha, 1.508; beta,
(1) This explosive is also known as 1.870; and gamma, 1.907. The heat of combustion of
ammonium 2,4,6-trinitrophenolate, explosive D, and ammonium picrate at constant pressure is 2,745 calories
Dunnite. The compound (figure 8-41) has a nitrogen per gram, from which is derived a heat of formation
content of 22.77 percent, an oxygen balance to C02 of- value of 95.82 kilogram-calories per mole. The heat of
52 percent, a maximum crystal density of 1.717 grams explosion is 706 calories per gram. Table 8-35 lists the
per cubic centimeter, a nominal density of 1.63 grams solubility of ammonium picrate in various solvents as a
per cubic centimeter, a melting point with decomposition function of temperature.
of about 280°C and a molecular weight of 246.
Ammonium picrate exists in a stable form as yellow,
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FRACTION OF
ORIGINAL SAMPLE
AS PERCENT OF
WEIGHT
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(4) The specifications for ammonium picrate press-loading of shells, while class 2 is used for the
cover one grade of material representing two classes manufacture of picratol and other compositions. The
with respect to granulation. Class 1 material, which is requirements are as follows:
the coarser of the two classes, is intended for use in the
Class1 Class 2
Surface moisture and volatile content (%), maximum: 0.10
Total moisture content (%), maximum: - 0.2
Ammonium picrate purity (%), minimum: 99 99
Sulfates (as sulfuric acid) (%), maximum: 0.10 0.10
Chloroform insoluble impurities (%), maximum: 0.10 -
Water insoluble material (%), maximum: 0.10 0.10
Irritant contaminants as parts 50 -
chlorine per million, maximum:
Ash (%), maximum: 0.1 0.1
Acidity and alkalinity (as picric acid or
ammonia (%), maximum: 0.025 0.025
Color Yellow to Yellow to
orange orange
The picric acid used to make class 2 ammonium picrate explosion as a function of temperature is shown in table
shall be made by the nitration of phenol and shall 8-36.
contain no material salvaged from trimmings or from
loading operations. Class 2 ammonium picrate shall Table 8-36. Ammonium Picrate Explosion
contain no reworked ammonium picrate made by way of Temperature
any process other than the phenol nitration process.
The irritant contaminants requirement is not applicable Temperature in
to ammonium picrate made from picric acid produced Time in seconds degrees centigrade
by the nitration of phenol. The color requirement is
intended to cover the unavoidable presence of a small 0.1 405
amount of the red form of ammonium picrate in 1 367
admixture with the yellow form. The requirement with 5 318
respect to irritant contaminants represents a control of 10 314
the purity of picric acid used in manufacture when this is 15 299
made by the dinitrochlorbenzene process. The 20 295
chloroform soluble matter requirement also represents a
control of the nature of impurities present in picric acid
The low degree of sensitivity of ammonium picrate to
manufactured by a process other than the nitration of
impact is paralleled by a relative insensitivity to
phenol.
initiation. In the sand test, ammonium picrate is not
detonated completely by either lead azide or mercury
(5) Ammonium picrate is distinctly less fulminate. A booster charge of 0.06 gram of tetryl is
sensitive to impact than TNT and is unaffected by the required for complete detonation. In this test, a
steel shoe in the pendulum friction test. A slightly minimum charge of 0.28 gram of diazodinitrophenol
greater sensitivity is indicated by the rifle bullet impact detonates ammonium picrate but a charge of only 0.15
test with three partially burned samples in ten trials. gram is required for the detonation of TNT. The
This is attributed to the lower temperature required for minimum charge of mercury fulminate required to
explosion for ammonium picrate, 318°C in the five initiate 0.4 grams of ammonium
second test, as opposed to 457°C for TNT. The time to
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picrate loaded at about 200 atmospheres of pressure is The critical diameter for a sample with density of 1.65
0.85 grams versus 0.26 grams of mercury fulminate grams per cubic centimeter is greater than 25.4
necessary to initiate 0.4 grams of TNT. Moisture has a millimeters. When exploded adiabatically at constant
marked effect on the sensitivity of ammonium picrate to volume, ammonium picrate produces a pressure of
initiation. The presence of 0.5, 1.0, and 2.0 percent of 8956 kilograms per square centimeter when pressed to
moisture requires increases in the minimum detonating a density of 1.5 grams per cubic centimeter, and 9553
charge of tetryl to 0.09, 0.11, and 0.14 gram, kilograms per square centimeter when pressed to a
respectively. Storage of either the yellow or red form at density of 1.6 grams per cubic centimeter. These
50°C for two years causes such an increase in values are 113 percent of the corresponding values for
sensitivity that initiation by mercury fulminate alone is TNT. Although the heat of explosion of ammonium
possible. Subsequent storage of the yellow form at picrate is only 86 percent that of TNT, the ballistic
magazine temperatures for two years causes pendulum test indicates a power of 98 percent of TNT.
desensitization to such an extent that a booster charge This combination of brisance and power, almost equal to
to tetryl is required for complete detonation and four those of TNT, together with relative insensitivity, has
years of such storage is required for return to the made ammonium picrate suitable for use in armor
original condition of insensitivity. Storage at 500C has piercing projectiles. However, the impracticality of melt-
the same effect on the sensitivity of red ammonium loading ammonium picrate has led to partial
picrate but subsequent storage at magazine replacement by picratol, which can be melt-loaded.
temperatures for four years merely increases the When ignited in an unconfined state, ammonium picrate
minimum detonating charge of mercury fulminate from burns slowly without detonation emitting dense, black
0.23 to 0.29 gram. The changes in sensitivity are not smoke. However, when confined and heated to the
accompanied by any change in brisance or in color. In ignition temperature, an explosion occurs. Complete
an electrostatic sensitivity test for material that passes detonation produces a dense, black cloud of smoke with
through a 100 mesh sieve, an energy of 6.0 joules was sooty deposits and an odor of ammonia. When
required for confined material and 0.025 joules for incomplete detonation occurs, yellow smoke is produced
unconfined material. Ammonium picrate which has along with unburned ammonium picrate particles.
been pressed into and removed from projectiles or other
ammo is much more sensitive to shock than new or (7) Ammonium picrate is of a very high order
unused material. Therefore, reclaimed material should of stability. In the 100°C heat test, 0.1 percent is lost in
not be pressed or loaded into ammo items until after the first 48 hours and 0.1 percent in the second 48
recrystallization. hours. No explosions occur in 100 hours. In the 130°C
heat test there is no acidity or explosion in 300 minutes.
(6) In the sand test, 37.5 grams to 39.5 grams The vacuum stability test at 100°C produced 0.2 cubic
of sand are crushed, which indicates a brisance of 78 to centimeters of gas in 40 hours, at 120°C, 0.4 cubic
82.5 percent of TNT. The plate dent test indicates a centimeters of gas are produced, and at 150°C, 0.4
brisance of 91 percent of TNT for a charge of cubic centimeters of gas are produced. The material
ammonium picrate with a density of 1.50 grams per has been found to withstand storage at ordinary
cubic centimeter. Fragmentation tests indicate a temperatures for a period of twenty years with no
brisance of 91 percent, 96 percent and 99 percent of evidence of deterioration, and at 50°C for more than
TNT for charges that have been pressed to density five years without marked deterioration. Moisture
values of 1.50, 1.53, and 1.55, respectively. The increases ammonium picrate's reactivity with metals
approximate velocity of detonation as a function of such as lead, potassium, copper, and iron. The
density is given by the equation: compounds produced are extremely sensitive. This
reactivity requires that all projectiles loaded with this
V =960+3800d material have contact areas covered with acid proof
paint. At 100°C ammonium picrate is compatible with
where V is in meters per second and d, the density, is in TNT or black powder but undergoes reactions with
grams per cubic centimeter. A charge diameter of 2.54 nitroglycerin, nitrocellulose, PETN, or tetryl. Figure 8-42
centimeters was used to determine the above equation. shows the DTA curve for ammonium picrate.
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b. 1,3-Diamino-2,4,6-Trinitrobenzene (DA TB). are 1260 calories per gram and 1150 calories per gram
for gaseous and liquid water, respectively. The specific
heat is given by the equation:
(1) This explosive is also known as
Cp =0.20+(1.11x10-3)T-
2,4,6trinitro-1,3-diaminobenzene; 2,4,6-trinitro-
(1.81 x10-6)T2 for 47°C < T < 200°C
7,3benzenediamine trinitro-m-phenylenediamine; or
2,4,6-trinitro-1 ,3-diaminobenzol and may be referred to
The heat of sublimation is 138 calories per gram. DATB
as DATNB. The compound (figure 8-43) is a yellow,
can be used as a pressed explosive or as a ballistic
crystalline solid with a nitrogen content of 28.81 percent,
modifier in some rocket propellents.
a melting point of 2860C to 301°C with decomposition,
and a molecular weight of 243.14. Two polymorphs of
DATB have been identified. Form I, which is stable to
2170C, has two molecules per unit cell and unit cell
lengths of a=7.30 Angstroms, b=5.20 Angstroms, c = 1
1.63 Angstroms. Form II has four molecules per unit
cell and unit cell lengths of a=7.76 Angstroms, b =9.04
Angstroms, c = 12.84 Angstroms. The maximum
density of form I is 1.837 grams per cubic centimeter
and the density of form II is 1.815 grams per cubic Figure 8-43. Structural formula for DATB.
centimeter. The nominal density of DATB is 1.79 grams
per cubic centimeter. DATB is slightly soluble in acetic (2) DATB can be prepared by nitrating m-
acid and only very slightly soluble in other solvents. dichlorobenzene to 2,4,6-trinitro-1,3dichlorobenzene and
The vapor pressure is given by the equation: aminating in methanol solutions. Another method of
preparation is by the amination of 2,4,6-trinitro-3-
log p =12.75-7492/T(°C) aminoanisole. In a third method of preparation
for 92.8°C < T < 176.8°C phosphorous oxytrichloride and dipyridinium styphnate
are reacted directly at steam bath temperature and a
The heat of formation is 97.1 to -1 19 calories per gram, suspension of the resulting 2,4,6-trinitro1,3-
the heat of combustion is-7115 kilocalories per mole, dichlorobenzene in methanol is treated with gaseous
the heat of detonation with liquid water was ammonia. Impact sensitivity is 200 percent that of TNT.
experimentally determined as 980 calories per gram and Table 8-37 shows the gap test results for DATB.
with gaseous water, 910 calories per gram. The
computed maximum values for the heat of detonation
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(3) The detonation velocity is given by the sample in 22 hours at 120°C. Figure 8-44 shows the
equation: DTA curve for DATB.
where D is in kilometers per second and p, the density, (1) This explosive is also known as bis
is in grams per cubic centimeter. The failure diameter (2,4,6trinitrophenyl)-diazene. HNAB forms blood red
of unconfined DATB at a density of 1.816 grams per prisms when crystallized from nitrobenzene, glacial
cubic centimeter is 5.3 millimeters. The detonation acetic acid, or concentrated nitric acid. The compound
pressure is 251 and 259 kilobars for samples with (figure 8-45) has a melting point of 215°C to 216°C, a
densities of 1.780 and 1.790 grams per cubic molecular weight of 452, and a density of 1.79 grams
centimeter, respectively. The plate dent test indicates a per cubic centimeter. HNAB has a heat of formation of-
brisance of 120 percent of TNT. 58 to-67.9 calories per mole and a heat of detonation of
1.47 kilocalories per gram for liquid water and 1.42
(4) In the vacuum stability test, less than 0.03 kilocalories per gram for gaseous water. The specific
cubic centimeters of gas are evolved in 48 hours at heat is 0.3 calories per gram per degree centigrade.
120°C. In the LLNL reactivity test, less than 0.03 cubic Table 8-38 shows the gap test results for HNAB.
centimeters of gas are evolved per 0.25 grams of
Density in
grams per cubic Percent Sensitivity
centimeter voids in millimeters
(2) One method of obtaining HNAB is to treat (1) This-explosive is also known as
picryl chloride, (NO2)3.C6H2.CI, with hydrazine, H2N.NH2, hexanitrodiphenyjethylene or 1,2 bis-(2,4,6-
to obtain hexanitrohydrazobenzene. The trinitrophenyl)ethylene or 1,1'-(1,2-ethenediyl) bis-
hexanitrohydrazobenzene is then oxidized by nitric acid (2,4,6trinitrobenzene). The compound (figure 8-47)
or nitrogen oxide gas in a glacial acetic acid solution to forms yellow needles when crystallized from
HNAB. The nitrogen oxide gas is obtained from the nitrobenzene. HNS has a nitrogen content of 18.67
reaction of nitric acid and As203. Another method of percent, a molecular weight of 450.24, and a melting
obtaining HNAB also involves two steps. The first step point of 316°C. The theoretical maximum density of
is to suspend a mixture of dinitrochlorobenzene, type I HNS is 1.740 grams per cubic centimeter with a
(NO2)2.C6H3.CI, with hydrazine in hot water that contains nominal density of 1.72 grams per cubic centimeter.
sodium or calcium carbonate to form The crystals are orthorhombic with unit cell dimensions
tetranitrohydrazobenzene, of a=22.13 Angstroms, b =5.57 Angstroms, c = 14.67
(NO2)2.C6H3.NH.HN.C6H3(NO2)2. The second step is to Angstroms. At the melting point decomposition and
treat the tetranitrohydrazobenzene with concentrated explosions occur. The heat of formation is 13.9 to -18.7
nitric acid. The nitric acid introduces the two required kilocalories per mole, the heat of sublimation is 94.9
N02 groups and also oxidizes the -NH.HNgroup to an - calories per gram, the heat of detonation with liquid
N: Ngroup to form HNAB. water is 1.42 kilocalories per gram, and the heat of
(3) HNAB is a very powerful and brisant high detonation with gaseous water is 1.36 kilocalories per
explosive. At a density of 1.77 grams per cubic gram. The specific heat is given by the equation:
centimeter, the detonation velocity is 7250 meters per
-3
second. Power, by the Trauzl test, is 123 percent of Cp=0.201 +(1.27x10 )T-
TNT. The DTA curve for HNAB is shown in figure 8-46. (2.39x10-6)T2 for 47°C < T < 220°C
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Density Sensitivity
in grams per cubic Percent in millimeters
centimeter voids
(5) At a density of 1.70 grams per cubic Angstroms, b=9.028 Angstroms, c=6.812 Angstroms,
centimeter, the velocity of detonation is 7,000 meters and alpha=108.590, beta=91.82°, and gamma= 119.97°.
per second and the detonation pressure is 262 kilobars. Continuous monitoring of the cell constants of TATB
The plate dent test indicates a power of 120 percent of between 214°K and 3770K allowed for the calculation of
TNT. a volume change of +5.1 percent for this molecular
(6) In the 100°C heat test, HNS loses less system. Expansion of the pure material is almost
than 1 percent weight in 48 hours. Less than one cubic exclusively a function of a 4 percent linear increase in
centimeter of gas is evolved in the 100°C vacuum the c axis, which is the perpendicular distance between
stability test. Figures 8-48 and 8-49 show the DTA and sheets of hydrogen-bonded TATB molecules. The
TGA curve for HNS, respectively. solubility of TATB is greater than 20 percent by weight
per volume of solution in super acids such as
e. 1,3,5Triamino-2, 4,6Trinitrobenzene (TA TB). concentrated sulfuric acid, chlorosulfonic acid,
fluorosulfonic acid, and trifluoromethane sulfuric acid.
Table 8-41 lists the solubility of TATB in various
(1) This explosive is also known as solvents.
2,4,6trinitro-1,3,5-benzenetriamine and may be referred
to as TATNB. TATB (figure 8-50) has a nitrogen content Table 8-41. Solubility of TATB in Various Solvents
of 32.56 percent, an oxygen balance to C02 of-55.78
percent, and a molecular weight of 258.18. TATB is Solubility,
yellow but exposure to sunlight or ultraviolet light causes
in parts
a green coloration which, with prolonged exposure, turns
Solvent per million
brown. The compound has a theoretical maximum
density of 1.937 grams per cubic centimeter and a Methanesulfonic acid 820
nominal density of 1.88 grams per cubic centimeter. An Hexamethylphosphortriamide 150
instantaneous hot bar decomposition temperature of Ethanesulfonic acid 120
450°C to 451 °C was reported with rapid thermal DMSO 70
decomposition above 320°C. The structure of the Hexafluoroacetone sesquihydrate 68
crystalline lattice of TATB (figure 8-51) contains many N-methyl-2-pyrrolidinone 58
unusual features. Some of these are the extremely long N,N-dimethylacetamide 33
C-C bonds in the benzene ring, the very short C-N DMF 27
bonds, amino bonds, and the six furcated hydrogen Tetramethylurea 26
bonds. Evidence of a strong intermolecular interaction, Dimethyl methylphosphonate 22
hydrogen bonds, in TATB is indicated by the lack of an N,N-dimethylpropionamide 16
observable melting point and very low solubility. The Bis(dimethylamino)phosphochloridate 14
intermolecular network results in a graphite-like lattice Gamma butyrolacetone 14
structure with the resulting properties of lubricity and Concentrated nitric acid 14
intercalaction. Physical properties of the triclinic unit
cell, which consists of two molecules, are a=9.010
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Basic solvents:
Tetramethylguanidine 485
Bu4NOH, 25% in methanol 390
N,N,N',N'-Tetramethylglycinamide 67
TATB is suitable for use in plastic explosives and in is sacrificed but handling safety is gained because the
explosives mixtures with TNT that can be cast. The main charge remains inert under the service
major military use is in special applications in warheads environments of high velocity impact and fire.
of high speed guided missiles. In this application energy
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FRACTION OF
ORIGINAL SAMPLE
AS PERCENT OF
WEIGHT
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(2) The preferred method of preparation in exceed 40°C, and hydrolysis of the product does not
the laboratory consists of the nitration of s- occur. The quenched reaction mixture is then pumped
trichlorobenzene with a mixture of nitric acid and oleum through the plate and frame press which discharges into
at a temperature of 150°C for three hours. A toluene a 60 gallon holding tank. Dynel cloth is used as the
solution of the trinitrotrichlorobenzene (TCTNB) filtering medium. Only two frames are needed for the
produced by the nitration is then aminated to yield amount of cake produced. The cake is washed with
TATB. The preferred manufacturing method to produce several 20 gallon quantities of water, each followed with
a particle size greater than 20 microns in 96 percent of an air blow. This is continued until the wash water pH is
the yield, suitable for PBXs and normal explosive 6 to 7. The cake is dried in open trays in a forced draft
compounds, is by the partially patented procedure that oven at 60°C for 16 hours. This completes the nitration
follows. The procedure is carried out in two steps; a step.
nitration step and an amination. (c) The materials required for the
(a) The equipment required is: amination step are 2724 grams of the TCTNB produced
1 A 38 liter (10-gallon), glass- during the nitration step, 27.24 kilograms of technical
lined Pfaudler reactor capable of operation over a range grade toluene, 681 grams of water, 1044 grams of
of 200 to 150°C and pressure of 70 torr to 670 refrigeration grade anhydrous ammonia. The quantity of
kilopascals (100 pounds per square inch), gauge, ammonia includes the amount for leakage and blow
agitation provided by an anchor type blade at speeds of down. The TATB yield will be two kilograms. First, the
20 to 200 revolutions per minute. TCTNB is dissolved in the toluene and the solution is
2 A glass-lined, concentric tube clarified by filtration using Celite filter aid before transfer
reflux condenser integral with the reactor. to the 10 gallon reactor. At this point 67 percent of the
contaminating ammonium chloride by-product can be
3 A 189 liter (50-gallon), stainless eliminated by adding 681 grams of water. The reactor
steel reactor with agitator used in ice quenching of the system is then sealed and heating is continued until the
nitration mixture. contents are at 145°C. Since the amination step is
4 Two 227 liter (60-gallon), moderately exothermic, the jacket steam is turned off at
stainless receivers used in filtrate storage and recovery. this time. Ammonia gas is then added to the reactor gas
5 A stainless steel, 28 phase through an opening on the top of the kettle. The
centimeterx28 centimeterx5 centimeter plate and frame ammonia is metered through a rotameter at a rate of
filter press, closed delivery washing type. about 3632 grams per hour. When the ammonia
(b) The materials required for the overpressure reaches about 34.5 kilopascals (five
nitration step are 2.5 kilograms of TCB with a melting pounds per square inch), the reactor system is purged of
point of 63°C to 64°C, 7.7 kilograms of NaNO3 granular residual air by venting through the reflux condenser.
AR sodium nitrate, and 57.2 kilograms of 30 percent The system is then resealed and the reaction is
oleum. The oleum is charged to the glass-lined reactor, continued for approximately three hours. Moderate
and the sodium nitrate is then added at a slow rate with agitation is used during this period. During most of the
full agitation. The reaction is quite exothermic, and three hour reaction period, conducted at 150°C, the
jacket cooling is used to keep the temperature at 60° to pressure is maintained at 241.3 to 275.8 kilopascals (35
70°C. When the entire amount of sodium nitrate has to 40 pounds per square inch, gauge). This represents
been added and the exotherm peak has passed, the an ammonia partial pressure of about 34.5 to 69
kettle contents are brought to a temperature of 100°C. kilopascals (5 to 10 pounds per square inch). As the
The TCB is then charged to the reactor and steam is reaction progresses, a small amount of jacket heating
applied to the jacket to bring the temperature quickly to may be necessary to maintain the 150°C temperature.
145° to 155°C. The reactor contents are maintained at The termination of the amination reaction is marked by
this temperature for a period of four hours. The small a sharp rise in system pressure to about 413.7
amounts of gas that are produced during the nitration kilopascals (60 pounds per square inch, gauge). After
are vented through the reflux condenser. At the end of the pressure rise, the ammonia flow is shut off and the
the four hour reaction period, the contents are cooled to system is cooled to about 60°C. The system is then
40°C and discharged into the 50 gallon stainless steel vented and approximately ten gallons of water is added
reactor which contains approximately 113 kilograms of to the reaction mixture with good agitation. The TATB
crushed ice. Full agitation is used during this quench product is recovered by filtration using the plate and
step and the nitrous fumes are removed using a water frame press equipped with cotton cloths backed with
sealed vacuum pump. The TCTNB product precipitates filter paper. One frame is sufficient for the amount of
in the form of heavy, white crystals. With the stated product pro
quantity of ice, the temperature during dilution does not
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duced. The cake is washed three times with 20 gallon the temperature brought to 150°C. The reaction time
portions of water, interspersed with air blows. This is varies between six and eight hours with completion
sufficient to remove by-product NH4CI. To-dry the cake indicated by a drop in ammonia flow as measured by the
and remove volatile impurities, the cake is steamed for mass flow meter, an increase in system pressure
about ten minutes and air-blown before removal from approaching the 413.7 kilopascals (60 pounds per
the press. The cake is then dried in open trays in a square inch, gauge) of the ammonia regulator and a
forced draft oven at 100°C for 16 hours. decrease in the heat generated as indicated by the
requirement of more steam to the reactor jacket.
(d) The yield of this process is 89.0 Product isolation involves cooling the reaction mixture
percent of the theoretical with 4 percent of the particles to about 100°C, adding 40 liters of water, and vigorously
below 20 microns in size. The crystal density of the stirring for half an hour. The warm mixture is isolated in
product is 1.93 grams per cubic centimeter. If water a plate and frame press, washed with 85°C water for
was added during the amination process to remove the one hour, and steamed for one hour. The product is
ammonium chloride contaminate the amount of chlorine then dried for a minimum of 16 hours at a temperature
impurities will be about 0.2 percent. If no water was of 115°C prior to sampling and packaging.
added, the chlorine impurities will amount to about 0.6
percent. The process used for the manufacture of finely (3) TATB has an impact sensitivity of 11
divided TATB suitable for use in booster pellets is inches by the Picatinny Arsenal apparatus for a seven
slightly different. Using this process 82±.5 percent of milligram sample. By the ERL apparatus using a 2.5
the product will pass through a 20 micron sieve. In this kilogram weight with type 12 tools and without grit, the
process all the amination reactions are conducted in a no detonation or reaction height is 200 centimeters. The
100 gallon stainless steel reactor heated with 517.125 point of 50 percent detonations is approximately 800
kilopascals (75 pounds per square inch) steam to the centimeters; the weight energy at this point is about 200
jacket. The reactor is fitted with an ammonia inlet, a joules. The shock input to cause detonation has been
vent tube for azeotroping water from the system, and a determined to be 9500 joules per square meter. The
thermowell. The TCTNB is first dissolved in toluene in a five second explosion temperature test result is 520°C,
feed vessel and passed through a 1.5 micrometer in-line and the auto ignition point is 320°C to 325°C. A charge
filter during transfer to the reactor. The solution is then of 0.30 grams of lead azide is required to initiate TATB.
heated to 140°C and the water azeotroped from the Table 8-43 lists the gap test results for TATB. Susan
system. The ullage is then backfilled with ammonia and test results are shown in figure 8-52.
Density
grams per cubic Percent Sensitivity
centimeter voids in millimeters
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D =2.480 +2.85p
Pressure at
Density Detonatio UH20 in explosive Detonation
n
in grams velocity detonation mH20 water Detonation energy in
per cubic in meters meters per meters per interface pressure in Isentropic calories
centimeter per second second in kilobars kilobars exponent per gram
second
The Chapman-Jouguet pressure at crystal density is calculated to be 313 kilobars. Under oxygen deficient conditions the
formation of detonation product gases proceeds according to the equation:
C6H6N606 3H2O(g) +3CO(g) +3N2(g) +3C(s)
(5) TATB has excellent thermal stability. isomers. The alpha isomer, which is the one of military
Differential Scanning Calorimeter measurements show interest (figure 8-54) is symmetrical and will be referred
exotherms at 330°C and 350°C when run at a heating to as TNT. The other five meta isomers will be
rate of 10°C per minute. In the 1000 heat test, identified by the Greek letters beta through eta
approximately .17 cubic centimeters of gas are evolved excluding zeta. TNT is a yellow, crystalline compound
in 48 hours. In the 200°C test for 48 hours 0.5 cubic with a nitrogen content of 18.5 percent, an oxygen
centimeters of gas are evolved; at 220°C for 48 hours balance to CO2 of-73.9 percent, a molecular weight of
2.3 cubic centimeters are evolved. At 260°C for one 227.13, and a melting point of 80°C to 81°C. The
hour approximately 1.2 cubic centimeters of gas are freezing point, which is a more reproduceable quantity
evolved. At 280°C 2.0 cubic centimeters of gas are than the melting point, is used in the specification for the
evolved. Figure 8-53 shows the DTA curve for TATB. two military types of TNT that are procured. The
freezing point is very sensitive to impurities. At
f. 2,4,6-Trinitrotoluene (TNT). atmospheric pressure, TNT boils at 345°C. Small
amounts can be distilled rapidly at atmospheric pressure
without an explosion, but explosions do occur with the
(1) This explosive is also known as trotyl, longer heating periods required for larger quantities.
tolit, triton, tritol, trilite, and 1-methyl-2,4,6- TNT boils at 190°C, 210°C to 212°C, and 245°C to
trinitrobenzene. TNT has been the most widely used 250°C at 2 torr, 10 to 12 torr, and 50 torr, respectively.
military explosive from World War I to the present time. Unlike some other high explosives TNT does not
The advantages of TNT include low cost, safety in undergo partial decomposition when melted. Samples
handling, fairly high explosive power, good chemical of TNT have been melted and solidified at least 60
and thermal stability, favorable physical properties, times with no significant decrease in the freezing point.
compatibility with other explosives, a low melting point The effect of moisture content on the freezing point is
favorable for melt casting operations, and moderate shown in table 8-45.
toxicity. There are six possible ring nitrated TNT
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Table 8-45. Effect of Moisture on the Freezing Point where D, the density, is in grams per cubic centimeter
of TNT and t is in degrees centigrade. Several crystalline
structures of TNT are known. Samples of TNT obtained
Percentage of water Freezing point in °C by sublimation onto a condensing surface held at a
temperature, 780C, very close to the melting point
0 80.59 consist solely of the simple monoclinic form. Freezing
0.1 80.35 the melts at a temperature very close to the melting
0.2 80.20 point also yields a monoclinic form. Crystallization from
0.3 79.99 solvents at room temperature or from strongly
0.5 79.78 supercooled melts yield primarily monoclinic variant
1.0 79.09 forms. Orthorhombic TNT is formed by crystallization
2.5 77.93 from solvents at low temperatures. The unit cell
dimensions of the monoclinic form are a=21.275
Removal of moisture from a sample of TNT by heating Angstroms, b=6.093 Angstroms, and c=15.025
at 1000C is slow as shown in table 8-46. The sample Angstroms with eight molecules per unit cell. The unit
started with a water content of 0.3 percent. cell dimensions of the orthorhomic form are a=15.007
Angstroms, b=20.029 Angstroms, and c=6.098
Table 8-46. Removal of Moisture from TNT Angstroms. At least seven morphological types of TNT
have been identified. Unusual crystal growth has been
Observed when TNT crystals are held near the melting
Hours of heating Freezing point of
point. Additives have a great effect on the
at 100°C sample in °C
crystallization process. Picryl chloride induces the
formation of the orthorhombic form. Other picryl
0 79.99 derivatives, especially 2,4,6-trinitrostilbene, drastically
2 80.30 reduce the linear crystallization rate. Two compounds,
3.5 80.46 hexanitrobibenzyl (HNBB) and
5 80.55 methylpentanitrodiphenylmethane (MPDM), which are
6 80.59 introduced during the purification phase of manufacture,
have the same effect. These compounds have adverse
At ordinary temperatures TNT is essentially nonvolatile. effects on melt loading operations. During the melt
TNT has a crystal density of 1.654 grams per cubic loading operation cracks and voids tend to form in the
centimeter, a cast density of 1.5 to 1.6 grams per cubic cast material. The cracks are caused by an 11 percent
centimeter and a maximum pressed density of 1.63 to shrinkage in the volume of the TNT upon solidification.
1.64 grams per cubic centimeter. Table 8-47 shows the The voids appear between the grains of the large
density of TNT as a function of loading pressure orthorhombic crystals which are formed. A method to
although densities as high as 1.64 grams per cubic preclude the cracks and voids involves a procedure for
centimeter have been reported. overcoming the strong tendency of molten TNT to
supercool with subsequent slow initial crystallization at
Table 8-47. Density as a Function of Loading the melt surface resulting from an insufficiency of crystal
Pressure for TNT nuclei. Addition of solid seed TNT crystals to the melt
while stirring yields a smooth casting with the desired
Pressure in Density in grams very fine, randomly-oriented, monoclinic crystals. TNT
Pressure in pounds per per cubic prepared in this fashion undergoes irreversible crystal
kilopascals square inch centimeter growth upon thermal cycling if the maximum
temperature is above about 30°C to 35°C. For
20,685 3,000 1.34 temperatures above 35°C a linear relationship exists
34,475 5,000 1.40 between the growth with a corresponding decrease in
68,950 10,000 1.47 density and the maximum temperature attained in the
82,740 12,000 1.49 cycle. The growth correlates with the quantity of
103,425 15,000 1.52 impurities present. However, the high viscosity of the
137,900 20,000 1.55 mixture and the fine temperature control required, make
this procedure impractical. Another procedure involves
The density of the liquid in the temperature range of the addition of less than 2 percent HNS. The crystals
83°C to 120°C is given as a function of temperature by formed are largely monoclinic and the casts are of
the equation: sufficient quality. This method is a promising
procedure, however TNT
3
D=1.5446-1.016x10 t
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Cast TNT with a density of 1.62 grams per cubic
surveillance test samples containing 0.5 percent HNS centimeter has a compressive strength of 9,515 to 9,653
submitted to thermal cycling showed increased kilopascals (1,380 to 1,400 pounds per square inch).
exudation, irreversible crystal growth, decreasing The dielectric constant, measured at 35 giga hertz, is
density, and, eventually, complete crumbling. shown in table 8-49 for crystal and flaked TNT.
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Values for the heat of combustion for the crystal range where T, the temperature, is in units of degrees
from 809.18 to 817.2 kilocalories per mole. The heat of centigrade. For the range 83°C to 117°C the relative
formation for the liquid or crystal is between 10 and enthalpy is expressed by the following equation:
19.99 kilocalories per mole. The free energy of H -H0 = 12.450+0.45023 T-(4.0091 x 10 -4) T2
formation for the crystal is 50.92±0.83. The heat of In this equation T is also in units of degrees centigrade.
fusion computed by interpolation of enthalpy curve is The standard enthalpy is 113.2 ±1.5 kilojoules per mole.
23.53 calories per gram although values from 20.2 to The standard entropy for the crystal is 68.12±0.38
25.2 have been reported. Values for the heat of calories per degree Kelvin per mole. Thermal diffusivity
sublimation range from 23.2 to 33.7 kilocalories per as a function of temperature is shown in table 8-52.
mole. The Gibbs free energy of sublimation is 69.6 3.0
kilojoules per mole and the standard entropy of Table 8-52. Thermal Diffusivity of TNT
sublimation is 146.2±1.3 joules per mole per degree
Kelvin. The heat of vaporization is reported in the range Thermal diffusivity Density in grams
of 17 to 22.7 kilocalories per mole. The maximum in centimeters squared per cubic
calculated heat of detonation with liquid water is 1.41 per second x 104 at centimeter
kilocalories per gram; with gaseous water the value is 25°C
1.29 kilocalories per gram. For a charge with a density 19.7 0.64
of 1.54 grams per cubic centimeter, the measured 15.0 0.783
values are 1.09 kilocalories per gram with liquid water 12.1 0.980
and 1.02 kilocalories per gram with gaseous water. The TNT forms binary and ternary eutectics with various
enthalpy of TNT relative to the enthalpy at 0°C for the types of nitro compounds and nitrate esters. The
range 25°C to 68°C is expressed by the equation: dinitrotoluenes and the unsymmetrical TNT isomers
H -H0=0.045 +0.24625 T+(4.205 x 10 -4) T2 form
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KOH
PiCH3+RX PiCH2R +KX
PiCH3CH2O+R2NH PiCH2CH2NR2
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O
Alk
PiCH3+FC(NO2)3 PiCH2NO2
(1) DMF-POCI3
PiCH3 PiCH(CHO)2
(2) KOH
PiCH3+RN2CI PiCH2N=NR
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sulfide. A 37 percent yield of material of 99 percent
purity was so obtained.
3 Reduction of TNT with
ethanolic ammonium sulfide yields 2,4-diamio-6-
nitrotoluene. Reaction of TNT with ethyl alcoholic
hydrogen sulfide containing a small quantity of ammonia
gives a mixture comprising 22 percent unreacted TNT,
22 percent 4-amino-2,6- dinitrotoluene, 4 percent 2-
Figure 8-60. Seven member ring structure. amino-4,6-dinitrotoluene, 44 percent 4-hydroxylamino-
2,6-dinitrotoluene, and 8 per- cent 2-hydroxylamino-4,6-
4 TNT undergoes methyl group dinitrotoluene. The 4-hydroxylamino compound can be
halogenation as well as ring halogenation with loss of extracted from the reaction mixture. The 4-amino-2,6-
the nitro groups at 150°C to 200°C. dinitrotoluene is an intermediate for one procedure for
5 Ring cleavage to chloropicrin preparing the thermally-stable, insensitive explosive
occurs with alkaline hypochlorites. TNT can also be TATB. The reaction is shown in figure 8-62. Reaction
destroyed by treatment with ozone, in the presence of (A) involves an unusual demethylation as well as
base, or ultraviolet light. In both cases, the 2,4,6- nitration. The above partial reduction products of TNT,
trinitrobenzyl anion in generated, which is presumably among others, are formed during biodegradation and
the reactive species. during the destruction of TNT by reaction with sodium or
(c) Reactions of the nitro groups. ammonium sulfide. TNT does not undergo hydrolysis
1 TNT can be reduced to the during storage of a saturated solution in sea water over
triamino compound with tin and hydrochloric acid, or a period of several months at 25°C in active glassware.
with hydrogen using a Pd-BaSO4 catalyst as shown in (d) Some reactions involve both the
figure 8-61. nitro and methyl group. An important aspect of TNT
reactivity involves redox reactions between the reactive
methyl group and the nitro groups, a type of reaction
which can be initiated by various energetic stimuli
including thermal and photochemical as well as
chemical. The following discussion indicates the
reactions are both intra- and intermolecular, ultimately
leading to diverse monomeric and polymeric products.
The intramolecular type involves reaction between the
methyl group and an ortho nitro group. This reaction
occurs especially easily and is often the first step for
Figure 8-61. Reaction of TNT with hydrogen. other reactions. The reaction also applies to many other
2 4-Amini-2,6-dinitrotoluene can derivatives and analogues of 2-nitrotoluene.
be made by treating TNT in dioxane with ammonium
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1 All types of nitro compounds gives a red residue comprising about 50 percent TNT.
react easily with bases forming diverse types of Acetone carbanion forms a complex of structure (III).
products. In the case of TNT, 2,4,6-trinitrobenzyl anion Methoxide, ethoxide, and isopropoxide form complexes
(I) is formed initially and rapidly as shown in figure 8-63. of structure (II). T-butoxide ion yields structure (I) with
The ion is a highly reactive species thought to be TNT.
intermediate in the many reactions of TNT conducted 2 In some cases each mole of
under basic conditions. The anion is formed without TNT can add up to three moles of a base. The
side reactions by the action of 1,1',3,3'- compounds formed with potassium hydroxide in a dilute
tetramethylguanidine in dimethylformamide solvent. aqueous solution are shown in figure 8-64. The one to
Based on spectrophotometric evidence, the first one molar ratio compound is the same type compound
dissociation constant of TNT with NaOH is 1.02±0.2 x as structure (II) shown in figure 8-64. Three moles of
10-12. Highly-colored Jackson-Meisenheimer, or sigma, potassium ethoxide can also react. Addition of two
complexes of structure (II) or (III), also shown in figure moles of sodium sulfite is also possible.
8-63, are formed by addition to the ring system. These
compounds are formed in both aqueous and anhydrous
mediums and with a variety of organic and inorganic
nucleophiles. Sulfite ion forms a complex of structure
(III) which is a source of yield loss during the purification
of TNT if the pH exceeds eight. Cyanide ion also forms
a complex of structure (III). TNT as the anion (I) can
react with other TNT anion (I)'s and produce adducts of
structure (II). A similar reaction takes place with 1,3,5-
trinitrobenzene. Primary and secondary aliphatic
amines also form sigma complexes. Upon solution in
liquid ammonia, a complex of type (III) is initially formed
with no evidence of type (I) having been formed. With
time, a second NH2 group becomes attached to the ring
carbon with the methyl group; this compound has cis-
and trans-isomers. Removal of the ammonia
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3 Side reactions can occur, step except for the 3,4,5-isomer, which lacks the
especially in the presence of excess base at elevated adjacent methyl and nitro groups.
temperatures and prolonged times of reaction. (f) In the manufacturing process,
Potassium hydroxide and anhydrous ammonia can form absorption by activated carbon filters is commonly
nitrite ions by clevage of nitro groups. 2,4,5- employed to control pollution. The TNT is absorbed at
Trinitrophenol and 3,5- dinitrophenol have been isolated many of the numerous high-energy sites on the surface
from the reaction of TNT with NaOH. Redox reactions of the carbon. Basic materials, introduced during
give polymeric materials via the formation of azo and activation of the carbon by combustion and oxidation
azoxy groups, as shown in figure 8-65 for the case of are also present at these sites, then induce oxidation-
phenylhydrazine. Dimerization also occurs by the redox reduction reactions of the methyl with the nitro groups in
coupling of two molecules of TNT to form PiCH2CH2Pi. the TNT. This is manifested in the simplest form by the
The oxidant in this case is TNT. The complexes of formation of small amounts of trinitrobenzoic acid and
long-chain, primary-secondary aliphatic amines with trinitrobenzene. Coupling and polymerization also
TNT have low water solubility and may be useful for the occur, via generation of azo and azoxy linkages among
removal of TNT from aqueous solutions. The rapid others, yielding complex, high molecular-weight
reactions with isopropylamine in acetone has been materials which are irreversibly bound to the surface
studied as a possible procedure for the neutralization of and clog the pores of the carbon. This process is,
TNT in land mines. therefore, generally similar to that involved in the
(e) The degradation of TNT by electron thermal and basic decomposition of TNT. When TNT
impact has been studied. The initial step is a methyl- and activated carbon are dry-mixed at room
hydrogen transfer to an adjacent nitro-oxygen which is temperature, the TNT rapidly and completely displaces
followed by cleavage of the hydroxyl group. The the air absorbed on the carbon. The carbon has a
resulting ion then degrades further by several routes strong catalytic effect on the thermal decomposition of
which include the loss of small stable molecules such as TNT. At 120°C, a 90/10 TNT/carbon mixture
CO, NO, HC = CH, HCN, etc. All of the TNT isomers decomposes 12.3 times as fast as pure TNT, and a
undergo similar methyl-hydrogen transfer as the first 50/50 mixture 113 times as fast.
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The unsymmetrical isomers all differ from the number one. The mixed acid consists of nitric acid, 40
2,4,6isomer in having notably higher melting points and percent oleum, and water. Fortification with nitric acid is
in having one nitro group which is easily replaced by required between nitrators. The temperature of nitrator
treatment with various nucleophilic reagents; the number one is maintained at 50°C to 55°C. Each
position of this group is indicated in table 8-53. successive nitrator is maintained at a higher
Consequently, the reactions of 2,4,6-TNT under basic temperature than the one immediately proceeding.
conditions are entirely different from those of the other Nitrator number eight is maintained at about 100°C.
five isomers. All of the unsymmetrical isomers have Each nitrator is equipped with an agitator. The solubility
been found in crude TNT, ranging from about 2.5 of toluene and the nitrotoluenes in mixed acid is very
percent for the 2,4,5-isomer and 1.5 percent for the low. Therefore, the nitration proceeds in a two phase
2,3,4-isomer down to 0.006 percent for the 3,4,5-isomer. system and the rate of nitration depends on dispersion.
The meta isomers form low melting point eutectics with The dispersion depends on keeping the two phases well
TNT and so must be removed during the manufacturing stirred. Figure 8-66 shows the yield of mononitrotoluene
process. as a function of the rate of stirring with a mixed acid
(5) TNT is manufactured by the consisting of 11 percent nitric acid, 64 percent sulfuric
nitration of toluene in successive steps. In the first step acid, and 25 percent water for a nitration time of 30
toluene is nitrated to mononitrotoluene (MNT). The minutes. The results with the use of 40 percent oleum,
MNT is then nitrated to dinitrotoluene (DNT). The last which consists of 40 percent sulfur trioxide by weight
step is the nitration of DNT to TNT. The three steps are dissolved in sulfuric acid, are analogus. However oleum
carried out under different conditions. The trinitration is is more reactive than sulfuric acid. The mononitration is
carried out at a higher temperature than the dinitration, carried out in the first nitrator where the temperature is
which is carried out at a higher temperature than the lowest and the mixed acid has the highest water
mononitration. The trinitration also requires a stronger content. The low temperature reduces the amount of
mixed acid than the dinitration, which requires a meta and of ring oxidation products formed.
stronger mixed acid than the mononitration. In the Mononitration at -110°C followed by dinitration at 0°C to
continuous production system installed at Radford Army 25°C yields a product with one tenth the amount of
Ammunition Plant these requirements are met with a these impurities as when nitration is carried out under
counter flow process. The system consists of eight normal conditions. This process, however, is much
nitrators. Toluene is introduced into nitrator number one more costly than the one carried out at higher
and moves successively through each nitrator to nitrator temperatures so is not used. Less degradation occurs
number eight where nitration to TNT is completed. because of the higher water content of the mixed acid.
Mixed acid is introduced into nitrator number eight and
moves successively through each nitrator to nitrator
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Toluene is much easier to nitrate than benzene because that both have the same nitric acid requirement.
of the presence of a methyl group compared with Radford usage of sulfuric acid is about 79 percent that
benzene. The reaction of introducing the first nitro of the ROF process, calculating both on the basis of a
group therefore proceeds very quickly, however the strength of 96 percent. The ROF system employs a
methyl group is readily oxidized. Mononitration also lower temperature for mononitration, 35°C to 42°C vs
leads to oxidation of the ring and the formation of 50°C to 56°C for the Radford process. In West
cresols. If the mixed acid is poor in nitric acid or if an Germany, mononitration is affected by a continuous
insufficient amount of mixed acid is used, tar formation process, but di- and trinitration are conducted batchwise,
may take place. To counteract these undesirable because of a high purity requirement. Trinitration is
effects an excess of mixed acid that is rich in nitric acid affected with mixed acid comprising 24 percent HNO3,
could be used. On the other hand, both excess HNO3 70 percent H2SO4, and 6 percent SO3. The reaction
and excess mixed acid favor oxidation processes. Thus requires six hours with slowly rising temperatures.
a trade-off must be achieved. Other oxidation reactions These conditions remove the dinitrotoluene isomers
proceed especially readily under drastic conditions more completely than is possible with the much shorter
which introduce several nitro groups at a high reaction time used in continuous operation.
temperature. This effect is minimized by having
multiple nitrators with small temperature differentials
between them. A concentration gradient for DNT and
TNT exists across the production line. Table 8-54
shows the change in concentration of the nitro body,
nitrated material in a six nitrator system. Six nitrators
were used in the three Radford production lines before
an explosion destroyed one of the lines. The explosion
occurred during faulty manual removal of white
compound which had coated the nitrator cooling coils.
To stop the formation of white compound, an oxidation
product, the number of nitrators was increased from six
to eight. Each nitrator was also fitted with a centrifugal
separator rather than a gravity separator, as the six
original nitrators had. This reduced the amount of Figure 8-66. Agitation versus MNT yield.
nitrobody in the system at any given time. Another (6) A problem associated with TNT production is the
design of continuous process in current use is the British disposal of tetranitromethane (TNM), a toxic, odorous,
ROF Process. This procedure also involves multistage and explosive material which is obtained in the exit gas
countercurrent contacting, with the monoto-trinitration from the trinitration step to the extent of about 136
unit comprising a rectangular box-shaped vessel grams to 227 grams per 45.4 grams of TNT. Venting
subdivided into eight stirred nitrator stages with TNM to the atmosphere is now illegal. The TNM can be
intervening unstirred nitrobody-acid transfer sections. recovered by scrubbing the gas with aqueous sodium
Mononitration is conducted separately in a smaller, carbonate containing stabilized hydrogen peroxide,
similar vessel. This design desirably eliminates all which converts the TNM to nitroform. Nitroform is a raw
interstage pipework and ductwork connections. This material for making energetic plasticizers. Another
equipment applies to the use of 96 percent sulfuric acid, objectionable effluent from TNT production is oxides of
which requires more staging to affect complete nitration nitrogen (NOx). These can be removed ( >95 percent)
than in the case of the Radford plant, which employs 40 by oxidation to nitric acid, followed by scrubbing with
percent oleum. A comparison of the two systems shows sulfuric acid.
that both give an 85 percent yield based on toluene, and
Nitrator 1 2 3 4 5 6
Temperature (°C) 50-55 70 80-85 90 95 100
Composition of
nitrobody:
MNT(°/o) 71.1% - - - - -
DNT(%/o) 18.2 70.9 30.4 10.3 1.6 0.2
TNT(%/o) 4.2 28.9 69.3 89.5 98.2 99.7
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(7) After nitration, the crude TNT requires (b) The oily products can penetrate into
purification. The ultimate objective of TNT purification the threaded parts of the shell and form "fire channels"
is to remove all those products produced during nitration through which the ignition of propellent can ignite the
which are more reactive than TNT or which can easily charge.
give oily exudation products. Oil exudation from TNT is (c) The oily products can penetrate into
an undesirable characteristic for the following reasons: the detonating fuze if the explosive of the fuze is not
(a) Exudation produces porosity of the protected by a metal envelope, and reduce the
TNT charge and the corresponding reduction in density. detonating power of the fuze.
This reduces the explosive effect. In artillery shells this (8) Table 8-55 lists the impurities that are
can produce a dislocation of the charge on firing, formed during the manufacture of TNT and the amounts
compression of the air included in the cavities, and contained in the product after purification. The
premature explosion. concentrations listed in the table are maximum values;
the actual values are lower.
Of the TNT isomers formed, only the first two listed in sodium sulfite called sellite. The meta TNT isomers
the table, the 2,4,5- and 2,3,4-isomers, are present in react with the sodium sulfite to form water-soluble
significant quantities. The dinitrotoluenes result from sulfonates by the following reaction:
incomplete nitration. The next eight compounds listed
in the table result, directly or indirectly, from oxidation of CH3C6H2(NO2)3 + Na2SO3
the methyl group during nitration, while the last three are CH3C6H2(NO2)2SO3Na+ NaNO2
introduced during purification. The purification process
currently in use involves treating TNT with aqueous
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Current American practice entails continuous treatment percent or more extrudate. A typical analysis of exudate
of molten TNT, at a temperature greater than 80°C, with from specification-grade TNT made in 1973 at the
an aqueous solution containing about 0.1 part anhydrous Radford Army Ammunition Plant by the continuous
sodium sulfite per part TNT. This corresponds to about process is as follows:
four times the theoretical requirement according to the
equation given above. The liquids are countercurrently 2,4,6-TNT 88.19%
contacted in three washers each of which is followed by 2,3,4-TNT 1.99%
a centrifugal separator. This purification process is quite 2,4,5-TNT 0.67%
sensitive to pH. Yield loss rises sharply above pH 7.5 2,4-DNT 7.65%
because of the formation of the water soluble complex 2,6-DNT 0.98%
of 2,4,6-TNT with sodium sulfite. In addition, at pH 2,5-DNT 0.19%
values above about 8 the formation of the two by-
products hexanitrobibenzyl (HNBB) and HNBB and MPDM also form eutectics with TNT. Two
methylpentanitrodiphenylmethane (MPDM) increases approaches have been considered for minimizing
strongly. These compounds have an adverse effect on extrudation. One approach to solving the extrudation
the mode of crystallization of TNT. Table 8-55 shows problem is to produce TNT with smaller amounts of
that meta TNT isomers are not completely removed and impurities. This can be done by carrying out nitration
that the amounts of all of the DNT isomers and of five of under more drastic conditions, which adds to the
the oxidation products remain unchanged. The ROF process cost, and closely controlling the sellite process
TNT Process also employs continuous purification, to minimize production of HNBB and MPDM.
using a compartmented reactor generally similar to that Crystallization from nitric acid removes all DNT isomers.
used by them for nitration. However, the TNT is Another approach is to add materials to the TNT that
contacted as a solid at 67.5°C, rather than as a liquid, as absorb the eutectics. Cellulose esters, in the amount of
in the American process. This is said to result in a about 0.6 percent, absorb the extrudate and reduce the
higher yield of purer TNT with a requirement of about tendency of the TNT to crack. Polyurethanes remove
two-thirds as much sodium sulfite. HNBB and MPDM extrudate and double the compressive strength of the
are not formed. Advantage is taken of the fact that the cast.
unsymmetrical isomers form a eutectic which migrates (10) Two types of TNT are specified for
to the crystal surface. This type of process is also military use:
employed in West Germany. The process is operated
batchwise using 4 to 10 parts Na2SO3 per 100 parts TNT Type I Type II
with a reaction time of 30 minutes. Use of this Form Flake or Crystalline
purification procedure, taken with a batch trinitration crystalline
method which removes nearly all of the DNT isomers, Color No darker than Light yellow
yields a TNT of unusually high purity. The solidification number 30257
point of the product is 80.65°C to 80.80°C. This type of
process has also been used in the past in the United Solidification point (°C), 80.20 80.40
States. Disposal of the waste sellite solution, known as minimum
red water, is a serious pollution control problem. TNT Moisture (%), maximum 0.10 0.10
can be purified by recrystallization from nitric acid. This Acidity (%), maximum 0.005 0.005
process has been used for many years in Sweden. The Alkalinity None None
nitric acid, after crystallization and filtration of the 2,4,6- Toluene insoluble matter 0.05 0.05
isomer, is recovered by distillation leaving a mixture (%), maximum
consisting of about 50 percent 2,4,6-TNT, 25 percent Sodium (%), maximum 0.001 0.001
TNT meta isomers, and 25 percent dinitrotoluenes and Granulation
oxidation products known as isotrioil. The isotrioil is through a US standard 95 100
then sold as an ingredient in commercial dynamite. number 14 sieve
Sweden has had trouble marketing isotrioil, which is the through a US standard - 95
major reason this otherwise attractive process has not number 100 sieve
been adopted elsewhere. Even after purification,
military grade TNT typically shows 0.6 percent to 1.2
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For type I flake form the average thickness of the flakes Table 8-56. Impact Sensitivity of TNT
shall not be more than 0.63 millimeters (0.025 inches)
and any individual flake shall be no more than 0.1 Inches on
millimeters (0.004 inches). Picatinny Arsenal
(11 ) TNT is one of the least sensitive of military Temperature apparatus with
explosives; only ammonium picrate, nitroguanidine, and in °C 2 kilogram weight
ammonium nitrate are less sensitive. Impact tests yield
high values relative to other military explosives, but -40 17
impact sensitivity increases sharply with increasing Room 14
temperature, as shown in table 8-56. Diminishing 80 7
sensitivity has been reported down to- 196°C. Gap and 90 3
projectile test results indicate cast TNT is less sensitive 05 2 (five explosions
than the pressed materiel. Test results from the mod- in 20 trials)
ified gap test for cast and pressed TNT are shown in minimum detonating charge values for initiation by lead
table 8-57. Finely divided TNT, as obtained by fume azide or mercury fulminate. The dry material can be
condensation, is more sensitive to impact than the detonated by a number six electric blasting cap but the
crystalline material. TNT which has been exposed to presence of only 7 percent moisture prevents
light is also more sensitive. The pendulum friction test detonation. This is compared to 14 percent and 35
does not affect TNT. The material is insensitive to rifle percent moisture required for the desensitization of RDX
bullet impact at room temperature whether unconfined and PETN respectively. TNT pellets pressed from flake
or confined in iron, tin, or cardboard bombs. The same TNT undergo substantial reductions in the rate of
results are obtained at the temperature between 105°C detonation and sensitivity to initiation after storage for
and 110°C with tin or cardboard bombs and in the iron one week at 65°C. These changes are accompanied by
bomb with an airspace. In an iron bomb with no exudation of oily impurities, recrystallization, and
airspace 70 percent of the trials resulted in explosions. sementation of the TNT. TNT is not classified as
The explosion temperature for unconfined TNT is 475°C dangerous with respect to hazard from electric sparks.
which is much higher than for other commonly used The sensitivity to electric discharge for 100 mesh TNT is
military explosives. Explosion temperatures for 0.06 joules unconfined and 4.4 joules confined. The
confined samples depend on the purity of the sample fine dust of TNT is sensitive to electric sparks. When
and test conditions. Results in the range of 275°C to ignited in free air, the dust burns completely without
295°C are obtained. Heating in a closed glass capillary detonation; and the temperature of the liquid phase
tube yields a value of 320°C to 325°C. TNT has high must be 510°C if detonation is to
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result from burning. Even when it is under a gas where D is in kilometers per second and p, the density,
pressure of 100 psi, the liquid phase temperature must is in grams per cubic centimeter. Detonation velocities
be greater than 285°C if TNT is to burn with subsequent of stick charges can be substantially increased by the
explosion. Figure 8-67 shows the results of trials of the presence of an axial channel. The detonation
Susan test for TNT. temperature also increases with density. At densities of
1.0 and 1.59 grams per cubic centimeter the detonation
temperature is 3,000°K and 3,450°K, respectively. The
detonation pressure as a function of density is shown in
table 8-58.
PROJECTILE VELOCITY AT IMPACT - M/S In the copper and lead cylinder compression tests the
cylinders are compressed 3.5 and 16 millimeters,
Figure 8-67. Susan test results for TNT. respectively. The depth of the dent in the plate dent test
is about 0.205 millimeters. The energy of detonation at
(12) TNT is the standard explosive to which all the other 1.65 grams per cubic centimeter is 1,265 calories per
explosives are compared. In the sand test, 48 grams of gram or 4.10 joules per gram. At 1.62 and 1.64 grams
sand are crushed. The detonation velocity may be per cubic centimeter 684 and 690 liters of gas are
computed by the following equations: evolved, respectively. Fragmentation effects of pressed
D=1.873+3.187p for 0.9 <p < 1.534 and cast TNT charges are shown in table 8-59.
D =6.762+3.187(p-1.534) -25.1(p - 1.534)2
for 1.534 <p < 1.636
The Chapman-Jouguet particle velocity at 1.59 grams charges of the same density have very different critical
per cubic centimeter is 1.83 kilometers per second. The diameters. The reaction time of pressed TNT is less
Von Neumann peak pressure at 1.614 grams per cubic than half that of the cast material. Axially oriented TNT
centimeter is 237 kilobars. The critical charge diameter crystals show unstable detonation while radially oriented
of stick charges of TNT is influenced by several factors crystals detonate smoothly. TNT detonation products
including initial density, grain size, initial temperature, vary with the degree of confinement as shown in table 8-
and degree of crystallivity. TNT cast with many 60. Increasing confinement shifts the formation of
crystallization centers, as is obtained by adding TNT carbon monoxide to that of solid carbon, and the
seed crystals to the melt just before solidification, has a formation of hydrogen gas to that of water. The degree
smaller critical diameter than that made by conventional of conversion of the nitrogen atoms to elemental
crystallization from a clear melt. Cast and pressed nitrogen remains consistent regardless of confinement.
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Trace amounts of methane, hydrogen cyanide, and correspondingly be converted to azo or azoxy
ethane were also detected. In the Trauzl test, 10 grams compounds or to an anthranil by inter- and
of TNT expand the cavity by 285 to 305 cubic intramolecular reaction, respectively, with the methyl
centimeters. groups. The most likely type of azoxy compound
(13) TNT shows no deterioration after 20 years formed is shown in figure 8-71. Polymerization and
storage in a magazine or after two years storage as a crosslinking by reactions of this type can explain the
liquid at 85°C. Only a small amount of decomposition formation of the explosive coke. The compound of the
occurs after storage at 150°C for 40 hours. Above that gases evolved was found to vary with the extent of
temperature slow decomposition occurs. Autoignition reaction and with the temperature. The complicated
occurs after about 38 hours at 200°C. The thermal nature of the process is shown by the fact that the
decomposition of liquid TNT is characterized by the evolved gases contain not only water, corresponding to
sigmodial curve typical of an autocatalytic reaction. the formation of the products cited above, but also CO,
Explosions occur after an induction period that varies N2, NO, N20, and even acetylene. Rupture of the C-H
with temperature. However, heating at the boiling point bond in the methyl group is the rate determining step in
causes distillation but not explosion in small samples. thermal decomposition of TNT. The activation energy
TNT vapor was found to undergo no decomposition over of thermal decomposition is 40.9±1.6 kilocalories per
the range 250°C to 301°C at 35 to 500 torr. Even at mole during the induction period and 30.2+0.6
357°C the vapor does not explode although kilocalories per mole for the post induction period.
decomposition is quite extensive. As shown in figure 8- Added nitroaromatic compounds have no effect on the
68, differential thermal analysis indicates an endotherm rate of thermal decomposition of TNT. Nitramine and
at 75°C to 100°C and an exotherm at 260°C to 310°C. aliphatic nitrated esters have only a slight effect. Strong
The TGA curve is shown in figure 8-69. Although at promoters of decomposition include potassium nitrate,
least 25 products are formed, the major products potassium chloride, certain iron and cobalt compounds,
obtained by heating a sample of TNT for 26 hours at and ammonia. Other active compounds include:
200°C are: hydroquinone, benzoic acid, activated carbon, various
Unreacted TNT 75-90% plastic materials used to seal or line ordnance,
Explosive coke 0-13% trinitrobenzaldehyde, 4,6-dinitroauthranil and explosive
4,6-Dinitroanthranil 2-4% coke. The last three compounds are thermal
2,4,6-Trinitrobenzaldehyde 1-2% decomposition products of TNT. Aluminum oxide has a
Azo and azoxy compounds 0.4% pronounced effect, while PbO, Fe, Al, and Fe203 are less
2,4,6-Trinitrobenzyl alcohol 0.2% effective in that order, and Sn and CuO have little or no
effect. Previous exposure to ultraviolet light for several
The structure of 4,6-dinitroanthranil is shown in figure 8- hours also accelerates thermal decomposition. Moisture
70. The explosive coke is a brown, intractable powder, has no effect on the stability of TNT, which is unaffected
apparently polymeric, melting about 360°C, and by immersion in sea water. However, at 50°C ethanol
containing nitro groups. The infrared spectrum indicates reacts with alpha or gamma but not beta TNT. In case
the presence of the nitro groups. Since similar results of alpha TNT the products are ethyl nitrite and an
were obtained from heating TNT in a inert atmosphere unidentified nitrocompound that melts at 77.5°to 77.9°C
and exposed TNT to air, oxidation must have occurred and is soluble in exudate oil.
at the expense of nitro groups which would
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FRACTION OF
ORIGINAL SAMPLE
AS PERCENT OF
WEIGHT
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The density of the molten material in grams per cubic pressure and 18°C for solid ammonium nitrate with all
centimeter is 1.402 and 1.36 at 175°C and 200°C, decomposition products in gaseous form. None of these
respectively. When heated at atmospheric pressure, reactions occur as a single reaction, but are always
decomposition occurs at 230°C and deflagration occurs accompanied by other reactions. The predominate
at 325°C. There may even be decomposition at reactions are the ones listed in (2) and the two listed in
temperatures as low as 100°C since constant weight (7):
cannot be obtained at this temperature and (1) NH4NO3 HNO3+NH3+38.30
decomposition is quite perceptible above the melting kilocalories. This reaction takes place at a temperature
point. The boiling point of the pure material is 210°C. somewhat above the melting point of ammonium nitrate.
Distillation without decomposition can be carried out at The corresponding value for the solid salt is-41.70
11 torr. On the Mohs scale a scratch hardness of 1.1 is kilocalories.
reported. Specific heat values as a function of (2) NH4NO3 N20+2H20+13.20
temperature are listed in table 8-62. kilocalories with H20 gas and 33.10 kilocalories for H20
liquid. For the same reaction the value of-10.7
kilocalories has been reported. This reaction takes
Table 8-62. Specific Heat of Ammonium Nitrate place in the temperature range of 180°C to 200°C when
the ammonium nitrate is unconfined. Oxides other than
Temperature in °C Specific heat in N20 form at 203°C to 285°C. Decomposition at 260°C
calories per gram is accompanied by puffs of white smoke.
per degree centigrade (3) NH4NO3 H2+0.502+2H20+30.50
- 200 0.07 kilocalories for H20 gas or 50.40 for H20 liquid. For the
-150 0.19 same reaction, values from 27.72 to 30.50 kilocalories
-100 0.30 are reported for H20 gas. This reaction takes place
- 80 0.35 when ammonium nitrate is heated under strong
- 50 0.37 confinement or when initiated by a powerful detonator.
0 0.40 This is the principal reaction of complete detonation of
50 0.414 ammonium nitrate. According to calculations, this
100 0.428 reaction develops an approximate temperature of
1,500°C and pressure of 11,200 kilograms per square
The heat of fusion is 18.23 calories per gram. The heat centimeter. The gas evolved is calculated to be 980
of formation is 88.6 kilocalories per mole. Under liters per kilogram at standard temperature and
constant pressure, the heat of combustion is 49.4 pressure.
kilocalories per mole and at constant volume, the heat is (4) NH4NO3 NO+0.5N2+2H20 +9.0
50.3 kilocalories per mole. At 25°C the latent heat of kilocalories for H20 gas or 28.90 kilocalories for H20
sublimation is 41.8 kilocalories per mole. liquid. A value of 6.87 kilocalories has also been
reported for the reaction with the H20 gas. This may be
one of the side reactions taking place during incomplete
detonation. A pressure of 4,860 kilograms per square
centimeter and a temperature of approximately 518°C
are developed.
(5) NH4NO3 0.5HN3+0.75NO2
+0.25NO +0.25N2 + 1.25H20-21.20 kilocalories. This is
a reaction of decomposition that occurs when
Figure 8-73. Structural formula for ammonium nitrate. ammonium nitrate is under confinement at 200°C to
260°C. This endothermic reaction is followed, at 260°C t
300°C, by explosion of the gaseous products of reaction.
b. Ammonium nitrate can decompose according to This explosion is an exothermic reaction liberating 48.49
any of the nine equations listed below. Unless otherwise kilocalories of heat which is more than 1.5 times as
stated, the heats of decomposition are based on solid great as the heat liberated by reaction (3) above.
phase ammonium nitrate. For molten ammonium (6) 3NH4NO3 2N2+N203+6H20+20.80
nitrate add about 4,000 calories per mole to the values. kilocalories for H20 gas or 40.60 for H20 liquid. A value
The values for the heat liberated are at constant of 21.80 has also been reported for the reaction with the
H20 gas. This reaction cannot take place alone
because N203 exists only in the dissociated state as
NO+ NO2.
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(7) 4NH4NO3 2NO2+3N2+8H20+29.80 are formed. The grains are called prills. In the third
kilocalories for H20 gas or 49.80 kilocalories for H20 method crystals are formed by vacuum evaporation at
liquid. A value of 24.46 has been reported for the two torr, centrifuging, and drying to remove the
reaction with the H20 gas. This is another possible side remaining one to two percent moisture.
reaction occurring during incomplete detonation. For e. Ammonium nitrate used for military purposes
this reaction, a similar endothermic reaction can take must meet the following requirements:
place:
4NH4NO3 3NO2+5H20 + N2+NH3+NO
-84.88 kilocalories Moisture:
If the gaseous products are heated, an explosive Maximum, 0.15 percent.
exothermic reaction takes place. Ether-soluble material:
(8) 5NH4NO3 2HNO3+4N2+9H20 Maximum, 0.05 percent.
+35.10 kilocalories for H20 gas or about 55 kilocalories Water-insoluble material of ether-extract:
for H20 liquid with HNO3 dissolved. This reaction takes Maximum, 0.10 percent.
place under certain conditions such as in the presence Water-insoluble material:
of spongy platinum and gaseous HNO3. Retained on a 250 micron (No. 60) sieve, none.
(9) 8NH4NO3 16H20+2NO2+5N2 Retained on a 125 micron (No. 120) sieve.
+16.58 kilocalories. This reaction takes place during Maximum, 0.01 percent.
incomplete detonation and is accompanied by a yellow Acidity, as nitric acid:
flame. The calculated value for the total gas developed Maximum, 0.02 percent.
by this reaction is 945 liters per kilogram. Nitrites:
c. Ammonium nitrate decomposed by strong None.
alkalies liberates ammonia and decomposed by sulfuric Chlorides, as ammonium chloride:
acid forms ammonium sulfate and nitric acid. In the Maximum, 0.02 percent.
presence of moisture, ammonium nitrate reacts with Phosphates, as diammonium phosphate:
copper to form tetraminocupric nitrate, Cu (NO3)2 0.21 ± 0.04 percent.
4NH3, which has the same sensitivity to impact and Sulfates, as diammonium sulfate:
brisance as lead azide. For this reason tools of brass 0.007 to 0.014 percent.
and bronze are not used in operations with explosives Boric acid:
containing ammonium nitrate. 0.14±0.03 percent.
Ammonium nitrate:
d. Ammonium nitrate can be manufactured by
Minimum, 98.5 percent.
several methods. The most common method is by
Density:
passing ammonia gas into 40 percent to 60 percent
Particle, g/ml.
nitric acid. Both the ammonia and nitric acid are
Minimum, 1.50.
produced by a catalytic process from atmospheric
Bulk, g/ml.
nitrogen, so the ammonium nitrate obtained is of very
Minimum, 0.80.
high purity. The solution is then concentrated in
Bulk, Ibs/cu ft.
evaporating pans provided with air agitation and heating
Minimum, 50.0.
coils. To form ammonium nitrate crystals, one of three
pH:
methods is used. One method involves transferring the
5.9 ±0.2.
material that has fudged in the evaporating pan to a flat
grainer that is equipped with slowly rotating stainless
Granulation (percent by weight):
steel paddles. Stirring in the open cools the syrup,
Through a 3360 micron (No. 6) sieve.
drives off the remainder of the water and produces
Minimum, 99.0.
small, rounded crystals of ammonium nitrate. Another
Retained on a 1680 micron (No. 12) sieve.
method involves transferring the solution, which has
50.0 - 85.0.
been concentrated to about 95 percent, from the
Retained on a 840 micron (No. 20) sieve.
evaporating pan to the top of a spraying tower. In the
Minimum, 97.0.
tower the solution is sprayed and allowed to fall where
Through a 500 micron (No. 35) sieve.
the remainder of the moisture evaporates and spherical
Minimum, 0.5
grains, about the size of buck shot, of ammonium nitrate
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The material must be free of nitrite and alkali. The quantities cannot be detonated completely at densities
granulation of ammonium nitrate is closely controlled so greater than 1.1. The admixture of up to eight percent
that satisfactory fluidity and density can be obtained in of nonexplosive carbonaceous material somewhat
composition explosives. sensitizes ammonium nitrate to initiation.
f. Ammonium nitrate is the least sensitive to
impact of any of the military explosives. Impact g. The brisance of ammonium nitrate cannot be
sensitivity varies with temperature as shown by the measured in the sand test because of a failure to
following data: completely detonate. The lead cylinder compression
test indicates a brisance of 54 percent of TNT for a
Temperature in °C Impact height in inches sample with a density of 1.3 grams per cubic centimeter.
(Picatinny apparatus) Ammonium nitrate has a very low ability to propagate a
detonating wave. In unconfined charges that are long
25 31 and small in diameter, the detonating wave dies out
100 27 before reaching the opposite end of the cartridge.
150 27 Ammonium nitrate has a very low velocity of detonation.
175 12 Factors affecting the velocity of detonation are density,
degree of confinement, charge diameter, particle size,
strength of the initiating impulse, temperature of the
The material is unaffected by the steel shoe in the sample, and the presence of certain impurities such as
pendulum friction test and does not explode in the five organic materials or oxidizable metals. The rate of
second explosion temperature test. Heating pure, detonation increases with decreasing particle size. A
unconfined ammonium nitrate produces a more or less decrease in the apparent density of the charge and an
rapid decomposition accompanied by a flash and a increase in confinement causes an increase in the
hissing sound but no explosions. If a crystal or a piece velocity of detonation. An increase in the temperature
of cast ammonium nitrate is thrown upon a hot plate at a of the charge from 15°C to 140°C results in an increase
temperature of about 500°C, the material immediately of 400 meters per second in the rate of detonation.
catches fire and burns rapidly with a yellowish flame and Within certain limits an increase in the strength of the
a crackling or hissing sound, but leaves no residue. If a initiating agent, the diameter of the charge, and
large piece of cast ammonium nitrate is thrown upon a presence of organic compounds or oxidizable metals
red hot plate, the decomposition proceeds quickly can increase the rate of detonation. The velocity of
enough to resemble an explosion. The minimum detonation varies from 1,100 meters per second to
temperature at which a confined charge will explode is 3,000 meters per second. The Trauzl test indicates
around 260°C to 300°C under a pressure of about ammonium nitrate is 75 percent as powerful as TNT and
17,237 kilopascals (2,500 pounds per square inch). The the ballistic mortar test indicates a power of 79 percent
sensitivity may be increased by the addition of of TNT at a density of 1.0 grams per cubic centimeter.
powdered copper, iron, aluminum, zinc, chromium h. The vacuum stability test at 150°C indicates
oxide, or chromium nitrate. Powdered limestone, ammonium nitrate is a very stable material even at that
kieselguhr, and clay reduce the sensitivity to heat. No temperature. Heating for 100 days at 100°C causes no
explosions occur in the rifle bullet impact test. In the appreciable decomposition. Decomposition does not
sand test, only partial explosion of ammonium nitrate appear to begin until the compound melts. At 220°C
results even if boosted with a charge of tetryl or RDX. nitrous oxide, water, and nitrogen are formed. High
Larger charges, when properly combined, can be temperature decomposition is used to manufacture
detonated by means of a booster charge of tetryl but not nitrous oxide. If an organic material such as cellulose is
by means of a lead azide or mercury fulminate blasting present, decomposition of the mixture begins at 100°C
cap. If ammonium nitrate is unconfined, a number eight and is pronounced at 120°C. The DTA curve for
blasting cap will not cause complete detonation. The ammonium nitrate is shown in figure 8-74 and the TGA
molten material is easier to initiate than the solid and curve is shown in figure 8-75. Admixture with TNT has
the dry material easier to initiate than the moist. The little if any effect on the stability of ammonium nitrate at
sensitivity of ammonium nitrate to initiation decreases temperatures less than 120°C.
with increases in loading density. If the density exceeds
0.9, charges of one to three pounds cannot be
detonated completely by large booster charges. Larger
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FRACTION OF
ORIGINAL SAMPLE
AS A PERCENT OF
WEIGHT
8-6. Compositions. Compositions are explosives in (a) Amatols are binary mixtures of
which two or more explosive compounds are mixed to ammonium nitrate and TNT. The percentages of
produce an explosive with more suitable characteristics ammonium nitrate and TNT are reflected in the
for a particular application. Generally, the nomenclature for each mixture, for example, 80/20
characteristics of the composition are intermediate amatol consists of 80 percent ammonium nitrate and 20
between the characteristics of the individual explosive percent TNT. Ammonium nitrate is insoluble in TNT.
ingredients. For example, the addition of TNT to RDX The chemical and physical properties of the constituents
reduces brisance somewhat but considerably improves determine the properties of the amatol. The mixture
sensitivity. The composition explosives are categorized begins to melt at TNT's melting point but the ammonium
by the number of ingredients contained in the mixture. nitrate, which has a higher melting point, remains solid.
a. Binary Mixtures. The two ingredients may be dissolved separately. Table
(1) Amatols. 8-63 compares the properties of some of the common
amatol compositions. Amatols can be used for shell and
bomb filling.
Amatol composition
Properties 80/20 60/40 50/50 45/55 40/60
Nitrogen content 31.7% 28.4% 26.8% 25.9% 25.1%
Oxygen balance to CO2 + 1.20% - 17.6% -27.0% -31.7% -36.4%
Oxygen balance to CO + 11.06% +2.13% -2.32% -4.55% -6.78%
Color Lt buff Lt buff Buff Buff Buff
Melting point, °C - - 81 - -
Heat of combustion
at constant volume 1,254 - 2,073 - 2,402
Specific heat
20°to 80°C - - 0.383 - -
Heat of detonation with
liquid water at
constant volume in
kilocalories per
gram 1,04-1,200 - 950 - 920
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Other experimental determinations of the velocity of very slight reaction between TNT and ammonium nitrate
detonation yields divergent results from those shown in at those temperatures. At temperatures below the
the table, at least partially due to the variations caused melting point of TNT, there is no evidence of reaction.
by the granulation of the ammonium nitrate. Amatols After storage at 50°C for three months, there is no
have better oxygen balance than TNT producing larger change in the sensitivity, brisance, or stability of 50/50
amounts of gaseous explosion products. This accounts amatol; and many additional months of such storage
for the greater power of the amatols. without effect might be anticipated. The DTA curve for
(e) The stability of 50/50 amatol is a little less 80/20 amatol is shown in figure 8-76. Amatols are
than that of TNT at temperatures of 100° and 120°C as hygroscopic due to the presence of the ammonium
indicated by vacuum stability tests. There evidently is nitrate.
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(f) 50/50 Amatol has an air blast and the granulation requirements for the RDX are
energy of 84 percent of TNT, a water shock energy of different. Composition A contains beeswax, while
94 percent of TNT, and a shaped charge efficiency of 54 composition A2 contains a synthetic wax. Compositions
percent of TNT. A and A2 are no longer used. All of the composition A
(g) Determination of the composition of explosives are press loaded. The density of
amatol can be made by extracting a weighted sample composition A3 is 1.47 and 1.65 grams per cubic
with benzene, drying the residue, and weighing this. centimeter when pressed to 20,685 kilopascals (3,000
The weight of the residue is calculated to percentage of pounds per square inch) and 82,740 kilopascals (12,000
ammonium nitrate and the difference between this and pounds per square inch), respectively. Composition A3
100 percent represents the percentage of TNT. may be completely dissolved in benzene and acetone,
(2) Composition A. when these solvents are used successively. The color
of the composition depends on the color of the particular
(a) Composition A explosives consist of desensitizer used. For composition A3 the heat of
a series of formulations of RDX and a desensitizer. formation is-24.8 to - 28.4 kilocalories per gram and the
Table 8-65 lists the composition of the explosives. heat of detonation is 1,210 kilocalories per gram.
Compositions A and A2 contain the same percentages
of materials as composition A3 but the type of wax used
Ingredients in percent
Desensitizing Stearic
Composition RDX wax acid Polyethylene Comments
A3 91.0±0.7 9.0±0.7 - - High explosive,
projectile filler
A3 type 11 90.8±0.9 - - 9.2±0.9 High explosive,
projectile filler
A4 97.0±0.5 3.0±0.5 - - Boosters
A5 type 1 98.5±0.5 - 1.5±0.5 - Shaped charges,
grenades
A5 type 11 98.0 minimum - 1.6 minimum - Also contains 0.4
percent lubricant
A6 86 14 - - Projectile filler
(b) The manufacture of composition A3 0.25 grams. The flammability index is 195 percent of
is carried out by heating a water slurry of RDX nearly TNT.
100°C and agitating. The wax, which contains a wetting (d) The sand test indicates composition
agent, is added during agitation and agitation is A3 is 107 to 115 percent as brisant as TNT and the plate
continued while the mixture is allowed to cool to a dent test indicates 126 percent. In the fragmentation
temperature less than the melting point of the wax. test a three inch shell containing 0.861 grams of
After being caught on a filter, the composition is air- composition A3 at a density of 1.64 grams per cubic
dried at 77°C. centimeter produced 710 fragments versus 514 for the
(c) The relative impact sensitivity of same weight of TNT. The fragment velocity at a
composition A3 is 125 percent of TNT. There are no distance of 2.75 meters (9 feet) is 853.44 meters per
initiations in the rifle bullet impact test or pendulum second (2,800 feet per second) and at a distance of 7.77
friction test with either the steel or fiber shoe. The five meters (25.5 feet) the fragment velocity is 771.14
second explosion temperature test result is 250°C to meters per second (2,530 feet per second). The
280°C. In the booster sensitivity test, with material detonation velocity for a sample of composition A3 at a
pressed to a density of 1.62 grams per cubic centimeter, density of 1.62 grams per cubic centimeter is 8,100 to
detonations in 50 percent of the trials are caused by 100 8,200 meters per second. The Trauzl test and ballistic
gram tetryl pellets separated from the composition A3 mortar indicate composition A3 is 144 percent and 135
by acrawax B pellets 4.318 centimeters (1.7 inches) percent of TNT, respectively.
thick. The minimum detonating charge of lead azide is
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8-101
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(3) Composition B. percent TNT. Other portions of RDX and TNT are called
(a) Composition B type explosives are cyclotols. Table 8-66 compares the properties of some
mixtures of RDX and TNT. Composition B refers to composition B type explosives.
mixtures of approximately 60 percent RDX and 40
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maximum density of 1.776 grams per cubic centimeter bombs or solidified into chips approximately 4.8 square
and a vacuum melt density of 1.74 to 1.75 grams per centimeters by .6 centimeters. The chips are produced
cubic centimeter. 70/30 Cyclotol has a theoretical when the composition B is to be stored or shipped for
maximum density of 1.765 grams per cubic centimeter use elsewhere.
and an open melt density of 1.71 to 1.73 grams per (e) Impact sensitivity for solid
cubic centimeter. composition B is between that of TNT and RDX. Cast
(c) RDX is slightly soluble in molten composition B is more sensitive than the powdered
TNT and the two compounds form an eutectic mixture material. As judged by the pendulum friction test,
that freezes at 79.0°C and contains 95.84 percent TNT powdered composition B is no more sensitive than TNT,
and 4.16 percent RDX. When heated, RDX undergoes and at 100°C the two explosives show no increase in
some softening at a relatively low temperature because sensitivity to friction. Like TNT, cast composition B can
of the melting of the wax present and further melting at be drilled without undue hazard. The explosion
the eutectic temperature. As the temperature is temperature test value of composition B (270°) is only
increased, some of the RDX is dissolved and at 100°C slightly greater than that of RDX, but the sensitivity of
there are in equilibrium 42.8 parts of molten solution and composition B to electrical sparks is more nearly that of
57.2 parts of solid RDX. The viscosity of composition B TNT than that of RDX. Composition B is intermediate
as cast is an important characteristic that is affected between TNT and RDX in sensitivity to initiation. Cast
markedly by the granulation of the RDX and the nature composition B is somewhat less sensitive to initiation
of the wax used, the wax causing an increase in the than the pressed material. Table 8-67 lists the gap test
viscosity. Representative viscosity values for results for composition B.
composition B at 83° and 95°C are 3.1 and 2.7 poises, (f) Composition B3 behaves
respectively. reasonably well in the Susan test. Ignition occurs at the
(d) Composition B is manufactured beginning of the pinch stage only after extensive
from TNT and water wet RDX. The TNT is melted at splitting and deformation of the nose cap. The threshold
approximately 100°C in a steam jacketed melting kettle velocity is about 55 meters per second. The reaction
equipped with a stirrer. The damp RDX is added slowly level as a function of projectile velocity is shown in
with stirring, and after addition of the RDX is completed, figure 8-79. Even at 457 meters per second the full
most of the water is poured off and heating and agitation potential of the reaction is not released. These results
are continued until all moisture has been driven off. The indicate composition B3 is difficult to ignite by
wax is then added and mixed thoroughly with the other mechanical means and has a low probability for violent
ingredients by stirring. The nature of the wax is reactions once ignited, provided confinement is light.
important since only certain waxes mix with the RDX Composition B3 has been observed to detonate in
and TNT and do not tend to segregate during cooling. impact geometries where there was good inertial
The thoroughly mixed composition B then is cooled with confinement at the time of ignition and where the impact
continued agitation until the fluidity is satisfactory for subjected the charge to mechanical work.
casting. The composition B is either cast directly into
Percent Sensitivity in
Density voids millimeters
LANL small scale gap test:
Composition B, grade A 1.710 (cast) 1.1 0.41 - 0.66
Composition B3 1.721 (cast) 1.8 1.1 - 1.4
75/25 1.753 (cast) 1.1 0.25 - 0.41
LANL large scale gap test:
Composition B, grade A 1.712 (cast) 2.2 44.58
Composition B3 1.727 (cast) 1.4 50.34
75/25 Cyclotol 1.757 (cast) 0.6 43.15
1.734 (cast) 2.2 45.74
PX gap test:
Composition B 1.714 (cast) 2.2 2
8-105
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8-106
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8-107
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8-108
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FRACTION OF
ORIGINAL SAMPLE
AS PERCENT OF
WEIGHT
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(e) The chemical stability of when exposed to air with 90 percent relative humidity at
composition C3 is acceptable, but the physical stability 30°C. Tests have shown composition C3 to be of
is not entirely satisfactory. The results of the 120°C unimpaired brisance after immersion in water for 24
heat test are: 3.20 percent loss in the first 48 hours, 1.63 hours. Storage at 77°C causes considerable exudation.
percent in the second 48 hours, and no explosions in In vacuum stability tests at 100°C and 120°C for 48
100 hours. Composition C3 is volatile to the extent of a hours, 1.21 and 11 + cubic centimeters of gas are
1.15 percent weight loss when exposed to air at 25°C for evolved, respectively. Figure 8-84 shows the DTA curve
five days, and hygroscopic to the extent of 2.4 percent for composition C3.
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(f) In an air blast the peak pressure is the mixture is 1.75 grams per cubic centimeter with a
105 percent of TNT and the impulse is 109 percent of nominal density of 1.72 grams per cubic centimeter.
TNT. The heat of formation is-32.9 to-33.3 calories per gram.
(g) Composition C3 hardens at-29°C The maximum heat of detonation with liquid water is
and has undesirable volatility and hygoscopicity 1.59 kilocalories per gram and with gaseous water 1.40
characteristics, so composition C4 has been developed. kilocalories per gram. Composition C4 remains plastic
The ingredients of the three classes of composition C4 between -57°C and +77°C with no exudation in this
are: temperature range. This explosive is considered a very
satisfactory demolition explosive and has almost entirely
Class I: 61 percent RDX class A or B, type A or B replaced all the other composition C explosives.
30 percent RDX class E, type A or B (h) Composition C4 is manufactured by
9 percent polyisobutylene placing the water wet RDX in a stainless steel mixing
Class II: 92 percent RDX class H, type A or B kettle and adding the plastic binder. The mass is
9 percent polyisobutylene blended by tumbling the kettle until a homogeneous
Class IV: 89.9-1 percent RDX mixture is obtained. The resulting dough is then dried in
10 +1 percent polyisobutylene trays by forced air at 50°C to 60°C. About 16 hours of
0.2+0.02 percent dye composition drying are required to reduce the moisture content to
which consists of: below 0.25 percent.
90 percent lead chromate (i) The detonation characteristics of
10 percent lamp black the composition C explosives are listed in table 8-68.
The detonation pressure is 257 kilobars for composition
Composition C4 is a pufflike material of dirty white to C4 with a density of 1.58 grams per cubic centimeter.
light brown color. The theoretical maximum density of
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(8) Octols.
(a) Octols are mixtures of HMX and
TNT. The properties of the two most commonly used
octols are summarized in table 8-69.
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Type I Type II
Sensitivity to setback pressure in
kilopascals at 71°C
Probability of reaction:
0.1 percent 655,025 551,600
50 percent 820,505 820,505
99.9 percent 1,027,355 1,213,520
0 percent 524,020 634,340
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(b) Octol is used as an oil well formation (c) The gap test results for 75/25 octol are
agent and in fragmentation and shaped charges. In given in table 8-71.
fragmentation tests using a 105 millimeter M1 shell, 15 (d) As shown in figure 8-87, 75/25 octol has
percent more fragments are produced and the average both good and bad properties. The threshold velocity
velocity of the fragments is 100 meters per second for reaction is about 55 meters per second which is
faster than with a similar shell loaded with composition typical of TNT bonded cast explosives. On the other
B. This improvement is attributed to both the higher hand reaction levels become moderately high at
rate of detonation of octol and the greater density of relatively low velocity. The variability of results is less
octol which permits a greater weight of explosive in the than that observed with 75/25 octol. This data indicates
same volume. Table 8-70 compares the performance of 75/25 octol is rather difficult to ignite accidentally by
TNT, composition B, and octol in producing craters in a mechanical means but capable of a large reaction once
105 millimeter shaped charge shell. ignited under some conditions.
(e) In the manufacture of octols, TNT is
Table 8-70. Crater Volume in Mild Steel Targets melted in a steam jacketed kettle equipped with an
agitator. The temperature of the TNT is maintained at
Depth of Volume in cubic centimeters about 100°C and water wet HMX is added slowly.
penetration in Stirring is continued until the water is driven off. The
centimeters kettle temperature is then reduced until a viscosity
Compo- suitable for casting is obtained. The viscosity of the
TNT sition B Octol slurry has a strong dependence on the particle size
4 23.8 33.1 37.0 distribution and polymorphic variety of HMX used. In
8 36.2 49.7 57.4 order for the slurry to have an efflux time of less than 15
12 43.2 61.4 68.9 seconds the solid HMX must consist of the beta
16 49.1 69.2 78.7 polymorph having particle diameters in the range of 500
20 53.0 75.1 85.0 to 800 microns. Even when octol is cast at a
24 56.2 79.4 89.9 temperature of less than 90°C, there is a large amount
28 58.6 83.0 94.0 of settling of HMX crystals while the charge is still
32 61.8 86.2 98.1 molten. This can lead to erratic performance of the
36 64.3 89.3 101.8 ammunition loaded. Several methods to prevent the
40 - 92.3 105.3 settling are being considered. Casting temperature is
44 - - 110.4 kept as low as possible to prevent air entrapment in the
cast. Figure 8-88 shows the DTA curve for 75/25 octol.
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The presence of rust or grit increases the sensitivity of withstands 10 remelting operations at approximately
pentolite. A mixture of equal weights of pentolite and 98°C without becoming unduly instable or unduly acid,
dry rust has an impact test value of 21 centimeters but subsequent storage at 65°C for six months renders
compared with 32 centimeters for the pentolite used to the sample unduly acid. Slow decomposition starts at
make the mixture. 110°C and is followed by the main pyrolysis reactions
(e) Sand test shows 50/50 pentolite to be as which generate NO2 rapidly. The rate of the pyrolysis of
brisant as tetryl and 114 percent as brisant as TNT. the mixture is faster than that of either TNT or PETN.
Fragmentation tests of shell charges, however, show While storage at 65°C has only a limited effect on the
pentolite to be 13 percent as brisant as TNT and plate chemical stability of pentolite, some exudation occurs
dent tests indicate the ratio to be 126 percent. The for storage temperatures above 50°C. This may be due
approximate velocity of detonation as a function of to the formation of a eutectic mixture of TNT and
packing density is given by the equation: impurities in PETN. One of the impurities present in
D =5480 +3100(p -I) PETN is dipentaerythritol hexanitrate, which melts at
73.6°C and forms a eutectic mixture with TNT that
where D is in meters per second and p, the density, is in freezes at only 57.9°C.
grams per cubic centimeter. This ideal velocity of
(g) Because of the somewhat lower stability
detonation is applicable to charges with a diameter of
and greater sensitivity of PETN as compared with RDX,
one inch. The variation in detonation velocity as a
the corresponding relationship of pentolite to
function of temperature is given by the equation:
composition B, and the tendency of pentolite to undergo
D-Do =(-0.4x10 -3)(T-To) some exudation above 50°C, pentolite has generally
where T is in degrees centigrade and D is in millimeters been replaced by composition B. Figure 8-89 shows the
per microsecond. Do is the initial detonation velocity at DTA curve for pentolite.
temperature To, and D is the detonation velocity at (h) The composition of pentolite is
temperature T. The Chapman-Jouquet detonation determined by extracting a weighed sample with
pressure is 232 to 255 kilobars. In deflagration to chloroform saturated with PETN, drying the residue, and
detonation transfer studies with pentolite that is heavily weighing. The weight of the residue and the loss in
confined and ignited by a hot wire, a low velocity weight are calculated to percentage of PETN and TNT,
detonation regime precedes steady state detonation for respectively.
30 to 80 microseconds. Compression waves precede
(i) Underwater blast for pentolite with a
the burning front in this predetonation region and appear
density of 1.6 grams per cubic centimeter are given by
to coalesce into a shock front. The Trauzl test indicates
the equations:
50/50 pentolite is 122 percent as powerful as TNT while
the ballistic mortar test indicates a power of 126 percent
of TNT. Peak pressure=2.25x 104(W1/3/R)1.3 psi
1/3 1/3 1.05
(f) Vacuum stability tests indicate 50/50 Impulse=2.18W (W /R) psi-sec
pentolite is slightly less stable than PETN although Energy=3.27x 10 W (W /R)2.12 inch lb/inch2
3 1/3 1/3
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where W is the charge weight in pounds and R is the picrate as measured by vacuum stability tests at 1000,
distance in feet from the center of a spherical charge. 1200, ar,d 150°C.
The ratio of underwater shock energy of pentolite to the These test results may indicate slight reaction between
total chemical energy is 0.57 to 0.59. the ammonium picrate and the molten TNT ingredients
at the elevated temperatures of the tests. At ordinary
temperatures, there is no evidence of such reaction and
(10) Picratol.
picratol appears to be of the same high order of stability
(a) Picratol is a mixture of 52 percent as its ingredients.
ammonium picrate and 48 percent TNT. Molten TNT
(f) The composition of picratol can be
has little or no solvent action on ammonium picrate, and
determined by extracting a weighed sample with cold
consequently, cast picratol consists essentially of a
ether that has been saturated with ammonium picrate.
physical mixture of crystals of the two explosives. The
The residue is dried and weighed and this and the loss
density of cast picratol is 1.61 to 1.63. This permits a
in weight are calculated to percentage of ammonium
weight of charge almost equal to that of ammonium
picrate and TNT, respectively.
picrate pressed under 68,950 to 82,740 kilopascals
(10,000 to 12,000 pounds per square inch). The
solubility and reactivity characteristics of picratol are (11) Tetrytols.
essentially that of the two ingredients. (a) Tetrytols are light yellow to buff mixtures
(b) Picratol is manufactured by heating TNT of TNT and tetryl. As is the case for tetryl, tetrytols are
to above 90°C in a steam jacketed melting kettle no longer used by the United States but are still being
equipped with a stirrer. The ammonium picrate is added used by other nations including various NATO allies.
slowly, without preheating, with continuous agitation and Tetrytols resemble tetryl more closely than they
this is continued for a short time after all the ammonium resemble TNT.
picrate has been added. The thick slurry is allowed to They are more powerful but less sensitive than TNT.
cool to about 85°C before being loaded into ammunition Tetrytols can be cast into munitions, which is an
components. Like molten TNT, picratol undergoes advantage over press loading. Table 8-73 compares
marked contraction in volume upon solidification. The the physical characteristics of various tetrytol
contraction is much less than in the case of TNT. compositions.
(c) The standard small scale impact tests The pressed density listed is for material that passed
indicate picratol to be as sensitive to impact as TNT, through a number 100 US standard sieve and was
rather than ammonium picrate and large scale impact subjected to a pressure of 20,685 kilopascals (3,000
tests of cast charges confirm this. Pendulum friction pounds per square inch). 70/30 Tetrytol is the most
tests show no difference between picratol, TNT, and commonly used form and has a voidless density of 1.71
ammonium picrate with respect to sensitivity to friction. grams per cubic centimeter. All of the tetrytols are
When subjected to the rifle bullet impact test, picratol subject to exudation above 65°C. TNT and tetryl form a
burns in about 40 percent of the trials but undergoes no eutectic mixture that has a freezing point of 67.5°C.
detonation. Ammonium picrate burns in about 30 The solubility characteristics and chemical reactivity of
percent of the trials. The explosive temperature test the tetrytols are essentially those of the individual
value of picratol, 285°C, is less than that of ammonium ingredients.
picrate, 318°C, and much less than that of TNT, 475°C. (b) Tetrytol is manufactured by heating TNT
Picratol is as insensitive to initiation as ammonium in a melting kettle equipped with an agitator until all the
picrate, having a minimum detonating charge value of TNT is melted and the temperature of the liquid slightly
0.06 gram of tetryl. The overall sensitivity of picratol, exceeds 100°C. The proper amount of tetryl is then
therefore, is not greater than that of TNT. added with continued stirring. Part of the tetryl
(d) 52/48 picratol is only 94 percent as brisant dissolves in the TNT. The temperature is then allowed
as TNT, as judged by the sand test, but the plate dent to decrease until the mixture has thickened somewhat
test indicates the two to be equally brisant, and the and is considered to be of the maximum viscosity
fragmentation of shell charges show picratol to be 102 suitable for pouring in the melt loading operation. The
percent as brisant as TNT. The rate of detonation of tetrytol is then poured into the ammunition component
cast picratol is 101 percent that of cast TNT. Picratol or a mold. As cast, tetrytol is a mixture of tetryl and the
and TNT are of equal power, as measured by the TNT-tetryl eutectic. The eutectic contains
ballistic pendulum test, and have equal blast effects. approximately 55 percent tetryl.
TM 9-1300-214 (e) The stability of picratol is very
slightly less than that of either TNT or ammonium
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(c) There is no difference in the impact grams per cubic centimeter has a brisance of 117
sensitivity of 65/35, 70/30, or 75/25 tetrytol. All are less percent of TNT. The sand test indicates 70/30 tetrytol is
sensitive than tetryl and more sensitive than TNT. All 97.5 percent and 111 percent as brisant as tetryl and
tetrytols are unaffected by the steel and fiber shoes in TNT, respectively. The following detonation velocities
the pendulum friction test. The rifle bullet impact test, in were measured in one inch diameter charges without
which a 30 caliber bullet is fired into the open end of a confinement. For cast 75/25 tetrytol with a density
pipe confined charge, yields the following results: range of 1.55 to 1.60 grams per cubic centimeter and an
average of 1.57 grams per cubic centimeter, the
Partially measured detonation velocities ranged from 7,290 to
Unaffected affected 7,410 meters per second with an average of 7,350
percentage percentage meters per second. For cast 65/35 tetrytol with a density
80/20 Tetrytol 80 20 range of 1.56 to 1.61 grams per cubic centimeter and an
75/25 Tetrytol 70 30 average of 1.58 grams per cubic centimeter, the
70/30 Tetrytol 45 55 measured detonation velocities ranged from 7,310
65/35 Tetrytol 90 10 meters per second to 7,370 meters per second with an
average of 7,340 meters per second. The ballistic
In a wax gap test 75/25 tetrytol is somewhat more mortar test indicates 75/25 and 70/30 tetrytols are 122
sensitive than composition B, but appreciably less percent and 120 percent of TNT, respectively.
sensitive than pentolite. The following shows the (e) 70/30 Tetrytol is slightly less stable than
minimum priming charge required for the tetrytols. tetryl at 100°C and higher temperatures, as shown by
vacuum stability tests. However, at 65°C and lower
Grams temperatures, samples have been stored for two years
Grams mercury with no change in stability, acid content, sensitivity, or
lead azide fulminate brisance. Although tetryl undergoes partial
80/20 Tetrytol 0.17 0.22 decomposition on melting, the melting of tetrytol does
75/25 Tetrytol 0.19 0.23 not have the same effect. Tetrytol that has been melted
70/30 Tetrytol 0.22 0.23 and solidified 12 times shows no change in freezing
65/35 Tetrytol 0.23 0.23 point, sensitivity to impact, or 100°C vacuum stability
test value although the temperature was each time
raised to 107°C and maintained at that value for half an
For a priming charge of diazodinitrophenol (DDNP) the hour prior to solidification by cooling. Storage at 65°C
minimum charge required is 0.19 grams for pressed causes some separation of an oily extrudate and
75/25 tetrytol at a density of 1.4 grams per cubic distortion of blocks of tetrytol, so the maximum storage
centimeter and 0.31 grams for cast 75/25 tetrytol. temperature is less than 65°C. This low storage
(d) In the plate dent test the brisance of 75/25 temperature has caused the United States to
tetrytol at densities of 1.66 grams per cubic centimeter discontinue the use of tetrytol. Tetrytol
and 1.62 grams per cubic centimeter is 118 percent and
114 percent of TNT, respectively. 70/30 Tetrytol at 1.60
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is incompatible with 3M adhesives EC8708 and (c) 80/20 Tritonal is manufactured from TNT
EC1099. Dry tetrytol is compatible with copper, brass, and grained aluminum. The TNT and aluminum are run
aluminum, magnesium, stainless steel, mild steel coated slowly through separate chutes into a steam heated
with acid proof paint, and mild steel plated with copper, melting kettle equipped with a stirrer which is kept in
cadmium, zinc or nickel. Magnesium-aluminum alloys motion while the ingredients are being added. Heating
are slightly affected by dry tetrytol. Wet tetrytol is and mixing are continued until all the TNT is melted, the
compatible with stainless steel and mild steel coated temperature is greater than 81°C, and the fluidity of the
with acid proof black paint. Copper, brass, aluminum, mixture is considered satisfactory. The tritonal is then
magnesium, magnesium-aluminum alloy, mild steel, loaded by pouring into bombs, using at least the same
and mild steel plated with cadmium, copper, zinc, or precautions and techniques used in the melt loading of
nickel are slightly affected by wet tetrytol. TNT.
(f) The shaped charge effectiveness of 70/30 (d) Although the pendulum friction test shows
tetrytol at a density of 1.64 grams per cubic centimeter, no measurable difference in sensitivity between tritonal
as gauged in a constant volume test, is appreciably and TNT, impact tests indicate tritonal to be somewhat
lower than composition B, octol, and composition A, more sensitive to impact that TNT and less so than
when all are at roughly equivalent packing densities. tetryl. The rifle bullet impact test value for tritonal is
60/40 Tetrytol is as efficient a shaped charge filler as more similar to that of tetryl than that of TNT. The
50/50 pentolite and somewhat better than TNT. Both explosion temperature test value of tritonal, 470°C, is
75/25 and 65/35 tetrytols are approximately 1.2 to 1.25 almost identical with that of TNT. Liquid tritonal at 90°C
times more effective shaped charge fillers than TNT. is slightly more sensitive than the solid, as judged by
(g) Determination of the composition of a rifle bullet impact tests. As indicated by the sand test,
sample of tetrytol can be made by treating a weighed the minimum detonating charge of lead azide, 0.30
sample with sufficient boiling carbon tetrachloride to gram, is slightly greater than that required for TNT.
dissolve the TNT present, cooling to 0°C, evaporating a Nonstandard initiation sensitivity tests with
weighed portion of the solution to dryness, and diazodinitrophenol as the initiator show tritonal and TNT
correcting for the amount of tetryl dissolved by the to be of essentially the same sensitivity to initiation.
carbon tetrachloride at 0°C. (e) The sand test indicates 80/20 tritonal is
(12) Tritonal. 108 to 114 percent as brisant as TNT. The plate dent
(a) Tritonal is a silvery solid that contains: test and the fragmentation test indicate a brisance of 93
percent and 91 percent of TNT respectively. The rate of
TNT 80 percent detonation of cast tritonal is approximately 97 percent
Flaked aluminum 20 percent that of cast TNT. The heat of explosion of tritonal is 59
percent greater than that of TNT, but tritonal is only 124
percent as powerful as TNT, as measured by the
Metallic aluminum is insoluble in TNT so tritonal begins
ballistic pendulum test. The Trauzl test indicates tritonal
to melt at the melting point of TNT. Tritonal has a heat
is 153 percent as powerful as TNT.
of combustion of 4,315 calories per gram per degree
centigrade at constant pressure and a thermal (f) As tritonal has the same 150°C vacuum
conductivity of 0.0011 calories per gram per degree stability test value as TNT, aluminum and TNT do not
centigrade at 0°C. These values are 120 percent and react at that or lower temperatures. Tritonal, therefore,
200 percent of those for TNT. At 20°C the calculated has the same stability as TNT, if free from moisture.
specific heat is 0.305 calorie per gram per degree Deterioration in the presence of moisture is not serious,
centigrade. Like TNT, tritonal undergoes considerable probably because the formation of a layer of oxide on
expansion on melting and contraction on freezing. The the surface of the particles of aluminum prevents or
solubility characteristics of tritonal are essentially those retards further reaction. Tritonal, like TNT, can undergo
of TNT. Tritonal is used as a filler in bombs and shells. exudation if stored at elevated temperatures, but this
The density of the cast material is 1.73 grams per cubic tendency is less than that of TNT because of the
centimeter. presence of 20 percent by weight of metallic particles
(b) The chemical reactivity of tritonal is that that tend to hold oily exudate by surface tension. This
of TNT and aluminum. In addition in the presence of prevents the oily exudate from coalescing and exuding.
moisture, the TNT and aluminum undergo slight reaction (g) When tested for blast effect, tritonal has a
with the evolution of gas. This is not of practical peak pressure of 113 percent of TNT and an impulse
importance because of the very slight hygroscopicity of value of 118 percent of TNT.
TNT and the fact that any moisture present is driven off
by heat during the manufacture of tritonal.
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(h) The composition of a sample of tritonal is Both these reactions are highly exothermic and develop
determined by extracting a weighed sample with much additional heat which causes greater expansion of
benzene, drying the residue, and weighing the sample. the gases and consequently greater blast effect.
The loss in weight represents TNT and the weight of Many different combinations of ingredients have been
residue represents aluminum. Each is calculated to a used, both militarily and commercially. The most recent
percentage basis. United States military ammonal consists of 22 percent
ammonium nitrate, 67 percent TNT, and 11 percent
b. Ternary Mixtures. flaked aluminum. The oxygen balance of the compound
(1) Amatex 20. is 55 percent to CO2 and 22 percent to CO. The major
(a) Amatex 20 consists of: use of this composition is as a projectile filler.
RDX 40 percent (b) As in the case of ammonium nitrate in
TNT 40 percent amotols, the ammonium nitrate of ammonals might be
Ammonium nitrate 20 percent hydrolyzed in the presence of moisture with the
formation of ammonia but, due to the presence of
The mixture has a nominal density of 1.61 grams per aluminum, the amount of ammonia will be much
cubic centimeter and is used as a filler in ammunition greater. This amount might be as much as three times
items. greater with ammonals than with 80/20 amatol. The
ammonia reacts with TNT to form a complex addition
(b) Amatex 20 is slightly less sensitive than compound which ignites at 67°C. In addition, the
TNT, with impact test results of 15 to 18 inches on the reaction between aluminum and moisture produces
Picatinny Arsenal apparatus. In the rifle bullet impact hydrogen, which is highly inflammable in oxygen or
test of 100 trials, six detonated low order, three burned, compounds containing oxygen.
and the rest are unaffected. The relative gap test value (c) The general effect of incorporating
is 105 percent of TNT. The five second explosion aluminum in ammonium nitrate/TNT mixtures is as
temperature is 240°C. follows:
(c) The detonation velocity at 1.61 grams per
cubic centimeter is 6,944 meters per second, although 1. Increase in sensitivity to impact,
values of 6,830 meters per second at a density of 1.68 friction, and rifle bullet impact.
grams per cubic centimeter have been reported. A 2. Increase of temperatures of
detonation pressure of 240 kilobars has been reported detonation from about 1,700°C to about 3,914°C to
for a charge with a density of 1.68 grams per cubic 4,000°C.
centimeter. The ballistic mortar test indicates amatex 3. A 20 percent increase in power.
20 is 110 percent as powerful as TNT. Vacuum stability
4. An increase in some cases of the
tests indicate amatex 20 is a highly stable explosive.
total volume of gas evolved on detonation.
(2) Ammonal.
5. A decrease in velocity of detonation
(a) Ammonals are mixtures containing, as and brisance.
principle ingredients, ammonium nitrate and powdered
(d) Ammonals are manufactured by a method
aluminum incorporated with high explosives such as
similar to that used for the preparation of amatols. The
TNT, DNT, and RDX. Powdered carbon was also used
calculated amount of TNT is placed in a kettle that is
in earlier ammonals. In the ammonals that do not
equipped with an agitator and steam jacket.
contain carbon, the mixture of ammonium nitrate and
high explosive detonates developing a very high The temperature of the kettle is raised to between 85°C
temperature which causes volatilization of the aluminum and 100°C. The calculated amount of ammonium
powder. Secondary reactions which follow involve the nitrate, which was previously heated to the same
oxidation of the vaporized aluminum, either by the air, if temperature as the contents of the kettle, is then added.
oxygen is present, or by the products formed on Finally aluminum powder is added and the mass cooled
detonation of TNT and ammonium nitrate according to while continuing the agitation. If the ammonal mixture
the following equations: contains less than 40 percent TNT, press loading is
3CO2 +2AI A1203+3CO necessary. For compositions with more than 40 percent
3H2O +2AI A1203+3H2 TNT, the mixture can be cast loaded.
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Change 4 8-125
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(2) Much of the advantage stemming from curing agent such as methyl ethyl ketone peroxide is
the use of PBX lies in the simplicity of the technique of then added. After another short mixing period, the
end item manufacture. About half of the developed explosive composition is poured into the desired mold.
PBX composites are used to directly cast end items. Vacuum casting has not been found necessary to obtain
For this procedure no elaborate melting equipment or good density provided that the mold design is not too
controlled cooling cycles are required. All operations intricate or the height-to-diameters ratio not too great.
may be conducted at ambient temperatures or, in some Another method of casting is called injection molding.
instances, can even be carried out in the field. This method is used to produce intricate shaped or small
However, where extraordinary mechanical strength is diameter castings. The PBX usually employed with this
required or where complicated shapes are desired, a technique has a high solid content of explosive such as
pressing or injection technique is applied using a PETN, which provides for steady state detonation in
molding powder or slurry of the PBX. The final PBX small cross-sectional channels or tubes. This method
product not only exhibits excellent technical properties was developed by the Navy to provide explosive logic
but also has the economical advantages of low links of less than .25 centimeters in diameter. Figure 8-
processing costs and the ready availability of all 91 illustrates the injection molding process. The
constituents from commercial sources. technique of injection molding involves movement of
In currently evolved compositions, recycling and explosive material at room temperature into a cavity or
disposal present no special difficulties because tubing from a reservoir. This is accomplished by
thermally degradable binders are used. Ideally, the applying about 82,740 kilopascals (12,000 pounds per
binders undergo controlled thermal degradation so that square inch) to the piston. This forces the explosive into
the material can be easily removed from explosive the cavity or tube. When the accepting device is full,
casings for the purpose of efficient recycling of the base pressure on the piston is relaxed and flow stops. The
explosive or low pollution disposal of the entire item. device is then removed and set aside to allow the
(3) Several manufacturing procedures are explosive to polymerize into an elastic, rubber-like solid.
currently used to produce PBX's. One of these A second manufacturing technique produces a molding
techniques is that of casting. This procedure, at first powder which is pressed into the desired end item shape
glance, merely involves combining a dried explosive, under pressure in excess of 206,850 kilopascals (30,000
such as HMX, with binder constituents and curing pounds per square inch). A slurry method can be used
initiators in a mixing vessel, blending to desired to prepare RDX type PBX's. In this method 42.5 grams
homogeneity, then casting into a given warhead or other of polystyrene and eight cubic centimeters of
ordnance item. Unfortunately, there are hazards dioctylphthalate were dissolved in 200 cubic centimeters
associated with the drying of large quantities of of toluene in a lacquer dissolver. Steam is introduced
explosives such as HMX or RDX. Hence, a into the jacket until the temperature is 65°C. The
desensitizing procedure must be added for production- lacquer is agitated constantly then added to a
scale operations. This procedure involves coating the granulator. This lacquer contains a four to one ratio of
water wet HMX or RDX with the alkyd or polyester plastic-plasticizer to toluene. The granulator which is
portion of the binder. The resulting lacquer is added agitated at 400 revolutions per minute, contains 450
slowly to an aqueous slurry of the HMX or RDX. grams of RDX and 4,500 grams of water which has been
Agitation at 250 revolutions per minute in the presence heated to 75°C. The lacquer solution is poured into the
of water causes the resin to precipitate onto the surface granulator followed by a solution of gelatin in water.
of the HMX or RDX, producing an insensitive powder Mixing is continued for five minutes to insure the RDX is
which may be safely dried, handled, shipped, and stored well dispersed. Granulation takes place at this point.
until ready for use in the final PBX composition. The Steam is introduced into the jacket again to distill the
precoated explosive is then combined in a mixing kettle solvent until the temperature reaches 98°C. Cooling
with sufficient copolymer to constitute the final binder water is then run into the jacket to cool the batch to
composition. At this point an accelerator such as cobalt 40°C. The coated material from the granulator is
naphthenate is added. The mixture is then stirred until collected on a Buchner funnel and dried in a tray at
homogeneous, at first under ambient pressure and 70°C for 24 hours.
finally in a partial vacuum to remove entrapped air. A
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These possess greater density and water resistance of detonation and heaving force values that render them
than straight active dope dynamites and so are more suitable for various types of blasting operations. At the
suitable for use under wet conditions. same time care must be taken that the compositions are
(c) The cost of glycerin and the tendency of oxygen balanced when the paraffined paper wrapper is
nitroglycerin to freeze at some atmospheric taken into consideration. Compositions overbalanced
temperatures prompted the partial replacement of with respect to oxygen produce nitrogen oxides on
nitroglycerin by antifreeze materials such as nitrated detonation while underbalanced compositions produce
diglycerin, sugars, and glycols. Antacid materials such some carbon monoxide instead of carbon dioxide.
as calcium carbonate or zinc oxide have been added to While many of the commercial dynamites are given
most dynamite compositions to neutralize any acidity strength designations on a percentage basis, this no
developed during storage. The inclusion of special longer means that they contain that percentage of
purpose ingredients such as sulfur, ferrosilicon, alum, nitroglycerin or have the same characteristics as a
nitrotoluenes, sodium chloride, copper sulfate, etc and mixture of kieselguhr and nitroglycerin containing that
the substitution of starch, ground peanut hulls, percentage of nitroglycerin. Representative
vegetable ivory, etc, for wood pulp have further compositions and characteristics of the various types of
increased the complexity of dynamite compositions. dynamite are given in table 8-77.
Usually, they are formulated so as to have certain rate
Straight dynamites:
Nitroglycerin 20.2 29.0 39.0 49.0 56.8 -
Sodium nitrate 59.3 53.3 45.5 34.4 22.6 -
Carbonaceous fuel 15.4 13.7 13.8 14.6 18.2 -
Sulfur 2.9 2.0 - - - -
Antacid 1.3 1.0 0.8 1.1 1.2 -
Moisture 0.9 1.0 0.9 1.2
Rate of detonation, m/sec 3,600 4,300 4,800 5,150 5,900 -
Ballistic pendulum, percent TNT 83 90 94.5 102.5 114 -
Ammonia dynamites:
Nitroglycerin 12.0 12.6 16.5 16.7 22.5 -
Sodium nitrate 57.3 46.2 37.5 25.1 15.2 -
Ammonium nitrate 11.8 25.1 31.4 43.1 50.3 -
Carbonaceous fuel 10.2 8.8 9.2 10.0 8.6 -
Sulfur 6.7 5.4 3.6 3.4 1.6 -
Antacid 1.2 1.1 1.1 0.8 1.1 -
Moisture 0.8 0.8 0.7 0.9 0.7 -
Rate of detonation, m/sec 2,700 - 3,300 3,900 4,600 -
Ballistic pendulum, percent TNT 81 - 91 99 109 -
Gelatin dynamites:
Nitroglycerin 20.2 25.4 32.0 40.1 49.6 91.02
Sodium nitrate 60.3 56.4 51.8 45.6 38.9 -
Nitrocellulose 0.4 0.5 0.7 0.8 1.2 7.9
Carbonaceous fuel 8.5 9.4 11.2 10.0 8.3 -
Sulfur 8.2 6.1 2.2 1.3 - -
Antacid 1.5 1.2 1.2 1.2 1.1 0.9
Moisture 0.9 1.0 0.9 1.0 0.9 0.2
Rate of detonation, m/sec 4,000 4,600 5,150 5,600 6,200 7,400
Ballistic pendulum, percent TNT 70 - 74 79 84.5 - 86 90.5 - 93 99 - 101 143
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(d) In addition to military dynamite (h below), when heated at 100°C for 48 hours and must have a
dynamites of the types described may be used for density of 1.75+0.10 when pressed.
military operations and are procured as commercial (f) Nitrostarch demolition explosive is
items. A composition having great heaving force and sensitive with respect to crumbling or breaking action.
relatively low rate of detonation is preferable for blasting No explosions occur in the pendulum friction test but
soft rock or earth, while a gelatin dynamite of low explosions do occur in the rifle bullet impact test. The
heaving force and high rate of detonation is used for initiation sensitivity is slightly greater than that of TNT.
hard tough rock. The sand test indicates a brisance of 90 percent of TNT
(e) A special demolition explosive and the ballistic pendulum test indicates a power of 96
standardized shortly before World War II is based on percent of TNT. The explosive is hygroscopic to the
nitrostarch instead of nitroglycerin. The explosive is extent of 2.1 percent when exposed to air of 90 percent
pressed into 1/4-pound pellets which are covered with relative humidity at 30°C. Long term storage tests
paper and one pound packages of the pellets are indicate a satisfactory stability. Some volatilization,
wrapped in paper with markings indicating the location rather than decomposition, occurs in the 100°C heat test
of holes for blasting caps in the pellets. The in 96 hours. A weight loss of one percent with no signs
composition used is as follows: of deterioration is reported in the 75°C international test.
Percent (g) During World War II, a cratering explosive
with the following composition was used.
Nitrostarch 34.5 +2.5
Barium nitrate 43.5 +1.5 Percent
TNT 15.0 +2.0 Ammonium nitrate 86.6
Aluminum 3.0 + 1.0 Dinitrotoluene 7.6
Graphite 2.0 + 1.0 Ferrosilicon 5.7
Coal dust 1.5 +0.5 Red dye 0.1
Paraffin 0.6 +0.6
Dicyandiamide 1.0 +0.5 This inexpensive and easily manufactured explosive is
Moisture 0.75 +0.75 very insensitive to shock and initiation, has a low rate of
detonation but high heaving force value, and is very
The barium nitrate is coated with the paraffin before the stable. As it is somewhat hygroscopic in spite of the
ingredients are mixed together and pressed into pellets. moistureproofing action of the dinitrotoluene, the
The composition must not undergo ignition or explosion explosive is packed in hermetically sealed containers.
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(h) Military dynamite M1, M2, and M3 is a (b) Extremely insensitive to initiation, ANFO
medium velocity (6,096 meters per second) blasting requires a high explosive booster containing 50/50
explosive in three cartridge sizes. Military dynamite M1, pentolite, composition B, or other similar high explosive.
M2, and M3 has been standardized for use in military Sensitivity does vary somewhat with oil content. The
construction, quarrying, and service demolition work. maximum sensitivity is at about two to four percent, with
The explosive composition is packaged in standard a substantial reduction for greater concentrations of oil.
dynamite cartridge waxed-paper wrappers. The models Sensitivity is decreased by the presence of water, but
differ only in the cartridge size. Cartridges are 1 1/4 decreasing the particle size or density of the ammonium
inches in diameter by 8 inches long for the M1, 1 1/2 nitrate prills increases sensitivity.
inches in diameter by 8 inches long for the M2, and 1
(c) The energy produced upon detonation is
1/2 inches in diameter by 12 inches long for the M3.
comparable to the energy produced by some of the less
The composition used is: Percent
powerful military explosives, however, the detonation
velocity is only about 4,300 meters per second in large
RDX 75 +1.0 diameter charges. With six percent oil, the detonation
TNT 15+0.5 velocity is at maximum, but maximum energy is
Grade SAE No. 10 engine oil plus 5 +0.5 obtained with 5.5 percent oil. Increased charge
polyisobutylene diameter, up to about 13 centimeters, and confinement
Cornstarch 5 +0.5 causes an increase in the velocity of detonation.
Desensitized RDX, which is coated with engine oil (3) Water gel and slurry explosives.
before mixing with the other ingredients, and grained (a) Along with ANFO explosives, the water
TNT are used in the manufacture of the dynamite. gel and slurry explosives have virtually replaced
Military dynamite M1, M2, and M3 is equivalent in dynamite in mining operations. Water gel and slurry
strength to 60 percent commercial dynamite. The explosives have a higher energy content than ANFO,
military dynamite is safer to transport, store, and handle smaller critical diameter, and can be used in wet
than 60 percent straight nitroglycerine commercial conditions. The gel explosives consist of ammonium
dynamite and is relatively insensitive to friction, drop nitrate with or without other oxidizing agents, explosive
impact, and rifle bullet impact. The composition or nonexplosive sensitizers, fuels, and gelatin forming
remains plastic at 57°C after 24 hours. Military compounds in an aqueous medium. Slurry explosives
dynamites are odorless, free from nitroglycerin toxicity, contain the same ingredients with additional compounds
nonhygroscopic, and chemically stable when exposed to that bond the solid particles and prevent water from
80 percent relative humidity at 71°C for one month. No defusing in and out of the slurry. The explosive
freezing occurs in cold storage or exudation in hot sensitizers are such compounds as pentolite, TNT,
storage. Turning of shipping containers during storage methylamine nitrate, smokeless powder, and nitrostarch.
is not necessary. Nonexplosive sensitizers can be finely granulated
aluminum, gas bubbles in suspension, gas contained in
(2) Ammonium nitrate fuel oil explosives (ANFO). small glass spheres, and porous solids. The fuels
include coal dust, urea, sulfur, and various types of
(a) When ammonium nitrate is mixed with
hydrocarbons. The gelatin forming compounds include
approximately 5.6 percent of a combustible material
guar gums, carboxymethyl cellulose, resins, and
such as fuel oil, the heat liberated on detonation is
synthetic thickeners. The viscosity of the mix can be
increased by almost three-fold. The reaction proceeds
altered by the addition of cross linking agents like
according to the equation:
sodium tetraborate and potassium dichromate.
Glycerol, methanol, and diethylene glycol may be added
3NH4NO3+(CH2)n as antifreezes.
3N2+7H2O +CO2+102.5 kilocalories per gram (b) The detonation characteristics of the
water and slurry explosives vary considerably with the
composition of the slurry. Detonation velocities vary
from 4,300 to 6,050 meters per second and detonation
pressures vary from 60 to 104 kilobar.
8-135(8-136 blank)
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CHAPTER 9
UNITED STATES PROPELLANTS
Nitrocellulose (NC), % 85.00 77.45 81.95 87.00 52.15 98.00 20.00 28.00 100.00 80.00
%/o Nitrogen in NC % 13.15 13.25 13.25 13.15 13.25 13.15 12.60 12.60 13.15 13.15
Nitroglycerin,% - 19.50 15.00 - 43.00 - 19.00 22.50 - 10.00
Barium nitrate, % - 1.40 1.40 - - - - - - -
Potassium nitrate, % - 0.75 0.75 - 1.25 - - - - -
a a -
Potassium sulfate, % - - - - - 1.00 - - 1.00
Lead carbonate, % - - - - - - - - - -
Nitroguanidine, % - - - - - - 54.70 47.70 - -
Dinitrotoluene, % 10.00 - - 10.00 - - - - 8.00b -
9-1
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a. The single-base propellants shown in table 9-2 d. Composite propellants, used in solid fuel
are M1, M6, M10, and IMR. Nitrocellulose is the rockets, contain a polymer binder, a fuel, and an
principal energetic material. These are low cost oxidizer.
propellants that have a low flame temperature and low
energy content. To reduce the flame temperature and 9-3. Thermochemistry. Thermochemical properties
barrel erosion, recent formulations of the IMR are prime considerations in formulating a propellant for
propellants do not use dinitrotoluene. Ethylene a specific application. The thermochemical properties
dimethacrylate and methyl centralite are among the include the flame temperature of the gases produced by
replacement materials which produce much lower flame the propellant under certain standard conditions, their
temperatures. IMR is considered a single-base average molecular weight, and covolume. The
propellant even though the formulation contains a small commonly used equation of state used with the
amount of nitroglycerin. combustion products of gun propellants (for gun
b. The double-base gun propellants shown in table applications) is:
9-2 are M2, M5, M8 and M18. In these formulations the P(V -b) =nRT
nitrocellulose is gelatinized by nitroglycerin. The
presence of an active gelatinizer makes double-base where P is the pressure, V is the volume, b is the
propellants more energetic than single-base propellants. covolume, n is the number of moles of the gas per unit
The ballistic potential is increased correspondingly. The mass, R is the universal gas constant, and T is the
flame temperature and resulting barrel erosion is also temperature. The ideal gas equation of state is obtained
increased. Other aliphatic nitrate esters are also used to in the case where b equals zero. The covolume is a
gelatinize the nitrocellulose. DEGN is the most widely correction factor to take into account the extremely high
used gelatinizer but DEGN has the undesirable property pressures, 137,900 to 482,650 kilopascals (20,000 to
of being more volatile than nitroglycerin and so, makes 70,000 pounds per square inch), that exist in a gun
the propellants less stable. barrel. Physically, the covolume is defined as the
c. The triple-base gun propellants contain volume actually occupied by the gas molecules.
nitroguanidine as additional energizer which increases Laboratories dealing with propellants have a variety of
the energy content of the formulation without raising the methods available, including computer programs, that
flame temperature. This reduces gun barrel erosion are used routinely to estimate the thermochemical
with no sacrifice in performance. In addition, the triple- properties of propellants from basic chemical data. The
base propellants have a substantially reduced simplest of these is the Hirschfelder-Sherman
concentration of combustibles such as hydrogen and calculation in which the adiabatic, isochoric flame
carbon monoxide in the product gas. This reduces the temperature Tv, heat of explosion Q, moles of gas per
flash from the gun barrel. gram n, impetus (force)
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F =nRTv, ratio of specific heats, and covolume are b. Bulk Density. This often is referred to by such
calculated. An equilibrium computer program called the terms as "gravimetric density" and "screen loading
BLAKE code, formulated on the basis of a virial density" depending on the test utilized. The values
coefficient equation of state, has been devised for gun reported are empirical and are greatly dependent on the
use. The usual input required for equilibrium propellant specific gravity of the propellant, the grain geometry,
performance calculations consists of the chemical surface characteristics, and the measuring technique.
composition, the heat of formation (Hf at 2980K), and The term "bulk density" often is confused with loading
the elemental formula of each ingredient. Several density, a term that the ballistician uses for the ratio of
extensive compilations of heat of formation data are the charge weight in a system to the chamber volume.
available.. Several techniques are available for c. Compressibility of Grains. This is a measure of
estimating the heat of formation of compounds by how much a propellant grain can be compressed before
addition of bond energies and/or group contribution cracks appear. The usual required minimum value for
where experimental data are lacking. A computer gun propellants at 25°C is 30 percent. That value is
program has been developed for estimation of chemical based on historical experience.
thermodynamic data called "Chetah" (chemical,
thermodynamic, and hazard appraisal). The estimated
values obtained by these methods are usually for 9-5. Manufacture. The manufacturing methods for
compounds in the ideal gaseous state. Therefore, the various types of propellants are given below.
heat of vaporization and, sometimes, the heat of fusion a. Single-Base Propellants. The manufacture of
must be taken into account to obtain the heat of nitrocellulose is discussed in chapter 8. Wet
formation of the compound in its normal state at 2980K. nitrocellulose from the manufacturing process is
Experience indicates that the results of propellant dehydrated after the moisture content has been reduced
performance calculations are not extremely sensitive to to approximately 28 percent by wringing. Dehydration is
errors in the heat of formation of the ingredients. accomplished by pressing the nitrocellulose at low
Recently, methods have been developed for calculating pressure so as to squeeze out some water, adding 95
certain transport properties (for example, the thermal percent ethanol, and pressing at about 24,133
conductivity and viscosity) of the combustion product kilopascals (3,500 pounds per square inch). A block
gases under specific conditions of temperature and containing 11.4 kilograms (25 pounds) of dry
pressure. nitrocellulose and about one-third that much of 90
percent ethanol is obtained. The wet block is broken up
9-4. Physical Properties. Gun propellants must into small lumps by means of a rotating drum containing
function reliably over a large ambient temperature range iron prongs and a screen. The nitrocellulose is
(for example, 54° to +74°C) and they must retain their transferred to a watercooled mixing machine of the
performance characteristics during many years of dough-mixer type and, while this is in operation, ether
storage. The propellant grains must retain their integrity equal to approximately two-thirds of the weight of dry
in the face of a severe blast from the ignition system. nitrocellulose is added.
This quality must be demonstrated particularly at low Any plasticizing agents and stabilizers to be included in
temperatures where the propellants tend to be brittle. the composition are dissolved in or mixed with the ether
The propellant grains must not soften excessively at prior to addition to the nitrocellulose. After addition of
high temperature because then they can be deformed the ether is complete, materials such as potassium
by the ignition pulse. If this occurs, the propellant bed nitrate are added. Mixing of the ingredients is continued
might be compressed so tightly that the ignition gases for about one hour. A partially colloided mixture which
might not percolate satisfactorily through the bed. A resembles dry oatmeal is produced. By pressing this at
number of physical properties of propellants are approximately 20,685 kilopascals (3,000 pounds per
occasionally of interest to the ammunition designer. square inch) so as to form a block, the degree of
Among these properties are thermal expansion, thermal colloiding is increased rapidly. This effect is further
conductivity, specific heat, and thermal diffusivity. The increased and uniformity of the mixture is improved by
following properties are of direct interest to the charge subjecting it to a pressure of about 24,133 kilopascals
designer: (3,500 pounds per square inch) in a macaroni press.
a. Density. Conventional single and double-base Here the material is squeezed through a series of
propellants have values of approximately 1.60 grams screens and perforated plates and emerges in a form
per cubic centimeter, while triple-base (nitroguanidine) resembling that of macaroni. This is pressed again to
propellants are slightly higher. This is advantageous for form a block of well colloided material. This is placed in
tank ammunition where the maximum amount of a graining press and extruded through a carefully
propellant charge is required to meet the desired designed die by the application of pressure. The
ballistic levels. material emerges as a cord with one or more cylindrical
perforations.
9-3
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The cord is cut into pieces of predetermined length. large grains for use in rockets may be as thick as 3.18 '
Removal of the volatile solvent, with shrinkage of the millimeters (0.125 inch).
grains to their final dimensions, is accomplished by c. Triple-Base Propellants. The manufacturing
three operations. In the solvent recovery operation, the process used for the nitroguanidine triple-base
powder is placed in a large tank and warm air or other propellants in the United States has been uniformly
gas is passed through the mass. With careful control, solvent extrusion. The amount of solvent used is quite
so as to prevent surface hardening, the temperature of low so the propellant is very soft during extrusion. The
the air is gradually increased to not more than 65°C. soft strands may require partial drying before cutting in
The solvent recovery operation requires from 2 to 14 order not to deform the cross section at the cut.
days, depending upon the size of the grain, and reduces Removal of solvent from the triple-base propellant is
the solvent content to approximately six percent. The rapid, possibly due to diffusion of solvent within the
water dry operation consists of placing the partially dried grain along the crystal-plastic interfaces. In order to
powder in water at about 25°C and gradually increasing make a good quality grain, lower drying temperature
the temperature to a maximum of 55°C. After a number gradients are used in order to avoid steep solvent
of days, the residual solvent is reduced to 0.3 to 5 gradients resulting in distortion and cracking.
percent, depending upon the grain size. The powder d. Composite Propellants. A composite propellant
now is air dried to remove surface moisture and is manufactured by a simple mixing operation, cured,
screened to remove dust and grain clusters. The final and molded into grains or poured directly into the rocket
operation before packing is to blend all the powder in a case and cured by heating in controlled ovens.
lot, which may vary from 22,700 to 227,000 kilograms
Operational temperatures extend from -40°to +60=C.
depending on the type of powder. This is accomplished
by transferring the powder from one conical bin to The high solid content requires great resin strength and
another by gravity flow. This blending improves good elastic properties to withstand low temperatures.
uniformity of the lot with respect to composition and Precise control of the oxidizer particle size is needed to
external moisture content. control ballistic properties. Rockets up to 6.6 meters in
b. Double-Base Propellants. Double-base diameter and weighing up to 45,400 kilograms have
propellants are manufactured by two methods. The been fired successfully. The dense smoke produced by
solvent process is similar to that used for single-base these propellants limits their use to long range systems
powders except that a mixture of ethanol and acetone is where the signature of the rocket does not easily reveal
used as the solvent and the solvent recovery procedure the firing point.
is omitted because of the hazard involved in recovering e. Ball Propellants. Ball propellants are used for
solvents containing nitroglycerin. The solventless small arms. The nitrocellulose used to make the
process is used when the nitroglycerin and any other propellant is extracted from waste single-base
colloiding agents constitute approximately 40 percent of propellant. To produce the propellant in ball form,
the composition. In this process the wet nitrocellulose is water-wet nitrocellulose is mixed with ethyl acetate,
blended with the nitroglycerin in a tank filled with water. colloided with animal glue, and agitated; excess water
Ethyl centralite is mixed in and the bulk of the excess causes the propellant to precipitate in a ball. The
water is removed by centrifuging. The resulting paste is animal glue is washed away using hot water. The
put in cotton bags and subjected to heated air currents propellant is screened to size and nitroglycerin is added
to reduce the moisture content. The remaining in the presence of ethyl acetate. The nitroglycerin is
constituents are then blended with the partly dried paste. absorbed by the ball propellant, the ethyl acetate is
Repeated rolling between heated steel rollers removes driven off, and the ball is carried to a roll mill to cause
the rest of the water and completes colloiding of the cracks, that serve as combustion sites, to form in the
nitrocellulose. The thickness of the sheet formed is ball. The propellant is then dried and a deterrent
controlled carefully and varies with use. If the sheet is coating such as Dibutylphthalate is added. The
to be cut into flakes for use in small arms or mortars, the deterrent reduces the burn rate of the propellant to an
thickness is between 0.08 and 0.32 millimeter (0.003 acceptable level.
and 0.0125 inch). Sheets to be extruded in the form of
Change 1 9-4
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9-6. Propellant Grain Geometry. The burning time of burning rate, the burn time can be varied by varying the
a propellant charge depends on two factors. One factor web thickness. The web thickness, shown in figure 9-2,
is the velocity at which the exothermic decomposition is the average dimension of the outer web and inner
reaction occurs. This is called burning rate. The other web. In general, the finer the web the shorter is the
factor is the total surface area of propellant exposed. In burning time of the propellant charge. The grain
order to control the surface area available for reaction, dimensions also influence the burning time. The finer
propelling charges consist of numerous propellant the web the higher the pressure produced. A cannon is
grains. Propellant grains can have a variety of shapes designed to operate with a maximum pressure. This
as shown in figure 9-1. An additional grain geometry, pressure must be taken into account when designing the
the flake, is also used in mortars. The shape of the grain web. The same projectile velocity can be attained
grain determines how much surface area is exposed as with a smaller amount of propellant with fine web and
burning proceeds. For example, as a cord burns, the with a larger amount of propellant with a coarse web.
surface area of exposed propellant decreases. This is However, the pressure with the former is considerably
called a degressive grain. As a single perforated grain greater than the latter. In general, the heavier the
burns, the exposed surface area remains nearly projectile or the greater the prescribed velocity, the
constant because the outer surface area decreases as larger the powder grain and web used. As shown in
the inner surface area increases. This is called a neutral figure 9-2, the burning of a seven perforation grain
grain. In a progressive grain, for example the multi- produces 12 unburned slivers or pieces of triangular
perforated and rosette, the surface area increases cross section that represent approximately 15 percent of
during burning. The grain geometry and burning rate the total weight of the grain. These slivers burn
are interrelated. The burning time of a propelling charge digressively and usually are burned in the bore of the
that contains a propellant with a high burning rate and weapon; but if the tube is relatively short or a reduced
strongly digressive grain geometry could be equal to the charge of propellant is fired, incompletely burned slivers
burning time of a charge that contains a propellant with may be expelled from the muzzle. The rosette or Walsh
a low burning rate and strongly progressive grain grain (figure 9-1) with a scalloped outer periphery,
geometry. European nations have favored the use of reduces the number of slivers produced by a multi-
single perforation, strip, and cord propellants. The perforation grain and therefore reduces or eliminates the
United States uses single perforation and multi- amount of unburned powder ejected. In practice, there
perforation propellants. The single perforation grains are certain general relationships between the
may be slotted or unslotted. The slotted grain has the dimensions of powder grains. These dimensions must
desirable characteristic of venting gas during remain within fairly narrow limits. Specification
combustion. All countries use ball propellants for small requirements for cannon powders include the relative
arms. In a multi-perforation or rosette grain that dimensions which follow.
consists of a propelling compound with a specific linear
9-5
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Figure 9-2. Web thickness and direction of burning through a progressively burning grain.
a. The ratio of average grain length (L) to average relative quickness (RQ) of gun propellants. In this
grain diameter (D) is 2.10 to 2.50 for multi-perforation determination, a test propellant is fired in a closed bomb
grains and 3 to 6 for single perforation grains. and the results are compared with those obtained with a
b. The ratio of average grain diameter (D) to the reference propellant fired under identical conditions. RF
average diameter of perforations (d) is 5 to 15 for multi- is defined as
perforation grains and approximately three for single RF = Pmax test propellant
perforation grains. Pmax reference propellant
c. The difference between the average outer web
thickness (Wo) and the average inner web thickness RQ is defined as
(Wi) of multi-perforation powder is not more than 15
percent of the average web thickness (Wa). RQ = dP/dt test propellant
dP/dt reference propellant
9-7. Burning Rates. Ballisticians view the propellant
grains as burning in parallel layers, where the burning where dP/dt is the rate of change of pressure with time.
proceeds in a direction perpendicular to the surface. b. Burning rate vs pressure data commonly are fitted to
This universally accepted concept is known as Piobert's an equation of the form
law and is supported by the experience of many
investigators drawing their conclusions from many r =bPn
different approaches. The linear burning rate vs
pressure behavior of a gun propellant (the rate at which known as de Saint Robert's equation. Plots of the log of
burning proceeds normal to the surface) is a the burning rate vs the log of the pressure of many
characteristic of the composition and is a required input propellants yield straight lines. Under that condition, b
for most interior ballistics calculations. and n are constants. Table 9-3 gives values of b and n
a. The burning rate is independent of grain for several of the standard propellants. Using the
geometry. Results of the two tests usually used to values specified, the burning rate equation yields r in
determine burning rates (the strand burner and closed inches per second when P is in pounds per square inch.
bomb) are the same for cord, single perforation, and
seven perforation grains. The closed bomb is used
most commonly to determine relative force (RF) and
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Table 9-3. Burning Rate Parameters for Several Standard Gun Propellants
c. The burning rate of gun propellants generally 9-8. Ignitabllity. Ignition of a propellant charge is
increases with initial propellant temperature. The accomplished by raising the temperature of the
temperature coefficient of the burning rate is defined as propellant surface to the ignition temperature. The
the ratio of the change in burning rate and the change in simultaneous ignition of all the exposed surfaces is
temperature at constant pressure. Typical values for the desirable for many gun applications. Black powder is
temperature coefficient are 0.077 percent per degree used extensively for artillery and rocket propelling
centigrade at 206,850 kilopascals (30,000 pounds per charge ignition.
square inch) for M 10 and 0.05 percent for M30 under Black powder is a more efficient igniter than finely
the same conditions. divided propellant, which is used in mortars, because it
d. The burning rate of conventional propellants does not produce as much gas per unit weight as
increases with increasing flame temperature. Several propellant, its use reduces ignition shock, it yields high
empirical correlations have been developed which initial pressures, and the hot particles in its combustion
provide a means for estimating burning rates of different products assist in transferring heat to the propellant
propellant formulations from the adiabatic flame surface.
temperature. a. An increase in the nitrogen content of the
e. Propellants used in small arms usually have a nitrocellulose causes slight increase in ignitability.
deterrent impregnated into their surface which alters the b. The substitution of nitroglycerin for part of the
chemical composition of the outer portion of the grains nitrocellulose in a composition increases ignitability to a
to slow the initial burning rate. Commonly used marked extent.
deterrents include dinitrotoluene and ethyl centralite. c. The inclusion of an inert, gelatinizing agent,
The deterrent has a moistureproofing effect and usually such as Dibutylphthalate or triacetin, in a propellant
a melting point of less than 1 00°C. A coating of composition results in a decrease in ignitability.
deterrent is applied by tumbling the propellant powder in
a "sweetie" barrel in a water slurry with the deterrent at a d. The inclusion of TNT or dinitrotoluene in a
temperature above the melting point of the deterrent. composition causes measureable decrease in
ignitability.
f. The burning rate of solid propellants increases
with increasing product gas velocity near the surface. e. The inclusion of five percent or less of
potassium nitrate in a composition causes a significant
This phenomenon is referred to as erosive burning. The increase in ignitability.
extent of erosive burning depends on grain geometry
and composition. Relatively "hot" propellants are f. The presence of a deterrent on a propellant
apparently less subject to erosive burning than are causes retardation of ignition.
"cool" ones. The inner surface of long tubes does not, g. As the initial temperature of the propellant
apparently, burn in an even, uniform manner. The holes decreases, the ignitability decreases.
increase in size faster at the ends. Slotted tubes burn
closely in conformance to Piobert's law. 9-9. Charge Design Considerations. The selection
g. The actual burning rate of solid propellants also of a propellant for a particular application is determined
deviates from the steady-state or expected value under by cost, by the interior ballistics requirements, by
rapid pressure excursions. That is, the instantaneous propellant/weapon interface considerations, and by
burning rate then will differ significantly from that limitations with respect to muzzle effects. The
expected for the corresponding instantaneous pressure. propellant with the lowest cost formulation and the
This phenomenon, called dynamic burning, has not lowest flame temperature that still will meet the velocity
been studied enough to present corrections to the and pressure requirements is generally used. Other
burning rate equation. important considerations are the effects on ballistic
performance of various propellant grain shapes and the
problem of matching the gas production rate
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from propellant burning to the rate of increase of volume effect on the acceleration of a projectile, is called
in the gun behind the accelerating projectile. The shape interior ballistics. Figure 9-3 shows a representative
of the grain also affects the amount that can be loaded pressure travel curve for a projectile in a gun. The
in a given space and can control the generation of further the point of maximum pressure (points A, B, and
pressure waves in large caliber guns. The charge C) is from the powder chamber, the greater the velocity
weight sometimes is restricted in large caliber guns by acquired by the projectile. This is the reason the United
the momentum limit. The gas expelled from the muzzle States favors the use of multiperforated grains.
adds to the total forward momentum. The propellant a. There are four general equations which form the
charge plays a major role in gun fouling and erosion. basis of interior ballistics.
This field is receiving considerable attention at this time (1) The burning rate equation is the first of
and in recent years, erosion often has been reduced the four. This equation has already been discussed.
dramatically by means of wear-reducing materials that (2) The equation of the form takes into
are added to the propellant composition or to the charge account the propellant grain geometry. The web
as cartridge case liners. Efforts usually are made to fraction, Wf, is defined by the equation:
minimize muzzle flash and smoke. Muzzle flash and
smoke are related in a sense and have been
Wf = 2Rrdt
investigated extensively. Two components contribute to
Wo
muzzle flash: the primary flash and the secondary flash.
The primary flash is caused by incandescent hot gases
where r is the burning rate, R is the burning rate
emerging from the muzzle or heated to incandescence
conversion factor, and Wo is the original web thickness.
by the shock following the projectile out of the gun. The
The factor of two is present since the web is being
secondary flash is caused by the burning of combustible
burned from two opposite surfaces and R is included to
muzzle gas when mixed with air and heated to ignition
compensate for burning rate peculiarities. The amount
by the shock wave. Ignition of the gas cloud is also
of gas generated can be found as a function of We by
caused by the early, bright burning of tracers. This is a
the following two equations:
voluminous, relatively long lived event and is far more
objectionable than the primary flash. In small caliber
weapons, secondary muzzle flash is suppressed
effectively in many weapons by means of mechanical
devices attached to the muzzle. Various chemical
additives, especially alkali metal salts, are very effective
and widely used to suppress secondary flash. The salts
may be incorporated into the compositions, or they may
be loaded as separate components in the charge. where G is the mass of gas generated, C is the original
Secondary flash is also reduced by reduction of the charge mass, Ko-K3 and K'-K3are coefficients
propellant composition flame temperature and by determined by the grains geometry and Wi is the
reduction of the proportion of combustible gases fraction of web remaining. The first equation is
produced by the propellant. Gun smoke is due to employed during non-splintered burning (WtO0) and the
particulate, usually inorganic, material emerging from second is used after grain splintering has occurred
the gun behind the projectile. Primer and igniter (WI<0). Slivering is typical of multi-perforation grain
combustion products, barrel scrapings, and solid types. In these grain types there is residual propellant
combustion products from the propellants are the major when the web fraction is burned to zero. This remaining
constituents of gun smoke. The visibility of the smoke or propellant is then burned as slivers. In simulations
smoke density is due largely to the products from the containing more than one grain type, each granulation is
alkali metal salt flash suppressant. These constituents handled separately. The total gas generated is simply
also are responsible for the substantial increase of their sum.
smoke density under humid conditions. (3) As propellants burn, the total energy
available from a unit mass of propellant can be
9-10. Ballistic Effects. The study of the combustion of computed by the equation:
a propellant in a confined volume, and the resultant rate E = FG
of gas generation combined with its g-1
where E is the energy liberated, G is the ratio of specific
heats of the propellant gas, F is the propellant impetus
Change 1 9-8
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(the amount of energy per unit mass). In cases where individual ingredients, nitroglycerin and/or nitrocellulose.
more than one grain type or more than one propellant From a practical standpoint, the hazards associated with
type are used, the energy generated by each distinct a propellant are mainly heat, spark, and very high
granulation-propellant combination is calculated energy impact.
separately and summed to compute the total energy
released. The energy released by the burning a. To a great extent, the degree of confinement
propellants is dissipated in several ways. The potential determines whether a propellant will deflagrate or
energy of the confined gas is increased (PV energy). detonate. Experiments have shown that the
Energy is spent accelerating the projectile and the gas confinement afforded by the upper part of a column of
itself (kinetic energy). Energy is lost through thermal propellant may be sufficient to cause explosion if the
and frictional processes which results in an increase of powder at the bottom of the pile is ignited. Various
the gas temperature. The energy balance equation is powder compositions were found to have
correspondingly varying critical heights of column, the
critical height varying inversely with the energy content
of the composition. For the same composition, the
critical height was found to vary directly with the
where PE is the potential energy of the confined gas, E average web of the powder. If the temperature of the
is the total energy released by the propellants, Meff is powder is 50°C instead of 20°C, the critical height of a
the effective mass of the projectile and gases, Bf is the composition is only 30 to 50 percent as much as at the
energy loss coefficient, V is the velocity of the projectile, lower temperature. Propellants for small arms, chiefly
and y is the specific heat ratio of the propellant gas. The nitrocellulose, were found to have critical height values
effective mass used in this calculation is given by the of 38.1 to 50.8 centimeters. Single based cannon
equation: powders of larger grain sizes and containing moderants
Meff =Wt.CF3.Mp have critical height values of 76.2 centimeters or more.
Propellants can be detonated by initiating compounds or
where Wt is a correction for projectile twisting, CF3 is a booster explosives.
Piddock-Kent coefficient, and Mp is the projectile mass. b. Propellants are sensitive to electric sparks only
The factor Wt is included since the projectile is if the material is in the form of a dust. Some test results
undergoing rotational acceleration in addition to linear indicate the powder dust is much more ignitable by a
acceleration. Wt is normally set at 1.02 which provides static electricity spark than is nitrocellulose. Dry-house
an excellent approximation. and blending-towerfires have occurred that were
(4) Projectile motion is determined by the attributed to the primary ignition of powder dust by static
application of Newton's third law electricity sparks. Atmospheric relative humidity above
60 percent prevents such spark discharges and
ignitions. The humidity must be measured where the
operation is going on.
c. Propellants can be ignited by the friction and
where a is the projectile's acceleration, Pe is the base impact of small arms bullets. Detonation or deflagration
pressure, A is the bore cross sectional area, and Mp is occurs according to confinement. Recently a great deal
the projectile's mass. The velocity and position may be of attention has been placed on very high kinetic energy
obtained by integrating this expression one and two impacts such as the impact of a shaped charge jet spall.
times, respectively with respect to time. These concerns are obviously from the standpoint of
b. Several computer programs are used to perform practical application.
interior ballistic calculations. One such program is the
Interior Ballistic Interactive Simulation (IBIS) code. IBIS 9-12. Stability. The stability of nitrocellulose, which
computes propellant charge weight, web dimensions, was discussed in Chapter 8, is relatively poor. The
and grain dimensions from the pressure parameters of stability of nitrocellulose based propellants is
the cannon, projectile weight, muzzle velocity, bore correspondingly poor. The degradation of nitrocellulose
cross sectional area, force of the propellant, and burning proceeds by two chemical reactions. In the first
rate of the propellant. degradation reaction, nitrocellulose loses nitrogen
oxides. The loss of nitrogen oxides
9-11. Sensitivity. The colloidal structure of propellants
reduces sensitivity to a point well below that of the
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9-11
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CHAPTER 10
UNITED STATES PYROTECHNICS
10-1. Categories of Pyrotechnic Devices. diluents, while others take part in the combustion
reaction at a much slower rate than the metallic fuels.
Calcium carbonate, sodium oxalate, strontium resinate,
a. General. All pyrotechnic compositions contain
titanium dioxide, polyvinyl chloride, ethyl cellulose,
oxidizers and fuels. Additional ingredients present in
paraffin, linseed oil, castor oil, asphaltum, and sulfur are
most compositions include binding agents, retardants,
the most important retardants used. Certain of these
and waterproofing agents. Ingredients such as smoke
serve other purposes as well. For example, sodium
dyes and color intensifiers are present in the appropriate
oxalate and polyvinyl chloride act also as color
types of compositions.
intensifiers, titanium dioxide is a source of incandescent
(1) Oxidizers are substances in which an solid particles in the flame produced by the composition,
oxidizing agent is liberated at the high temperatures of and the waxes and oils act as fuels, binding agents, and
the chemical reaction involved. Two oxidizing agents, waterproofing agents as well as retardants.
oxygen and fluorine, are currently used in pyrotechnic
(5) Waterproofing agents are necessary in
compositions. Oxygen is provided by the nitrates of
many pyrotechnic compositions because of the
barium, strontium, sodium, and potassium, the
susceptibility of metallic magnesium to reaction with
perchlorates of ammonium and potassium, or the
moisture, the reactivity of metallic aluminum with certain
peroxides of barium, strontium, and lead. Use of a
compounds in the presence of moisture, and the
specific oxidant is determined by the desired burning
hygroscopicity of nitrates and peroxides. Waterproofing
rate, luminosity, and color. Fluorine is usually provided
agents are applied as a coating on metallic fuels, such
by polytetrafluoroethylene or chlorotrifluoroethylene.
as a coating of dried linseed oil on magnesium, or as an
Pyrotechnic compositions do not usually contain a
ingredient uniformly distributed throughout the rest of
stoichiometric proportion of oxidizer, the balance of the
the composition. In some cases, the metallic fuel is
requirement for fuel oxidation is provided by
given a coating by treatment with a solution of acidic or
atmospheric oxygen.
acidified potassium dichromate. Waxes, resinates of
(2) Fuels include finely powdered aluminum, metals, and natural and synthetic resins are used for
magnesium, metal hydrides, red phosphorus, sulfur, distribution throughout the composition. Many of these
charcoal, boron, silicon, and suicides. The most serve also as binding agents.
frequently used are powdered aluminum and
(6) Color intensifiers are highly chlorinated
magnesium.
organic compounds such as hexachloroethane (C2CI6),
Additional materials such as binding agents, hexachlorobenzene (C6CI6), polyvinyl chloride, and
waterproofing agents, and color intensifiers also act as dechlorane (C1oCI12). These agents are effective
fuels. because of their decomposition during combustion and
(3) Binding agents include resins, waxes, the formation of metallic chlorides which produce
plastics, and oils. These materials make the finely characteristic color bands in the flame spectrum. The
divided particles adhere to each other when compressed portion of the intensifier other than chlorine acts as a
into pyrotechnic items. They also prevent segregation part of the fuel in the composition. Since they are less
and ensure a more uniformly blended composition. reactive than metallic fuels, color intensifiers act to
Binders also help to obtain maximum density and some extent as retardants of combustion. Certain
increased burning efficiency. In addition, they serve, in intensifiers such as polyvinyl chloride, because of their
some cases, to reduce the sensitivity of compositions physical characteristics, can serve also as binding
that otherwise would be unduly sensitive to shock and agents.
friction. (7) Smoke dyes are azo and anthraquinone
(4) Retardants are materials that are used to dyes. These dyes provide the color in smokes used for
reduce the burning rate of the fuel-oxidizing agent signaling, marking, and spotting.
mixture, with a minimum effect on the color intensity of
the composition. Some retardants act only as inert
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(a) Venturi thermal generator type. The intensity is just invisible when observed through a layer
smoke producing material and the pyrotechnic fuel block of approximately 30 meters. The amount of smoke
required to volatilize the smoke material are in separate agents required to produce one cubic meter of standard
compartments. The smoke producing material is smoke is given in table 10-3.
atomized and vaporized in the venturi nozzle by the hot Table 10-3. Amount of Smoke Agent per Cubic
gases formed by the burning of the fuel block. An Meter of Standard Smoke
example of this type smoke generator is the oil smoke Material Grams per
pot which is powered by a slow burning, gassy cubic meter
pyrotechnic mixture such as ammonium nitrate and White phosphorus 0.064
ammonium chloride with a small amount of Sulfur trioxide 0.099
carbonaceous fuel. The resulting gas jet pulls a stream FS agent 0.116
of oil from a reservoir and injects it into a venturi where HC mixture 0.127
the formation of the aerosol takes place. FM agent 0.159
(b) Burning type. Burning type smoke Crude oil 2.11
compositions are intimate mixtures of chemicals. (2) The preferred method of dispersing
Smoke is produced from these mixtures by either of two colored smokes involves the vaporization and
methods. In the first method, a product of combustion condensation of a colored organic volatile dye. The
forms the smoke or the product reacts with constituents problem has always been one of selecting dyes which
of the atmosphere to form a smoke. In the second are thermally stable and which vaporize without
method, the heat of combustion of the pyrotechnic decomposition at temperatures below 400°C. There are
serves to volatilize a component of the mixture which a very large number of dyes. The following are
then condenses to form the smoke. White phosphorus, representative of dyes selected by the US as
either in bulk or in solution, is one example of the satisfactory agents for producing burning type colored
burning type of smoke generator. The resulting colloidal smokes:
suspension of phosphorus pentoxide is quickly
Yellow: Auramine hydrochloride
hydrolyzed by moisture to become phosphoric acid
Green: 1,4-Di-p-toluidinoanthraquinone with
droplets which are the actual visible constituent of the
auramine hydrochloride
smoke. Various other burning type smoke generators
Red: 1-Methylanthraquinone
exist such as those used for signaling purposes and
Blue: Not suitable for signaling because of
those which use red phosphorus, metallic phosphides, or
excessive light scatter.
phosphorus trichloride as the source of the particulate
cloud. Another important burning type of smoke
These dyes are mixed to the extent of about 50 percent
generator is the HC smoke mixture which has been
with a fuel such as lactose (20 percent) and an oxidizer
prepared with a number of combinations of zinc with a
(30 percent) for which potassium chlorate is preferred.
chlorine carrier to form, on combustion, zinc chloride.
If the mixtures should still burn too hot (and thereby
For example,
destroy the dye), sodium or potassium bicarbonate are
2AI +C2CI6 +3ZnO A12O3+2C+3ZnCI2 added as cooling agents. Colored smoke compositions
(c) Explosive dissemination type. The smoke are usually used in a compressed state without a binder.
producing material is pulverized or atomized and then A major concern at present is the reported carcinogenic
vaporized, or a preground solid is dispersed by the nature of organic dyes and elaborate programs have
explosion of a bursting charge. The explosive been initiated for their destruction. In addition to the
dissemination smoke generator may contain metallic smoke grenades which function by burning, others
chlorides which upon dispersal, hydrolyze in air. produce smoke by volatization of the dye from a
Examples are titanium, silicon, and stannic separate dye compartment. These dyes should
tetrachloride. An effective smoke agent, whether preferably have melting points below 150°C and be
mechanically dispersed from an aircraft spray tank or stable in the vapor phase. The following are currently
vaporized thermally, is a mixture of sulfur trioxide and used dyes:
chlorosulfonic acid (FS smoke agent) which upon
hydrolysis forms sulfuric and hydrochloric acid Orange: 1-(4-Phenylazo)-2-naphthol
dispersions. Of course, all such formulations are highly Yellow: N, N-Dimethyl-p-phenylazoaniline
corrosive, and, if not outright toxic, then conducive to Blue: 1,4-Diamylaminoanthraqdinone
pulmonary edema. The so-called standard smoke is a
smoke of such a density that a light of 25 candela
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Mixtures of these dyes produce muddy colors of various between the two types is the method of tracking. The
hues. Lastly, dyes can be dispersed by explosive more frequently used tracer uses the light produced by
charges. These generate colored clouds (about 10 x the burning tracer composition for tracking. Smoke
20m) which are formed instantaneously and which have tracers leave a trail of colored smoke for tracking. Red
a life expectancy, depending on environmental is the flame color most often employed in tracers. Red
conditions, from 65 to 85 seconds, whereas aerial has a longer wavelength and so can penetrate haze,
burning of the aforementioned burning type produces dust, and fog better than the other colors. A tracer may
streamers about one meter across which last for about be directly ignited by the flame from a propellant charge
57 to 120 seconds. or, as is the case in larger caliber shells, the ignition
d. Tracers and Fumers. The principal small arms may be delayed to hide the position of a cannon. Table
application of military pyrotechnics is in tracer munitions 10-4 lists several tracer and delay compositions.
where they serve as incendiaries, spotters, and as fire
control. Two types of tracers are used. The difference
Compositions have also been developed for electro- phosphorus, and napalm. In addition, the case of the
optical devices. These compositions consist of calcium bomb may be constructed of a material such as
resinate, barium and strontium peroxides, and magnesium that will burn at a high temperature once
magnesium carbonate. The mechanism of tracer ignited. The burning material may be explosively
reactions is a complex one; the burning rate and scattered over a wide area. The more recently
brightness decrease with altitude but increase with developed type of incendiary uses metals which produce
increasing spin rate of the bullet. Smoke tracer pyrophoric, or burning, fragments. Three properties
compositions contain about 70 percent strontium have been identified as important for metals which are
peroxide, 10 percent calcium resinate, 10 percent suitable for use as incendiaries. The heat of formation
catechol, and 10 percent smoke dye. of the oxide must be greater than 400 kilojoules per
Methylaminoanthraquinone is the dye used in red smoke mole of oxygen consumed. The ratio of the oxide
and auramine is used for greenish-yellow smoke. A volume to metal volume must be greater than one.
fumer, or gas generating tracer, uses the gaseous The metal must also have electrons in the conduction
products of the burning tracer to fill the vacuum created band. Formation of an intermetallic compound that
behind the moving projectile. This increases range and reduces the number of electrons in the conduction band
decreases time of flight. reduces the pyrophoricity of the compound. Table 10-5
e. Incendiaries. Two types of incendiaries are lists the properties of metals considered suitable for
commonly used. The traditional type is a bomb incendiary use.
containing a flammable material. These materials
include thermite (a mixture of aluminum and rust),
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For straight incendiary applications the sponge form of Depleted uranium is used extensively in pyrotechnics
these metals is used because this form provides a large which have armor piercing capabilities. Depleted
surface area. Metals which are used in this application uranium deficient in the more radioactive isotope U235,
include zirconium, titanium, and mischmetal. is the waste product of the uranium enrichment process.
Polytetraflouroethylene can be used as an oxidizing The depleted uranium is formed into projectiles that can
agent. The heat of the reaction for several metals is penetrate armor because of their high density and
shown in table 10-6. The numerical values given are mechanical properties. The impact of the projectile
strongly affected by the stoichiometry and the effective causes the uranium to form many pyrophoric fragments
density of the reactants. which can ignite fuel and munition items.
Table 10-6. Maximum Volumetric Heats of f. Delays and Fuses. Delay compositions are
mixtures of oxidants and powdered metals which
Reaction for Metals Reacting with Fluorocarbons
produce very little gas during combustion. Work on
Kilojoules
delay systems continues because the existing delay
per cubic
mixtures do not store well and scale-up is not as flexible
Metal Product centimeter
and as precise as is desired. A basic reason is that
gasless delay mixtures are not truly gasless because
Be BeF2 -24.0 gaseous reagents are present in the flame front or in the
La LaF3 -21.0 ignition mix. The gaseous reagents contribute to the
U UF3 -19.8 pressure in the column so that the burn time is not
Mg MgF2 -19.8 strictly a linear function of the column length. This
Hf HfF3 -19.0 phenomenon has been called the anticipatory effect.
U UF4 -18.9 Table 10-7 lists the most important delay compositions
Zr ZrF3 -18.6 in use at the present time.
Zr ZrF4 -18.6
Hf HfF4 -18.2
Ti TiF3 -17.0
Ti FiF4 -14.6
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The delay time change, or aging, is caused by the corrosion of the metallic fuels. The rate of corrosion is increased by
the presence of moisture. In general the burn time of the delay is adjusted within stated limits by controlling the
percentage of fuel in the composition. The chromate oxidizers may be carcinogenic.
g. Photoflash Compositions. Photoflash compositions are the single most hazardous class of pyrotechnic mixtures.
The particle size of the ingredients is so small that burning resembles an explosion. The various photoflash devices are
similar, differing principally in size and the amount of delay. When fired, each photoflash cartridge, after one, two, or
four seconds, produces a flash having a peak intensity of approximately 50 million candela with a total output of five
million candela seconds, whereas photoflash bombs generate above 5 x 109 candela. The most commonly used fuels
include aluminum and magnesium. The most commonly used oxidizers include barium nitrate and potassium
perchlorate. While atomized magnesium gives higher intensities in consolidated compositions, atomized aluminum
performs better in loose compositions than do other fuels. Potassium perchlorate produces the highest heat of reaction
with atomized aluminum. The output is highest for fuel rich compositions and alkaline earth nitrates which are far
superior to alkali metal nitrates. Constant aluminum particle sizes of 22±+8 micrometers resulted in optimum efficiency
at all altitudes. At high altitudes zirconium performs better. Photoflash compositions containing halfnium and potassium
perchlorate possess greater luminous efficiency on a volume basis than do other formulations. Zirconium, for example,
when burned in oxygen has an average color temperature of 4,883°K compared with 5,235°K for halfnium at peak
intensity. In pyrotechnic flash units, substitution of aluminum with halfnium and titanium produced comparable peak
output, but inferior output when zirconium and cesium were substituted.
h. Igniters and Initiators. Black powder is used extensively as an igniter for artillery propellant charges.
Table 10-8 lists various black powder compositions used by the United States.
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Table 10-8. Black Powders Used in Pyrotechnics order detonation. Coarse unpressed powders which are
confined have approximate burning rates of 170 meters
Formulas per second. Fine, unpressed, confined powders have
Components (%) 146 147 148 burning rates of approximately 950 meters per second.
Potassium nitrate 74.0 70 - A newer formulation of black powder called pyrodex
Sodium nitrate - - 72 consists of six percent sulfur, 10 percent charcoal, 83
Charcoal 15.6 - 16 percent potassium nitrate, and one percent calcium
Coal - 14 - carbonate. This mixture has an ignition temperature
(semibituminous) above 260°C compared with 125°C for regular black
Sulfur 10.4 16 12 powder. Other mixtures called either first fire, ignition
mixtures, or starters are used. The names are
A small amount of graphite is added as a glazing during somewhat misleading. The mixtures are intermediates
the finishing process. The burning rate of black powder between the primary igniter and main charge. Table 10-
is dependent on the granulation of the ingredients and 9 lists some of the numerous formulations of this type
the grain size. The burning can be described as low mixture.
Components, % Formulas
60 68 69 164 165 173 174 175 176 177 178 179 180 181 182 183 184
10-7
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i. Simulator Compositions. Simulator compositions attrition mill a stream of high velocity air is used to
are used to simulate the functioning of ammunition accellerate particles of the powder. The collisions of the
items during training exercises. Simulators can particles with one another break them down further.
harmlessly duplicate the effects of air bursts, c. Classification. After grinding, the powders are
boobytraps, ground bursts, gunflashes, and hand classified by size. For powders above 44 microns,
grenades. Simulators which must produce a loud noise sieves are used. For powders below 44 microns,
may use black powder or such compositions as a cyclones are used. Cyclones are funnel shaped
mixture of aluminum powder, potassium perchlorate, chambers into which the powder is fed. An air current is
and barium nitrate. These simulators also produce maintained which centrifugially separates the powders
white smoke. Grey or black smoke can be produced by by size. The coarser materials are forced to the wall of
carbon rich compounds such as naphthalene which do the container.
not oxidize completely. Simulators can also contain
colored smoke compositions for marking the positions of d. Weighing. To obtain the proper performance
certain types of hits such as chemical or incendiary from a pyrotechnic composition accurate weighing is
projectile impact. Some simulators contain a necessary.
pyrotechnic whistle. Picric acid and such other organic e. Blending. Two methods are used for the
acids as gallic, salicylic, and benzoic having the same blending of pyrotechnic compositions, dry and wet. The
characteristic odor, are the major ingredients in dry method is used for insensitive material. Passing the
pyrotechnic whistles. Combinations of these acids with ingredients through sieves is used for small quantity
potassium chlorate, perchlorate, or nitrate, compressed production. A ball mill which uses rubber balls is used
in short tubes, emit a shrill whistling sound of varying for larger quantities. Wet mixing is accomplished with
pitch when ignited. Size, especially length of the tube in the ingredients suspended in a liquid. This method is
which the composition is pressed, determines pitch. used to blend more sensitive materials.
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(a) Usually, large volumes of smoke of interface filters, which cover the visible spectral
issue from the test flare. The smoke can reflect light or region. The filters are chosen to have a uniform
obscure the flame depending upon the motion of the spectral response at a precisely chosen peak
smoke. Blowers and dampers are used to adjust the wavelength. Photocells and associated circuits are
wind velocity to maintain control of this variable. positioned behind the filters. The output of the
(b) Power density radiated by the flare photocells can be digitized and interfaced directly with a
is a variable. The flare is not truly an isoentropic computer. Correction for human eye response can be
source, as assumed in calculations, because flux is not made automatically. Candlepower can be computed by
radiated uniformly over the entire burning surface. integration of the luminous intensity over the wavelength
Radiation from the cylindrical sides may be twice that range of interest. Dominant wavelength and purity are
from end on. Measurements in tunnels are usually determined by multiplying the radiant energy distribution
made from the side of the flare. by the three color distributions of the International
(c) The area of the flare in the field of Commission of Illumination, wavelength by wavelength.
the photocell is a variable. Intensity readings will be Chromaticity coordinates are calculated from the
incorrect if the field of the optical system includes only a integrals under the three product curves and plotted in a
portion of the flame produced by the flare. The entire chromaticity diagram to determine dominant wavelength
flame produced by the flare should be in the field of and purity.
view of the photocell, and any light reflected from the
smoke in the vicinity of the burning flare should be kept c. Smoke.
to a minimum.
(d) The reflectivity of the background is (1) General. In early stages of development,
a variable. Background reflections can produce when gross effects are sought, much is gained by
particularly large errors in measurements of light output. simple visual observation of the smoke produced.
Apparent increases of 40 percent have occurred Visual observation is usually followed by still and motion
because of reflections from the tunnel floor. This photography to make better estimates of volume and
condition is corrected by restricting the view of the color. In the case of screening smokes, quantitative
measuring instrument to that portion of the flare measurements of the obscuring power can be made by
producing the light. the attenuation of light by the smoke. Signalling smokes
(e) The accuracy of the spectral have four properties of importance to the military: color,
correlation and intensity calibration is a variable. visibility, duration, and volume. Since instability is one
Spectral correction conforming to the response of the of the main features of the smoke cloud, the ability to
International Commission of Illumination and intensity persist is usually judged by comparison with smoke from
calibration with standard sources for the test equipment a control that is being burned simultaneously within
are required. close proximity of the test smoke generator. Care must
be taken to observe that the two independent plumes
(3) Field tests. The flame size and volume of
are observed under similar atmospheric conditions.
smoke produced by some flares is too great for indoor
tests. Such flares are tested outdoors at test sites that (2) Laboratory tests. The test volume of the
are relatively flat, open areas approximately 120 meters equipment used to measure smoke production may vary
(400 feet) in diameter and that have a means of from a few cubic feet to several thousand cubic feet.
suspending the flare at least 24 meters (80 feet) above The test chambers usually provide a means of
the center of a plane containing the photocells. Often physically manipulating the sample under test including
the most practical method of evaluating light effects is parts or fittings for air, smoke, and exhaust; and an
visual observation supplemented with photography. optical system for obscuration measurements. The
This is particularly true of small arms tracers. screening values of smokes are determined by a figure
of merit known as the total obscuring power (TOP)
(4) Color measurement. The color of light
which is the area in square feet that can be obscured by
producing illuminants is assessed by visual observation
a pound of smoke formulation. TOP can be measured
of flare burning or by the use of instruments that can
directly by positioning a target in a smoke chamber until
dissect the light into characteristic colors or
the target is just obscured. TOP can also be determined
wavelengths. Quantitative spectral data allows the
engineer to observe dilution of a desired color by by measuring the attenuation of a light beam through a
unwanted colors, thus enabling corrections to be made. fixed distance of smoke. The intensity of the light as a
These procedures may also be used for quality control function of incident intensity is given by the equation:
during production. A flare radiometer consists of a
number (10 is used in the Picatinny Arsenal apparatus) I=Io exp(eCL) (10-1)
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where I is the observed light intensity, l0 is the intensity Wind tends to produce both good and bad effects in
with no smoke present, C is the concentration of the smoke production and use. In outdoor tests, wind speed
smoke in pounds per cubic foot, L is the path. length in and direction are normally recorded. Wind may aid in
feet, and e is the scattering or extinction coefficient in distributing the smoke for screening purposes. If the
feet squared per pound. TOP is defined by the smoke is produced continuously, wind often helps to
equation: pinpoint a marked area by observing the origin of the
plume. On the other hand, the wind may scatter the
smoke. In testing field ready smoke producers, each
TOP = I sample is numbered. The ignition time and burning time
Ct L t of each sample is recorded. Comments concerning out
of the ordinary conditions, such as excessive sparking
where Ct is the concentration of smoke required for on ignition, flame-ups while burning, and fuze failures
obscuration in pounds per cubic feet and Lt is the fixed are also recorded.
distance between the lamp and photocell in feet. The
concentration of smoke, C, from equation 10-1 is related (4) Photographic techniques. Smoke plumes
to the concentration in equation 10-2 by the relationship: can be studied with time exposure photography.
Exposure times of several minutes can be used to study
C=YCt (10-3) the diffusion of smoke into the atmosphere. Time
exposure during the daylight requires either an
where Y is the yield or the ratio of the weight of aerosol extremely slow film, a very small aperature, or the use
produced to the unit weight of the smoke producing of very dense filters. If these conditions cannot be
composition. Combining equations 10-1, 10-2, and 10-3 attained, the dispersion photographs can be made under
yields: twilight conditions.
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(4) Fuel spread and runoff during burning. b. Thermogravimetry. The same method
(5) Oxygen depletion or contamination. used in the analysis of explosives and discussed in
(6) Heating of the air in the vicinity of the Chapter 5 is used for pyrotechnic compositions. Either
target. method may be used on pyrotechnic compositions: the
weight can be monitored as the temperature is
(7) Damage capability as a function of target
programed to rise linearly with time or the weight can be
type.
monitored at a constant temperature. The former is the
preferred method.
e. Gas-Operated Devices. Pyrotechnic gas
generators may be designed to produce various c. Infrared Spectroscopy. This method is
quantities of gas at various rates and temperatures and discussed in Chapter 13.
under a variety of loading conditions. Gas operated
d. Thermal Conductimetric Analysis. In thermal
devices are tested under conditions nearly the same as
those anticipated during use. Special test fixtures may conductimetric analysis, the electrical conductance of
be required, but normally a closed bomb with a fixed the material under test is measured as a function of
volume approximately equal to the volume in the actual temperature. The variation in conductivity is caused by
application will suffice. Some test fixtures provide for such events as crystalline transitions which change the
expansion of the chamber with a moveable member as crystal lattice in such a way that the energy required to
pressure is applied from the pyrotechnic device. This cause electrons to go from the bound state into the
type of test measures the ability of the pyrotechnic conduction band is altered.
device to do some minimum amount of work. Both the e. Electrothermal Analysis. Electrothermal
pressure and the displacement of the moveable analysis consists of measuring two quantities as a
member are measured. Piezoelectric sensors are used function of temperature. The capacitance of the
for pressure measurement. Capacitance, inductance, or sample, which changes during a crystalline transition
resistance sensors are used for displacement between two stable forms, is measured. The dissipation
measurement. Piston, bellows, and dimple motors can factor is also measured. The dissipation factor is the
be actuated by the expanding gases. These motors are heat loss from an AC signal applied to the crystal. A
evaluated using force measuring transducers or by transition also causes the dissipation loss to increase
working them against springs. Testing includes during the change between the two stable states.
measuring the time from the initiation impulse and the
time from the start to the end of motion. The gas f. Classical Chemical Analysis.
producer and the pressure bomb must be properly (1) To test for positive ions, add 300
sealed. Copper washers are normally used for this milligrams of the sample to be tested to water and mix.
purpose. Filter the slurry and divide the filtered solution into two
parts. To one part of the solution add a drop of a
10-4. Analysis of Protechnic Compositions . The saturated sodium sulfate solution. Barium or strontium
following methods are used at the discretion of the will come out of the solution as a white precipitate. A
researcher to yield the particular data sought. flame test on a platinum wire, using the part of the
solution that was not treated with sodium sulfate,
a. Differential Thermal Analysis. The same identifies barium or strontium. A green flame is
method used in the analysis of explosives and produced by barium salts and a red flame is produced
discussed in Chapter 5 is used for pyrotechnic by strontium salts. To find the quantities of barium and
compositions. DTA can give qualitative information strontium, add sodium sulfate until no more precipitation
about the composition of a mixture. The presence of an is formed. Filter and weigh the precipitate. The
endotherm or exotherm, which is characteristic to a untreated aqueous solution may be flame tested for
particular compound, indicates the presence of the sodium and potassium. A yellow and violet flame is
compound in the mixture. The ignition temperature of produced respectively, although the potassium test is
the mixture can be determined. DTA can also be used diffcult. NH4 can be detected by an ammonia smell
to determine the purity of the sample since impurities after the solution has been made basic with sodium
greatly affect the melting point. A sharp endotherm at hydroxide.
the melting point indicates higher purity than a broad (2) To test for anions, the barium and
endotherm at a level slightly lower than the melting strontium ions must be removed by precipitation with an
point. excess of sodium sulfate.
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(a) To test for ClO3, add one milliliter of evolve hydrogen in five percent hydrochloric acid or five
the test solution to one milliliter of a solution that was percent sodium hydroxide. To test for iron, dissolve in
prepared from 20 grams of aniline hydrochloride and 50 dilute hydrochloric acid or nitric acid and add potassium
milliliters of hydrochloric acid. The presence of the ion ferrocyanide. A blue color indicates iron. To test for
is indicated by a pink violet or dark blue color. sulfur, dissolve in carbon disulfide or pyridine and dry
(b) To test for NO3, add two milliliters of the solvent. The characteristic yellow color indicates
the test solution to two milliliters of a solution that was sulfur. Charcoal will produce an orange flame in the
prepared from 25 grams of FeSO4 in 100 milliliters of flame test.
distilled water and 25 milliliters of concentrated sulfuric
acid. Hold the test tube at a slight angle and add one 10-5. Sensitivity.
milliliter of concentrated sulfuric acid to the wall of the
test tube. Manipulate the test tube to cause the drop to a. Impact. This test is performed on any of the
slide down the wall and into the solution. The drop of various impact sensitivity devices.
sulfuric acid will sink to the bottom. A brown color at the b. Friction. This test is performed on the
interface between the sulfuric acid and water indicates pendulum friction device.
the presence of the nitrate. c. Hygroscopicity. In this test a weighed sample of
(c) To test for ClO4, first prepare a the material is subjected to air at a specified
solution of 40 milliliters of 10 percent aqueous CuSO4, temperature and relative humidity. The weight gain is
19 milliliters pyridine, and 50 milliliters of distilled water. noted.
This solution must be stored in a tightly stoppered bottle d. Sensitivity to Heat. Three methods are used to
to avoid breathing the pyridine vapors. Add two measure sensitivity to heat.
milliliters of this solution to 3 milliliters of the solution
under test. A precipitate of blue or white crystals
(1) In the first method, a sample of the
indicates the presence of the perchlorate ion. If no
material is contained in a blasting cap and immersed in
precipitation forms in a few minutes, scratch the bottom
molten metal bath. The temperature of the bath is
of the test tube with a glass rod to try to induce
controlled so that a reaction occurs in five seconds.
crystallization.
(2) In the second method, isothermal heating,
(d) To determine the amount of the
a sample of the material is subjected to a preselected
chlorate quantitatively, add an excess of NaHSO3, and
temperature for an extended period. This method
then precipitate AgCI by adding an excess of silver
determines the induction period of the material at a
nitrate solution. Filter and weigh the precipitate. One
specified temperature.
gram of precipitate corresponds to 0.855 grams of
KC102 in the mixture. (3) In the third method, adiabatic heating, a
sample is placed in an oven or furnace and heated at a
(e) To determine the amount of the
slow rate. A thermocouple monitors the temperature at
perchlorate quantitatively, use tetraphenylphosphonium
the sample. When an exothermic reaction starts, the
chloride to precipitate the tetraphenylphosphonium salt.
temperature of the furnace is adjusted so no heat is
(f) To determine the amount of NO3, gained or lost by the sample. The temperature at which
the chlorate and perchlorate must be removed from the the reaction accelerates to deflagration is called the
solution. Then nitron is used to form a precipitate. autoignition or deflagration temperature.
Nitron is a standard reagent with the formula C20H16N4
and a molecular weight of 312.38.
e. Electrostatic Discharge. The standard
electrostatic discharge sensitivity device described in
(3) In the original test mixture the materials Chapter 5 is used for this test.
which did not dissolve in water are most likely either f. Compatibility. This test is performed by mixing
metals, sulfur, or charcoal. Magnesium will cause the a sample of the pyrotechnic composite with another
evolution of bubbles of hydrogen gas if five percent material and subjecting the mixture to the 120°C
acetic acid is added. Aluminum will not. Aluminum will vacuum stability test for 40 hours.
10-13/(10-14 blank)
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CHAPTER 11
FOREIGN ENERGETIC MATERIALS
11-1. Introduction. This chapter reflects the currently the monovalent radical -CO.NH2. Organic amides are
available, unclassified information on foreign energetic nonexplosive unless nitrated and are not considered
materials. Security restrictions may, in some cases, here. The metallic amides include:
date the material presented. Generally, foreign
energetic materials are the same as those used by the
United States although the composition of some of the (1) Auric imidoamide, Au (:NH)NH 2 or
composites varies. HN:Au.NH2, is an extremely explosive and sensitive
powder. The compound does not explode when wet and
11-2. French Energetic Materials. No information is so is stored under water. Storage at 100°C for several
presented on priming compositions or initiating hours causes auric imidoamide to become so sensitive
explosives. The French for fulminating explosives such that handling without an explosion is virtually
as mercury fulminate is explosifs fulminants. Table 11- impossible.
1 lists some of the secondary explosives used by the (2) Cadmium amide, Cd(NH3), is a white
French. powder which explodes upon rapid heating. The salt
can be prepared by treating cadmium iodide or KCd
Table 11-1. French Secondary Explosives cyanide with a solution of potassamide in liquid
ammonia. When heated to 180°C in vacuo, cadmium
English French amide loses ammonia leaving cadmium nitride, Cd3N2,
TNT Trotyl a black, amorphous powder that explodes when brought
Pyroxylin Pyroxyline, collodion in contact with water.
Pyrocellulose Coton-Poudre (CP)
Guncotton Coton-Poudre (CP) (3) Potassium amide, KNH2, is not used as
Nitroglycerin Nitroglycerine an explosive but is used as an intermediate in the
Nitrostarch Nitrate d' amidon preparation of other explosive amides. The normal
PETN Penthrite method of preparation is to add a small amount of
TEGN Dinitrate platinum black to a solution of liquid ammonia and
de triethyleneglycol metallic potassium. Without the platinum, the reaction
HMX Octogene, takes weeks or months.
cyclotetramethylenetetrnitramin (4) Silver amide, AgNH 2, is a white
RDX Hexogene, T4, precipitate which darkens and shrinks in volume on
cyclotrimethylene-trinitramine exposure to air. The compound can be prepared by
Picric acid Melinite mixing a solution of potassamide with silver nitrate or
iodide in liquid NH followed by washing by decantation
The following explosives are also used by the French: and careful drying. This compound is extremely
sensitive and can shatter test tubes and tear holes in
a. Explosif Amylace. These are the amide several layers of towels wrapped around the tube for the
explosives. An inorganic amide explosive, also called protection of the operator.
ammonobase, is a compound in which one hydrogen is
replaced by a metal. Metallic amides are prepared by (5) Sodium amide, NaNH2, consists of white
precipitation from liquid ammonia solutions by the action crystals with a melting point of 206.4°C. The compound
of potassium amide, KNH2. Potassium amide is also dissolves in liquid NH3 and is vigorously hydrolyzed by
referred to as potassamide. An organic amide contains water. Preparation is by means of metallic sodium
dissolved in ammonia, the reaction is catalyzed by iron
wire.
11-1
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d. Explosifs Couche. These are explosives with are actually CSE explosives. Other examples include:
temperatures of explosion of below 1,500°C which are 63-CSE-1949 which contains 67 percent ammonium
permitted for use in coal layers of fiery coal mines. For nitrate, 12 percent 20/80 pentolite, and 21 percent
example, Grisou naphthalite couche contains 95 percent aluminum powder; 68-CSE-1949 which contains 20
amtmonium nitrate and 5 percent trinitronaphthalene, percent ammonium nitrate, 20 percent PETN, 1.5
while Grisou dynamite couche contains 12 percent percent dinitronapthalene, and 58.5 percent sodium
nitroglycerin, 0.5 percent collodion cotton, and 87.5 chloride; 123-CSE-1948 which contains 17 percent
percent ammonium nitrate. Sodium chloride is also ammonium nitrate, 23 percent PETN, and 60 percent
used in couche to reduce the explosion temperature. sodium chloride; and 133-CSE-1948 which contains 22
e. Explosifs CSE. These are a series of percent ammonium nitrate, 20 percent PETN, 3 percent
explosives developed at the laboratory of the TNT, and 55 percent sodium chloride. These are used
Commission des Substances Explosives (CSE). The in fiery coal mines. Table 11-4 shows some of the
explosifs chlorates silicon CSE explosives.
11-3
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Some of the following plastic explosives were Table 11-5. German Secondary Explosives (Cont)
developed by the CSE. 33-CSE-1951 contains 75
percent RDX, 21 percent nitroglycerin, and 4 percent English German
nitropolystyrene. 34-CSE-1951 contains 88 percent PETN Peutrit, niperyth,
ammonium nitrate and 12 percent RDX. 36-CSE-1951 nitropenta (NP)
contains 82 percent RDX and a solution of 40 percent TEGN Triglykoldinitrat
polystyrene in liquid DNT. This explosive has a velocity EDDN Diamin
of detonation of 7,520 meters per second. 37-CSE- Nitroguanidine Gudol
1951 contains 85 percent ammonium nitrate and 15 TNT Fp 02
percent nitropolystyrene. 38-CSE-1951 contains 72.25
percent ammonium nitrate, 12.75 percent 11-4. Italian Energetic Materials. Italian explosives
nitropolystyrene, and 15 percent sodium chloride. are listed in table 11-6.
11-4
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The following explosives are used by the Italians: (5) Super BM. per galleria is a green powder
a. Afocite. Afocite is a blasting explosive which is slightly plastic. The powder contains aromatic
composition in two formulations. One formulation is 58 nitrocompounds with organic nitrates and plasticizers.
percent to 62 percent ammonium nitrate, 28 percent to
31 percent potassium nitrate, 7 percent to 9 percent (6) BM.a2 is a brown powder containing
carbon, and 2 to 3 percent sulfur. The other formulation ammonium nitrate, TNT, and thermite.
is 58 to 62 percent ammonium nitrate, 31 percent to 38 (7) Super BM. cava is a grey powder.
percent potassium nitrate, 3.5 percent to 4.5 percent
charcoal, 2 percent to 3 percent sulfur, and 1.5 percent (8) BM.2. per galleria is a grey powder
moisture. containing an inorganic nitrate, organic nitrocompounds,
and aluminum powder.
b. Amatolo. These are the amatols. The most
popular mixture is tipo 60/40, which has 60 percent (9) Carlsoniti are perchlorate based
ammonium nitrate and 40 percent TNT. Other explosives such as one formulation that contains 85
compositions used are tipo 80/20 and tipo 90/10. percent KCIO4 and 15 percent vaseline and another that
contains 88 percent KCIO4 and 12 percent
c. Ammonaftite. This is a mining explosive dinitrobenzene.
containing 76.7 percent ammonium nitrate, 15 percent
nitroglycerin, 0.3 percent collodion cotton, 0.3 percent i. Italian Dynamites. Italian dynamites are divided
grain flour, and 0.5 percent yellow ocher. into two groups, those with inert bases and those with
active bases.
d. Ammonal. These are mixtures containing
various percentages of ammonium nitrate, aluminum, (1) The inert base dynamites are:
and TNT. (a) Tipo I which consists of 70 to 75
percent nitroglycerin and 25 to 30 percent kieselguhr.
e. Ammonite No. 1. This is a blasting explosive (b) Tipo II which consists of 50 percent
consisting of 88 percent ammonium nitrate, 3 percent nitroglycerin and kieselguhr.
DNT, 3 percent nitroglycerin, 5 percent vegetable flour, (c) Dinamite nera (black dynamite)
and 1 percent diphenylamine. which consists of 45 to 55 percent nitroglycerin and 45
f. Antigrison. These are permissible explosives. to 55 percent coke.
Autigrison N.O contains 80.57 percent ammonium (d) Dinamite al carbonie di legno
nitrate, 6.36 percent dinitronaphthalene, and 13.02 (charcoal dynamite) which consists of 90 percent
percent ammonium chloride. Autigrison N.2 contains nitroglycerin and 10 percent charcoal.
81.49 percent ammonium nitrate, 11.11 percent (e) Dinamite rossa (red dynamite)
dinitronaphthalene, and 7.4 percent ammonium contains 68 percent nitroglycerin and 32 percent tripoli.
chloride. Autigrison N.3 contains 82 percent ammonium (f) Wetter-dinamite (permissible
nitrate, 5 percent trinitronaphthalene, and 13 percent dynamite) contains 35 to 40 percent nitroglycerin, 10 to
ammonium chloride. 14 percent kieselguhr, and 32 to 50 percent magnesium
g. Autonile. There are two explosive mixtures of sulfate.
ammonium nitrate and TNT. In one, used in quarries, (2) The active base dynamites are:
the oxygen content is 5.9 percent. The other, used in (a) Gelatinagomma (or gelatina
tunnels, has an oxygen content of 3.08 percent. esplodente) which is a blasting gelatin with the
composition of 92 to 93 percent nitroglycerin and 7 to 8
h. BM. These are a series of mining explosives. percent collodion cotton.
(1) BM.1. per galleria is a grey powder (b) Gelatina esplosiva da guerra
consisting of TNT, ammonium nitrate, and thermite. which is a military blasting gelatin with the composition
86.4 percent nitroglycerin, 9.6 percent collodion cotton,
(2) BM.as. per uso a cielo aperto is a reddish and 4 percent camphor.
powder consisting of ammonium nitrate, cyclic aliphatic (c) Gelatina dinamite is a gelatin
compounds, and metallic powders. dynamite containing 67 to 86 percent nitroglycerin, 3 to
(3) BM.ac. per uso a cielo aperto is a 5.5 percent collodion cotton, 5 to 25 percent potassium
brownish yellow powder containing ammonium nitrate nitrate, and 2 to 10 percent woodflour.
and TNT. (d) Ammon dinamite (gelatina 65
percent) contains 63 percent nitroglycerin, 2 percent
(4) BM.57. per uso a cielo aperto is a greyish collodion cotton, 30 percent ammonium nitrate, and 5
black powder based on ammonium nitrate. percent woodflour.
11-5
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ff. Oxiliquite. This is one of the liquid air rr. Tetranitroauilina. This is an explosive used
explosives prepared in situ by pouring liquid air or liquid in crystal form in some detonators.
oxygen into a mixture of three parts carbon impregnated ss. Tetritol. Italian for tetrytol.
with two parts petroleum. tt. Trinitrofloroglucinato di Piombo. This
gg. Oxilite. This is another liquid air or oxygen
compound is used in some initiating compositions in
explosive prepared in situ. The fuel in this explosive is place of lead styphnate.
fossil flour that has been impregnated with petroleum.
hh. Pentritolo. In Italian this is also called uu. Umbrite. There are two formulations of this
pentrol. The English name is pentolite. explosive. Umbrite A contains 48.4 percent
ii. PNP Esplosivo. This is an explosive used nitroguanidine, 37.3 percent ammonium nitrate, and
for press loaded projectiles that consists of 20 percent 14.3 percent ferrosilicon. Umbrite B contains 45.1
PETN, 77 percent ammonium nitrate, and 3 percent percent nitroguanidine, 41.4 percent ammonium nitrate,
wax. and 13.5 percent ferrosilicon. Both are used as bursting
jj. Polvere FB. There are 860 and 960 calorie charges in some projectiles.
types which contain 32 and 31 percent nitroglycerin, 57 11-5. Japanese Energetic Materials. Table 11-10 lists
and 61 percent nitrocellulose (12 percent nitrogen the Japanese explosives.
content), 9 and 5.5 percent butylphthalate, and 2 and
2.5 percent centralite. Both are used in rapid fire Table 11-10. Japanese Explosives
cannons. English Japanese
kk. Polvere FC. There are 860 and 960 calorie Lead azide Chikkgen, chikka namari
types which contain 28 and 32 percent nitroglycerin, 64 Mercury fulminate Raiko, raisan
and 62.5 percent nitrocellulose (12 percent nitrogen Nitrocellulose Shokamen
content), 4 and 3.5 percent centralite, and 1 and 0.5 Guncotton Menyaku
percent vaseline. Both are used in rapid fire cannons. Nitroglycerin Nitoroguriserin
ll. Polvere NAC. There are 860 and 960 PETN Shoeiyaku
calorie types which contain 27 and 32 percent RDX Shouyaku, tanayaku
nitroglycerin, 66 and 63 percent nitroacetylcellulose Tetryl Meiayaku, sanshoki,
(11.2 percent nitrogen content), 7 and 4 percent mechira nitroamin
centralite, and 0 and 1 percent DPhA. Both are used as Ammonium picrate Picurinsan ammonia
cannon propellants. TNT Chakatsuyaku,
mm. Polvere Nera. Italian for black powder. sanshokitoruoru
nn. Polvere al Nitrodiglical. There are 860 and Ammonium nitrate Ammon shosanen
730 calorie types which contain 68 and 27 percent
DEGN, 30 and 63.5 percent nitroacetylcellulose, 0 and 5 The following limited data is available on the most
percent acetylcellulose, and 2 and 4.5 percent centralite. currently used Japanese energetic material. Japan has
oo. Polvere al Nitrometriolo. These are no army but has a national self defense force.
propellants with TMETN. M4, M6, and M8 have Energetic material research is done for this organization.
compositions of 55.5, 57.5, and 59 percent TMETN; 40, Current developments and usage are along the lines of
36, and 33 percent nitrocellulose; 2.5, 4.5, and 5.9 that in the western countries.
percent acetylmetriol; 2, 2, and 2.5 percent centralite.
pp. Polveri da Lancio Senza Fumo. These are a. Akatsuki. This is an ammonium nitrate
the smokeless propellants. These are divided into explosive containing 73 to 75 percent ammonium
single based propellants with a volatile solvent, double nitrate, 5 to 6 percent nitroglycerin gel, 3 to 5 percent
based propellants with nitroglycerin, double-base cellulose, and 9 to 14 percent other ingredients. The
propellants without a volatile solvent, double-base explosive has a detonation velocity of 3,490 meters per
propellants with a volatile solvent, and propellants with second, an empirically determined detonation pressure
several components. of 42.3 kilobars, and a calculated detonation pressure of
qq. T4 Plastico. Two mixtures are known. One 33 kilobars.
has 89 percent RDX and 11 percent vaseline and the b. Ammonaru. This is the Japanese name for
other has 78.5 percent RDX, 17.5 percent DEGN (which ammonal.
contains 0.3 to 0.4 percent collodion cotton), and 3 c. Kokushokuyaku. This is the Japanese name for
percent vaseline. black powder.
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d. Chauyaku. This is the Japanese name for 50/50 Table 11-11. Russian Explosives (Cont)
cyclotol. English Russian
Tetracene Tetratsin
e. Dainamaito. This is the Japanese name for
Mercury fulminate Gremoochaya rtoof
dynamite. Japanese dynamites are based on Guncotton Khlopchatoboomazhnyi
nitroglycerin and are brown to buff in color. Some types porokh
of dynamites contain nitrocellulose and others contain Pyroxylin (N>12%) Kolloksilin, piroksilin
diatomaceous earth. Some gelatin dynamites, the so- Pyrocellulose Piroksilin No. 2,
called faint smoke dynamites, contain borax or salt. (11.5% <N <12%) pirokollodion
Nonfreezing dynamites contain nitroglycol or
Nitroglycerin Nitroglitserin
dinitroglycerol. The Japanese also produce ammonium
PETN Ten
nitrate and semigelatin dynamites.
HMX Oktoghen
f. Pentoriru. This is the Japanese term for 50/50 RDX Gheksoghen
pentolite. Tetryl Tetril
Ammonium picrate Pikrat ammoniya,
g. Shoanyaku. These are a series of mining pikrinovokislyi ammonii
explosives which consist of the following: TNT Toe, trotil
(1) No. 1 contains 70 percent ammonium Ammonium nitrate Ammoniynaya selitra
nitrate, 9 percent dinitronaphthalene, 1 percent
woodmeal, and 20 percent salt. The following energetic materials are used by the
Russians.
(2) No. 2 contains 79 percent ammonium
nitrate, 10 percent dinitronaphthalene, 1 percent saw-, a. A or AT. This is the Russian abbreviation for
dust, and 10 percent sodium chloride. amatol.
(3) No. 5 contains 64 percent ammonium b. A-IX-2. This is an explosive mixture used as a
nitrate, 12 percent TNT, 3 percent woodmeal, 1 percent projectile filler that contains 73 percent RDX, 23 percent
wheat starch, and 13 percent sodium chloride. aluminum powder, and 4 percent wax.
(4) No. 7 contains 75 percent ammonium c. Akvanity (Akvanites). These are a series of
nitrate, 9 percent dinitronaphthalene, 1.5 percent TNT, industrial explosives.
1.5 percent woodmeal, and 13 percent sodium chloride.
(1) Plastic akvanites No. 2 and No. 16 have,
(5) Special contains 64 percent ammonium in contrast to dynamites, a plasticizing base consisting
nitrate, 3 percent dinitronaphthalene, 7 percent TNT, 2 of an aqueous solution of potassium nitrate thickened to
percent nitroguanidine, 2 percent sodium nitrate, 2 a gel-like consistency in which ammonium nitrate and
percent woodmeal, and 20 percent sodium chloride. other constituents (such as combustibles) are also
h. Shotoyaku. This is the Japanese name for partially dissolved. Their liquid phase at normal
amatol. temperature is about 20 to 25 percent, of which 5 to 7
percent is water.
11-6. Russian Energetic Materials. Table 11-11 lists (2) Slurry-type akvanite 3L (where L stands
some explosives used by Russia. for l'yonshchiysya-pourable), uses as a base a thickened
aqueous solution of ammonium nitrate making up 45
Table 11-11. Russian Explosives percent of the liquid phase. Other ingredients are as in
dynamites. Akvanite 3L has a liquid-viscous
English Russian
consistency and therefore is suitable for charging
Lead azide Azid svintsa
descending blastholes and drillholes by the method of
Lead styphnate Stifnat svintsa,
casting or by compression under water.
teneres
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d. Akvatoly (Akvatols). These are industrial slurry rock oriented. The composition of these is shown in
explosives. Akvatol 65/35 contains granulated table 11-12.
ammonium nitrate as an oxidizer, 27 to 30 percent TNT
as a combustible and sensitizer, and 2.5 to 3.5 percent Table 11-12. Some Ammonits Formulations
of the sodium salt of carboxymethylcellulose which is a PZhV-20 AP-4ZhV AP-5ZhV
thickening agent. Akvatol M-15 contains granulated Ammonium nitrate (%) 64 68 70
ammonium nitrate, 12.5 to 13.2 percent coarse TNT (%) 16 17 18
aluminum powder, 21 to 22 percent TNT, and 1.0 to 1.5 Flame inhibitor (%) 20 15 12
percent of the sodium salt of carboxymethyl cellulose.
The water content of akvatol slurries must not exceed (3) Ammonit skal'nyi No. 1 is used in the
13 to 25 percent by weight. In some cases the sodium
carboxymethylcellulose can be replaced by other pressed state for blasting hard rocks in open or
binding agents such as borax or polyacrylamide powder. underground works.
Akvatols are usually prepared at plants and shipped in
the form of anhydrous friable mixtures, packed in paper (4) Ammonit V-3, shnekovannyi is used in
bags for the addition of water at the site of use. They flooded drill holes.
can also be shipped in ready to use water filled slurries.
(5) No. 9-2hV and No. 10-ZhV are
e. Alyumatoly (Alumatols). These are waterproof mixtures used for blasting soft or medium
combinations of ammonium nitrate, TNT, and rocks. Their compositions are:
aluminum. Russian alumatols are granulated and
waterproof. They are used in open cut work for breaking
very hard rock. No. 9 No. 10
Ammonium nitrate (%) 87 85
f. Alyumit No. 1. This is a Russian commercial
explosive that consists of 80 percent ammonium nitrate, TNT (%) 5 8
12 percent TNT, and 12 percent aluminum. Woodmeal (%) 8 7
g. Alyumotol. This is a granulated melt of TNT and (6) Ammonit sernyi No. 1 -ZhV, for use in
aluminum. sulfur mines, consists of 52 percent waterproof
h. Amatol. This is the same as amatol in English. ammonium nitrate, 11.5 percent TNT, 1.5 percent
woodmeal, 5 percent of a mixture of low freezing point
i. Ammoksily or Ammoxyly. This is a nitroesters, and 30 percent flame inhibitor.
nonpermissible mining explosive that consists of
ammonium nitrate and trinitroxylene. (7) Ammonit neftyanoy No. 3-ZhV, for use in
mines with petroleum vapors, consists of 52.5 percent
j. Ammonaly. This is the Russian name for ammonium nitrate, 7 percent TNT, 1.5 percent calcium
ammonals. stearate, 30 percent flame inhibitors, 9 percent
nitroesters, 0.3 percent collodion cotton, and 0.2 percent
k. Ammonity (Ammonits). Ammonits are soda.
ammonium nitrate mixtures of powdered structure in
which TNT or other aromatic nitrocompounds are used (8) Ammonit T-19, a safety explosive used in
as the explosive sensitizer and fuel. In grain or fiery mines, consists of 61 percent waterproof
granulated form they are known as zernogranulity. The ammonium nitrate, 19 percent TNT, and 20 percent
most current ammonits are: flame inhibitor.
(9) Shashki (demolition charges) skal'nago
ammonita are compressed charges which serve as
(1) No. 6-ZhV and No. 7-ZhV are waterproof. intermediate initiators for detonating nearly insensitive
The composition of the two is: explosives.
(2)
I. Ammonit Predokhranitel'nyi. This is a safety
No. 6 No. 7 commercial mine explosive which consists of 68 percent
Ammonium nitrate (%) 79 81.5 ammonium nitrate, 10 percent TNT, 2 percent powdered
TNT (%) 21 16 pine bark or oil cake, and 20 percent sodium chloride.
Woodmeal (0/o) - 2.5
m. Ammonit V-3V Poroshke. This is a powdered
explosive that contains 82 percent nonwaterproofed
(2) PZhV-20, AP-4ZhV, and AP-5ZhV are ammonium nitrate, 16.5 percent TNT, 1 percent asfal'tit,
and 0.5 percent paraffin.
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r. Detonity. These are powdery, water resistant v. Grammonal. These are powerful, granulated
explosives used in hard rock blasting. Table 11-15 lists ammonals with an increased aluminum content. They
typical compositions. are used in open pit blasting of hard rocks.
w. Granulity. These are granulated mining
explosives. Typical compositions are given in table 11-
16.
11-12
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Table 11-16. Granulity 11-7. Spanish Energetic Materials. Table 11-17 lists
Components, granulites: AC-8 AC-4 C-2 M some of the explosives used by the Spanish.
Ammonium nitrate,
granulated (%) 89.0 91.8 92.8 94.5
Aluminum,
Table 11-17. Spanish Explosives
powdered (%) 8.0 4.0 - - English Spanish
Woodmeal (%) - - 3.0 - Lead azide Azido de plomo,
Mineral oil (%) 3.0 4.2 4.2 5.5 nitruro de plomo, plumbazida
Detonation velocity,
meters per second 3,000 2,600 2,400 2,500 Lead styphnate Stifnato de plomo,
Trauzl test value, trinitroresorcinato de plomo,
cubic centimeters 410 390 320 320 triginato, tricinato
Tetracene Tetraceno
x. Igdanit. This is an ammonium nitrate, fuel oil Mercury fulminate Fulminato de mercurio
explosive that is prepared in situ just before use. Collodion cotton Algodon colodio,
Reported compositions vary from an ammonium nitrate (N about 12%) cotone colodio
composition of 94 to 97 percent. Guncotton (N>12%) Algodon fulminate,
algodon polvora, fulmicoton
y. Mansit. This is an explosive mixture that Nitroglycerin Nitroglicerina
consists of 72 percent ammonium nitrate, 23 percent aceite explosivo
ammonium picrate, and 5 percent petroleum asphalt. PETN Pentrita, nitropenta,
z. Miporit. This is an explosive used in gaseous nitropentaeritrita
mines that contains 65 percent waterproofed ammonium RDX Hexogeno, T4, exogeno,
nitrate, 15 percent TNT, 18 percent flame inhibitor, and ciclonita
2 percent foamed urea-formaldehyde resin. Tetryl Tetralita, tetralo,
tetranitrometilanilina
aa. Pobedit VP-4. This is a permissible Ammonium picrate Picrato amonico
explosive used in fire damp mines that consists of 65.5 TNT Trilita, trotilo,
percent water resistant ammonium nitrate, 9.0 percent tol, trinitrotolueno
low freezing point organic nitrates such as nitroglycerin Ammonium nitrate Nitrato amonico
and nitroglycol, 12 percent TNT, 12 percent flame
extinguisher, 1.5 percent woodmeal, 0.13 percent The following explosives are used by the Spanish.
collodion cotton, 0.1 percent calcium stearate, and 0.1 a. Amatolos. This is Spanish for amatols.
percent soda.
b. Amonales. This is Spanish for ammonal.
bb. Selectite No. 1 (Celektit No. 1). This is a
c. Amonitas. These are explosives that contain
granulated, friable, water resistant ammonium nitrate
from 50 to 100 percent ammonium nitrate, other nitrated
explosive with 10 percent low freezing point nitrate
products, and a small portion of other substances such
esters.
as nitroglycerin, sawdust, and dichromates. Some
explosives of this type are called explosivos favier,
cc. Slurry Explosives. These consist of
australita roburita, donarita, and perdita. Such mixtures
ammonium nitrate in a thickened, water based
are somewhat more sensitive to shock and friction and
suspension described in Chapter 8. Akvatols 65/35 and
have a lower rate of detonation than other ammonium
M-15 are considered slurry explosives.
nitrate explosives. Their hygroscopicity and relative
instability in prolonged storage are the principal
dd. Tetritoly. This is Russian for tetrytol.
disadvantages. They are used in mining operations and
as main charges in some projectiles.
ee. Uglenity. These explosives, which are also
called ooglenity, are coal mining explosives used in d. Anagon. This is an ammonal type explosive
firedamp and dusty environments. They are ammonium which contains 70 percent ammonium nitrate, 20
nitrate based. percent aluminum zinc alloy, and 10 percent charcoal.
11-13
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Table 11-18. Spanish Artigrisu Explosives aluminum. Organic combustibles such as vaseline,
No. 1 No. 2 No. 3 paraffin, or oils may also be used. These explosives are
Ammonium nitrate (%) 80.6 80.9 82.0 similar to ammonium nitrate but have a greater packing
Dinitronaphthalene (%) 6.4 11.7 density and are more sensitive to impact. The
Ammonium chloride (%) 13.0 7.4 13.0 explosives are used as a substitute for dynamite in
Trinitronaphthalene (%) - - 5.0 mining operations.
k. Explosivo Plastico "La Maranosa." This plastic
f. Baratol. These are high explosives that contain explosive consists of 85 percent RDX, 5.5 percent
from 10 to 70 percent barium nitrate and TNT. They are rubber, and 9.5 percent gelatinizing oil. The composite
used as bursting charges. is of low sensitivity. At 200°C decomposition without
g. Dinamitas. This is Spanish for dynamite. These explosion occurs but with the evolution of heavy nitrous
are considered industrial explosives. Spanish fumes. A carbonaceous residue is left.
dynamites can be divided into two groups with variable I. Hexogeno Plastico. These are also called
composition. plastex or PE. They correspond to American
(1) Dinamitas a base inerte are dynamites composition C. The explosive is prepared by coating
with an inert base. To this class belong the granular RDX with 12 percent vaseline and other oily
compositions containing 75, 50, or 30 percent substances. The product is a yellow colored, plastic
nitroglycerin with kieselguhr. They are called number 1, material which can be cut, perforated, and handled
2, and 3 depending upon the nitroglycerin content. without extra precaution. Initiation is relatively easy with
Dynamite 3 is the most popular type. a blasting cap or various detonators. In extreme
climates this explosive must be stored in protected
(2) Dinamitas a base activa are dynamites
areas. No casing is required in some demolition
with an active base. These dynamites contain a
applications.
combustible material or explosive material as the active
base. The type of base material further divides these m. Hexonitas. These consist of 80 or 50 percent
into classes. RDX and 20 or 50 percent nitroglycerin. The 50/50
composition can be further gelatinized and plasticized
(a) Dinamitas a base de nitratos use
with some collodion cotton. A mixture of 50 percent
nitrates of ammonium, sodium, or potassium and a
RDX, 46 percent nitroglycerin, and 4 percent collodion
combustible such as carbon, sawdust, or flour.
cotton is called hexonita gelatinizada.
(b) Dinamitas a base de chloratos use
n. Qxiliquita y Aire Liquido. This is an explosive of
potassium or sodium chlorate in place of nitrates.
liquid oxygen or liquid air with finely pulverized charcoal,
(c) Dinamitas gelatinas contain cork dust, or other absorbent fuel.
collodion cotton in sufficient proportion to gelatinize the
o. Polvoras Negras. This is Spanish for black
nitroglycerin. Compositions that contain only
nitroglycerin and collodion cotton are called goma. All powder. Spanish black powders are divided into three
others are called gelatina dinamita, nitrogelatina, or groups.
simply gelatina. If a dynamite less sensitive than gomas (1) Polora de guerra, military black powder,
is desired, three to five percent camphor is added. contains 75 percent potassium nitrate, 12.5 percent
Such compositions are called gelatinas explosivas de charcoal, and 12.5 percent sulfur.
guerra (military gelatins). (2) Polvora de caza, sporting powder,
h. Dinamones. Dinamones are permissible contains 80 percent potassium nitrate, 11 percent
explosives similar to amonitas except that they do not charcoal, and 9 percent sulfur.
contain aluminum or aromatic nitrocompounds. (3) Polvora de mina, blasting powder,
i. Donarita. This is a mining explosive that contains 80 percent potassium nitrate, charcoal, and
contains 80 percent ammonium nitrate, 12 percent TNT, sulfur. The exact percentages of charcoal and sulfur are
4 percent gelatinized nitroglycerin, and 4 percent unknown.
woodmeal. p. Tetritol. This is Spanish for tetrytol. The
j. Explosivos cloratado. This class of explosives Spanish use tetritol as a bursting charge and as a
contains 60 to 80 percent chlorates or perchlorates of booster.
sodium, potassium, or ammonium mixed with a q. Tonita. This is a mixture of 68 percent barium
combustible material such as carbon, sulfur, or nitrate, 13 percent dinitrobenzene, and 19 percent gun-
cotton.
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i. Nobelit. This is a permissible gelatin dynamite and 1.2 percent collodion cotton. Another formulation is
containing 28 percent nitroglycerin, 1 percent collodion 43 percent ammonium chlorate, 26 percent ammonium
cotton, 40 percent ammonium nitrate, 13.5 percent nitrate, and 31 percent of a mixture that contains 96
combustibles (such as flour, woodmeal, and dextrin), 17 percent TNT and 4 percent nitrocellulose. Territ is
percent sodium chloride, and 0.5 percent vegetable oil. comparable in properties to some low freezing point
dynamites and is safe to handle. The brisance of the
j. Reolit A, B, C, D, or Eand Reomex A or B. mixture is such that in mining coal or other mining
These are trade names for slurry blasting explosives. operations, no small dust particulates are formed. Territ
k. Seramin. This is an ammonium nitrate is sometimes difficult to detonate so present
dynamite consisting of 72.5 percent ammonium nitrate, formulations contain some nitroglycerin.
18 percent nitroglycerin, 8.7 percent sawdust or
charcoal, and 0.8 percent benzene or creosote. 11-9. Swiss Energetic Materials. In Switzerland the
production of black powder and propellants is a
I. Sprangdeg. These are plastic explosives that monopoly of the government. The Swiss government,
usually contain RDX or PETN with a desensitizing oil however, does not manufacture explosives except for
and special plasticizers. One such explosive consists of small quantities of primary explosives. Commercial
84 percent PETN and 16 percent mineral oil that is firms produce the explosives used by the army under
mixed by a special procedure. The product is moldable strict control by military authorities. Switzerland does
at temperatures below -1 50C. not generally export military explosives, however, during
times of low usage some export has taken place to keep
m. Spranggelatin. This is a blasting gelatin that is
facilities open. Table 11-21 lists some of the explosives
prepared by dissolving seven to eight percent collodion used by the Swiss.
cotton in slightly warm nitroglycerin. On cooling, a stiff
Table 11-21. Swiss Explosives
jelly is formed that is one of the most powerful
explosives known.
English Swiss
n. Startex A. This is another slurry blasting agent. Lead styphnate Bleitrinitroresorzinat,
bleistyphnat
o. Svartkrut. This is Swedish for black powder. Nitroglycerin Nitroglycerin
The composition falls within the following limits: PETN Pentaerythrit-tetranitrat,
potassium nitrate 74 to 78 percent, charcoal 12 to 15 nitropentaerythrit, pentrit
percent, and sulfur 10 to 12 percent. For different TNT Trinitrotoluol, trotyl
grades of black powder, charcoals of different origin and
methods of preparation are used. Powders used in
a. Aldofit. This is a permissible explosive that
shotgun shells contain charcoal from black alder
contains 81 percent ammonium nitrate, 17 percent TNT,
carbonized in furnaces. Ordinary powders use charcoal
and 2 percent woodmeal.
made from birch, alder, willow, or linden and blasting
powders use pinewood charred in kilns or furnaces. b. Ammonpentrinit. These are blasting explosives
with the compositions shown in table 11-22.
p. Territ. This is a cheddite type blasting explosive
that consists of 43 percent ammonium perchlorate, 28
percent sodium nitrate, 27.8 percent liquid DNT/TNT,
11-16
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Compositions with collodion cotton are also called that contains RDX and aluminum. The aluminum is
gelatinepentrinit. Aluminum can be incorporated to coated with a water insoluble wax to prevent
increase the blast effect of the explosives. wateraluminum reactions that release hydrogen.
c. Amolit. This is the trade name of afree flowing h. Hexonite. These are plastic explosives. One
bulk packaged ANFO. formulation consists of from 20 to 50 percent RDX and
d. Detonierande Zundschnur (Krallzundschnur). 80 to 50 percent nitroglycerin. Another formulation
This is Swiss for detonating cord. One such cord consists of 50 percent RDX, 46 percent nitroglycerin,
contains a core of PETN or RDX in a gel of collodion and 4 percent collodion cotton.
cotton and a liquid explosive such as nitroglycerin or i. Matter Explosives. These explosives are
nitroglycol. This formulation is coated on several textile named after their inventor 0. Matter. One explosive is
threads and covered with a fabric coating. a gelatin dynamite that consists of tar distillates mixed
e. Gelatine Cheddit. This is a plastic chlorate with inorganic oxidizers such as nitrates, chlorates or
explosive which contains 79 percent sodium chlorate, 5 perchlorates. Another formulation uses water soluble
percent of a liquid mixture of castor oil that coats the chlorinated hydrocarbons such as chloronaphthalene as
sodium chlorate, 2 percent liquid DNT, and 14 percent a fuel with a thickening agent.
TNT that has been preheated to 40°C. Some collodion j. Nitrogelatinedynamit. These are the gelatin
cotton may also be incorporated into the mixture. dynamites that contain 20 to 25 percent nitroglycerin
f. Gelatine Penthrinits. These are plastic, gelatinized with collodion cotton, ammonium nitrate, and
nonexudable, explosive blends of PETN and a liquid aromatic nitrocompound serving as a sensitizer.
nitroglycerin and other ingredients. If the amount of The nitroglycerin may be a 4:1 mixture of nitroglycerin
PETN in the formulation is below 60 percent, 6 to 7 and an antifreeze such as nitroglycol. The liquid
percent collodion cotton is added to improve plasticity. aromatic nitrocompound may be drip oil which is a
Compositions of some of the gelatine-penthrinit and byproduct of TNT manufacture. Some explosives which
penthrinit are given in table 11-23. belong to the class sicherheitsdynamite (safe to handle
g. Hexal. This is an antiaircraft ammunition filler and transport) include aldorfit, gamsit, and telsit.
Gelatine
Composition Penthrinits penthrinits
and properties
1 2 3 4 5 6 1 2 3 4
PETN (%) 80 85 70 50 40 80 50 59.0 15.5 50
Nitroglycerin (%) 20 15 30 50 60 15 46 24.7 77.5 46
Nitroglycol (%) - - - - - 5 - - - -
Collodion cotton (%) - - - - - - 4 0.6 7.0 4
NH4CIO4 (%) - - - - - - - 15.7 - -
Al (added) (%) - - - - - - - - - 30
k. Nizol. This is an explosive that contains meta n. Plastolit. This is a safe to handle plastic
dinitrobenzene made more sensitive to initiation by the explosive that contains 57 percent sodium nitrate, 15
addition of 30 percent PETN. The mixture is castable percent nitroglycerin, 4 percent nitroglycol, 1.3 percent
because of meta dinitrobenzene's low melting point, collodion cotton, 13 percent liquid DNT, 9.6 percent
800C. woodmeal, and 0.1 percent sodium bicarbonate.
I. Pentostit. This is the trade name for a military o. Totalit. This is a military explosive used as a
explosive in which PETN is desensitized with bursting charge that contains 95.5 percent ammonium
pentaerythritol tetrastearate. nitrate and 4.5 percent paraffin wax.
m. Pentro. This is petrtolite, which is also called p. Tramex. This is the trade name for a powdered
pentryl. nitroglycerin sensitized explosive.
11-17(11-18 blank)
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CHAPTER 12
12-1. General. This section contains general manual. Applicable information may be found in DoD
information about toxicity of military explosives. All 6055.9STD, Ammunition and Explosives Safety
tables indicating quantity distance separations, Standards.
minimum distances, etc., have been removed from this
12-2. Toxicity of United States Military Explosives. toxicity may vary from mild dermatitis or a
headache to serious damage to internal organs.
a. Many explosives, because of their chemical
structures, are somewhat toxic. To be b. Table 12-1 is a concise presentation of the
acceptable, a military explosive must be of toxicological properties of selected United
minimum toxicity. Careful attention must be States military explosives.
paid to this feature because the effects of
Inhalation of tetryl dust has recognized toxic effects. Avoid inhalation. Tolerance level
below 1.5 milligrams per cubic
meter in air.
Change 3 12-1
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Change 3 12-2
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Ammonium picrate Highly toxic by inhalation, ingestion, and skin Inhalation of the dust should be
absorption. minimized and frequent baths and
changes of clothes are desirable for
those working with the material in
quantity.
DBX Generally considered non toxic.
HBX-6 or H-6 Highly toxic by inhalation or ingestion. Avoid inhalation and ingestion.
TNT TNT exposures can occur by inhalation of the dust, Avoid inhalation and skin contact.
through ingestion, and via skin absorption. Among Tolerance level below 1.5 milli-
the first signs of TNT intoxication are changes in the grams per cubic meter in air.
blood: the red blood cell count and hemoglobin con-
tent decrease; abnormal red cells are seen; and there
is a transitory increase in leukocytes and lympho-
cytes. Rashes and skin eruption may be associated
with these effects. Increased capillary fragility leads
to nose bleeds and hemorrhages of the skin and
mucosa. At sufficiently high and prolonged expo-
sures, more serious blood phenomena appear.
These include methemoglobinemia, with consequent
cyanosis; hyperplasia of the bone marrow leading to
aplastic anemia (because the marrow no longer pro-
duces blood cells); and a drastic loss of blood
platelets. Petechiae often occur in conjunction with
aplastic anemia.
Change 3 12-3
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Tritonal Highly toxic by inhalation and ingestion. Avoid inhalation and ingestion.
Solid propellants
Single-base
propellants
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Nitroglycerin Nitroglycerin has been used as a vasodilator drug in Avoid inhalation or skin contact.
medicine, especially for the treatment of angina;
thus, there is a fairly extensive literature on its
biochemical and clinical aspects. The most common
medicinal dose is 0.65 milligrams (roughly 0.01 mil-
ligrams per kilogram), but many patients safely
receive 20 times this (about 0.2 milligrams per kilo-
gram) daily. Survival has been noted after quantities
up to 400 milligrams (about six milligrams per kilo-
gram) were administered orally or sublingually. Two
of the more noticeable symptoms are headache and
falling blood pressure.
Military pyrotechnics
HC smoke mixtures Moderately toxic by inhalation and ingestion. Skin Avoid inhalation, ingestion, and skin
contact can cause dermatitis. contact.
Black powder Moderately toxic by inhalation and ingestion. Avoid inhalation and ingestion.
TM 9-1300-214
CHAPTER 13
DETECTION AND IDENTIFICATION OF ENERGETIC MATERIALS
13-1. Introduction. This chapter discusses the 13-2. Wet Chemical Methods. When a test sample is
methods used to detect and identify energetic materials. treated with an appropriate reagent, a coloration is
Almost all of the analytical chemistry techniques are produced which is characteristic of the compound being
used. Normally, identification involves a series of tests, tested. These reactions are known as color reactions
each providing a clue to the identity of the compound. and may help identify the sample. The compound which
In addition to the techniques discussed in this chapter, produces the color change is called the color reagent.
identifying information can be obtained from physical Color reactions are used to some degree for preliminary
properties such as melting point, crystalline structure, identification and confirmation but have largely been
density, physical state, color, and indicies of refraction. replaced by the more modern instrumental techniques.
Table 13-1 lists some of the common color reactions
used to identify explosives.
1
Color appears immediately.
2
Sometimes explodes mildly (puffs) upon addition of sulfuric acid.
3
Tests of dried water extract.
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The tests are performed in the following manner. gives a pale blue-green color. RDX can be further
distinguished from HMX by repeating the test at 150°C.
a. Test 1. Place 0.05 gram of the explosive in a 5 Under these conditions RDX still gives a blue color, but
milliliter beaker, add 2 to 3 milliliters of distilled water, HMX produces an olive color.
and stir for 5 minutes.
(2) Composition A-3. Place 0.1 gram of the
(1) Observe color of liquid. material in a 10 milliliter beaker and add two or three
drops of acetone. Warm the mixture and allow to stand
(2) Wet one end of a strip of universal pH for five minutes. Evaporate the acetone by gently
indicator paper and note any change in color. warming on a steambath, cool, and add 2 milliliters of
(3) Add a drop of Nessler's reagent and note carbon tetrachloride. Cover the beaker and warm the
the color of any precipitate formed. Prepare the reagent contents, occasionally swirling the mixture. Cool the
by dissolving five grams of potassium iodide in a mixture and allow the undissolved material to settle.
minimum quantity of cold distilled water and adding a Decant the supernatant liquid into a 5 milliliter beaker,
saturated aqueous solution of mercuric iodide until a evaporate to dryness, and note if a waxy (not tarry)
faint precipitate is formed. Add 40 milliliters of 50- residue is obtained. Dry the undissolved material in the
percent potassium hydroxide solution. After the solution 10 milliliter beaker and test for RDX as described in (1)
has clarified by settling, dilute to 100 milliliters with above.
distilled water, allow to settle, and decant. (3) Composition B. Place 0.2 gram of the
pale yellow to medium brown material in a 10 milliliter
b. Test2. Place 0.05 gram of the unknown beaker and add 2 to 3 milliliters of chloroform. Cover
material in an indenture of a white porcelain spot-test the beaker. Warm and digest the mixture for 10
plate. Add two or three drops of a 65 to 68 percent minutes with occasional swirling. Decant the
aqueous solution of ethylenediamine and stir. Note the supernatant liquid through a filter paper and evaporate
color of the solution (not the solid). the filtrate to dryness. Repeat digestion of the insoluble
c. Test 3. Place 0.05 gram of the unknown residue in the beaker with three more portions of
material in an indenture of a white porcelain spot-test chloroform discarding the decanted liquid in each case.
plate and add three or four drops of a diphenylamine Dry the insoluble residue by evaporating any adherent
solution. Stir the mixture and, after one minute, note chloroform. If the original material was composition B,
the color of the solution. Prepare the diphenylamine the residue from the chloroform solution consists of TNT
solution by dissolving one gram of diphenylamine in 100 and wax. Test the TNT and wax mixture with
milliliters of concentrated CP sulfuric acid. ethylenediamine and diphenylamine as described
above. The insoluble residue obtained by extraction
d. Test 4. Place 0.05 gram of the unknown with chloroform consists of RDX. Test as described in
material in an indenture of a white porcelain spot-test (1) above.
plate. Add an equal amount of crystalline thymol and (4) Composition C-3. Place 0.2 gram of the
three drops of concentrated sulfuric acid. Stir the putty-like explosive in a 10 milliliter beaker and add 5
mixture and note its color after five minutes or more. milliliters of benzene. Mix and digest for 10 minutes
crushing any lumps present. Decant the supernatant
e. Additional Tests. If the unknown material is not
liquid through a filter paper and evaporate the benzene
identified completely by the tests in subparagraphs 13-2
with gentle heating. Note whether a dark, tarry residue
a. through d. and data listed in table 13-1, tests should
remains. Wash the insoluble residue left by benzene
be performed to determine whether the material is one
extraction with two or three, 3 milliliter portions of a 2: 1
of those indicated in (1) through (14) below.
ether-ethanol mixture and dry the washed residue. Test
(1) RDX. Place several milligrams of the this as described under RDX in (1) above. To the
white, unknown material in a test tube and add about decanted ether-ethanol washings, add 15 milliliters of
200 milligrams of thymol and six drops (0.3 ml) of distilled water and heat the mixture until all ether and
concentrated sulfuric acid. Warm the tube for five alcohol are removed. If a white precipitate
minutes at 100°C, and add 5 to 10 milliliters of ethanol. (nitrocellulose) is noted, catch the precipitate on a filter,
RDX produces a rich blue color. Under these conditions wash with ethanol, dry by evaporation of the ethanol,
sugars and aldehydes give a brown color, and HMX and test for nitrocellulose as indicated in table 13-1.
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(5) Torpex. Place 0.2 gram of the explosive (d) Transfer 2 milligrams of the sample
in a five milliliter beaker and extract with three, 3 to a5 milliliter beaker. Add 5 milliliters of a 10 percent
milliliter portions of acetone. Dry the insoluble residue aqueous solution of ferric chloride solution. A red color
and examine under a microscope. Note if the residue is formed which disappears slowly when 2 to 3 milliliters
has the characteristic appearance of metallic aluminum. of dilute mercuric chloride solution are added. This
Place 0.2 gram of the explosive in a 5 milliliter beaker confirms that the explosive is lead azide.
and digest with two, 3 milliliter portions of benzene,
decanting the benzene into a small evaporating dish. (10) Mercury fulminate.
Evaporate the benzene solution to dryness and test for (a) Test the explosive for solubility in
TNT as indicated in table 13-1. Dry the insoluble water. Mercury fulminate is insoluble in water.
residue from the benzene extraction and test for RDX as
described in (1) above. (b) Transfer 10 milligrams of the
sample explosive to a fritted glass crucible of medium
(6) Tritonal. Place 0.2 gram of the explosive porosity. Extract the sample with a 20 percent aqueous
in a 10 milliliter beaker and add 5 milliliters of acetone. solution of sodium thiosulfate, catching the washings in
Stir, allow any undissolved material to settle, and decant a 50-milliliter beaker containing 10 drops of a one
the liquid. Wash the insoluble matter with two, 5 percent phenolphthalein indicator solution. When the
milliliter portions of acetone, dry, and examine under a mercury fulminate is treated with sodium thiosulfate, it
microscope. Note if the insoluble matter has the dissolves with formation of alkali (NaOH) which changes
characteristic appearance of metallic aluminum. the color of the indicator solution from colorless to red.
Subject the separated explosive to the tests prescribed
for TNT in table 13-1. (c) Transfer 10 milligrams of the
sample to a 1 0-milliliter beaker and add three drops of
(7) Amatol. Place 0.2 gram of the yellow concentrated hydrochloric acid solution and 2 milliliters
material in a 5 milliliter beaker, add 3 milliliters of of water. Transfer the solution to another beaker
distilled water, and stir for five minutes. Decant the containing one drop of a five percent aqueous solution
liquid through a filter and evaporate to dryness. Test of potassium iodide. The formation of a bright red
the dried solid as prescribed for ammonium nitrate in precipitate indicates the presence of the mercuric ion.
table 13-1. Dry the water-insoluble residue and test as
prescribed for TNT above. (11) Diazodinitrophenol (DDNP). Dissolve
0.05 gram of the greenish-yellow to brown explosive in
(8) Ammonal. Place 0.2 gram of the acetone. Upon adding a larger volume of ice water, the
explosive in a 10 milliliter beaker and digest with 3 explosive should appear as bright yellow crystals.
milliliters of distilled water. Decant the liquid through a Prepare a saturated solution of the explosive in 200
filter and evaporate to dryness. Test the dried solid as milliliters of water. Add to this 5 milliliters of a 20
prescribed for ammonium nitrate. Digest the insoluble percent solution of sodium hydroxide and mix. The
residue in the beaker with three, 3 milliliter portions of evolution of a colorless gas and the appearance of a
acetone decanting these through a filter. Dry the reddish-brown color in the solution indicate the
insoluble residue and examine under a microscope. explosive to be diazodinitrophenol.
Note if the residue has the characteristic appearance of
metallic aluminum. Evaporate the filtrate to dryness by (12) Lead styphnate. Wet 0.1 gram of the
warming gently. Test the dried solid as prescribed for heavy, light orange to reddish-brown material with 10
TNT above. milliliters of water and then add slowly 10 milliliters of a
20 percent solution of ammonium acetate. Agitate the
(9) Lead azide. mixture until solution is complete. Add 10 milliliters of a
(a) Test the explosive for solubility in 10 percent aqueous solution of potassium dichromate.
water. Lead azide is insoluble in water. The appearance of a bright yellow precipitate indicates
the presence of lead. To 0.1 gram of the explosive in a
(b) Transfer 5 milligrams of the sample beaker add 10 milliliters of a 10 percent solution of
explosive to a 1 O0-milliliter beaker and add 10 drops of hydrochloric acid. Heat the mixture in a steambath and
a 1 0-percent ceric ammonium nitrate solution. A evaporate to dryness. Cool the beaker and contents
reaction accompanied by evolution of nitrogen oxides and add 10 milliliters of ether. Mix the contents and
(red fumes) is indicative of the presence of azide. allow to settle. Decant or filter off the yellow ether
solution and evaporate this to dryness at ordinary
(c) Treat the solution of the sample temperature. Dissolve the residue in 25 milliliters of
obtained in (b) above with a few drops of a 10 percent water and add 0.1 gram of solid potassium cyanide.
aqueous solution of potassium dichromate. A yellow to The absence of color indicates the explosive to be lead
reddishyellow precipitate is indicative of the presence of styphnate.
lead.
13-3
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(13) Tetracene. Wet 0.25 gram of the fluffy, each material under test. Column liquid
pale yellow explosive with 5 milliliters of a 10 percent chromatography has been implemented by other
solution of sodium hydroxide and warm the mixture in a modern chromatographic techniques because the
steambath until solution is complete. Note if there is an procedures are time consuming and tedious.
odor of ammonia. Cool the solution and add 1 milliliter
of a five percent solution of copper acetate. The b. Paper Chromatography. In paper
appearance of a bright blue precipitate indicates the chromatography both the stationary and mobile phase
explosive is tetracene. are liquids. The stationary phase liquid, which is
usually water, is supported on a filter paper. A spot of
(14) Black powder. Place 0.2 gram of the the mixture to be tested is placed on the filter paper.
black material in a 5 milliliter beaker, add 2 to 3 The spot is then dried. The filter paper is then placed in
milliliters of distilled water, and stir for five minutes. a trough which contains the mobile phase. The liquid
Decant the liquid through a filter and catch the filtrate in mobile phase is immiscible with the liquid of the
a beaker. Evaporate this to dryness and subject the stationary phase. The mobile phase is usually a mixture
dried white solid to the tests shown in table 13-1. Dry of organic solvents. The eluent is allowed to migrate
the water-insoluble residue in the beaker, cool, and either upward or downward on the paper. As the eluent
digest with two 5 milliliter portions of carbon disulfide, migrates, the compounds in the mixture separate, each
decanting these into an evaporating dish. Evaporate the traveling with the eluent but at a different rate. After the
carbon disulfide solution to dryness at room eluent front has advanced between 15 and 30
temperature. By means of a microscope, examine the centimeters the paper is removed from the trough and
yellow residue so obtained and the insoluble black dried. A color reagent is sprayed on the paper to locate
residue from the carbon disulfide extraction. Note if all the separated compounds. The ratio of the distance
they have the characteristic appearances of sulfur traveled by the separated compound to the distance
crystals and charcoal, respectively. traveled by the eluent front is then computed. In some
cases the filter paper is impregnated with hydrophobic
13-3. Chromatography.
substances such as oils or paraffins and the mobile
a. Column Liquid Chromatography. This is the phase is aqueous. This is called reverse phase paper
oldest form of chromatography and is sometimes called chromatography. Most work with energetic material has
column chromatography. The equipment consists of a been done using the reverse phase technique. Paper
vertical glass or quartz column which is constricted at chromatography is not generally used for identification
the lower end. The column is filled with a fine, of energetic material as is thin layer chromatography.
granulated material which is most commonly silica gel c. Thin Layer Chromatography. A thin layer
but may be metal oxides (alumina), sugars, etc. This is
chromatographic plate consists of a thin layer of
called the stationary phase. A chemical mixture in a
powdered material mixed with a binder that is applied to
suitable solvent is placed in the top of the column and
a smooth surface such as a glass, aluminum, or plastic
allowed to diffuse downward. The solvent is called the
sheet. The powdered material, which constitutes the
mobile phase. Vacuum is sometimes applied to the
stationary phase, usually consists of silica gel or
bottom of the column. The chemical components of the
aluminum oxide of uniform particle size. A solution of
mixture will diffuse at different rates due to their
the mixture to be tested is spotted near the bottom of
difference in affinity for the column material. After
the plate. The plate is then placed vertically in a trough
sufficient time the components will be separated into
of solvents, called the developing solvents, contained in
bands along the length of the column. If the
a closed developing tank. The level of the developing
components are colored, the bands can be easily
solvent in the trough is below the spot of test material.
detected. Colorless or white component bands can be
The developing solvents constitute the mobile phase.
detected by adding a fluorescent material to the column
The mobile phase is drawn up into the stationary phase
material contained in a quartz column and irradiating
by capillary action. As the level of the mobile phase
with ultraviolet light. The column is then extruded from
rises, the compounds of the test mixture are separated,
the tube and cut into bands. The separated compounds
each traveling with the mobile phase but at different
in the bands are eluted by suitable solvents and
rates. The liquid phase is allowed to rise to the desired
subjected to quantitative and qualitative analyses
level, usually near the top, and the plate is removed
procedures. The solvent has a significant effect on the
from the trough and dried. Colorless spots are detected
interaction between the material under test and the
by either spraying with a color reagent or incorporating a
column material. Therefore, the proper combination of
fluorescent material in the chromatographic plate such
column material and solvent must be used for
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that exposure to ultraviolet light will cause luminescence ionization detector measures the electrical conductivity
except where spots of ultraviolet absorbing compounds of the product gases when the carrier and test sample
are present. The rate of flow is defined as the ratio of are decomposed in an air/hydrogen flame. This type
the distance traveled by the compound to the distance detector is destructive but more sensitive and does not
traveled by the developing solvent. The rate of flow is have a great dependence on the gas temperature. The
affected by many factors such as the plate material, the current carried across the product gas is proportional to
developing solvent used, plate thickness, dryness of the the number of carbon atoms but inversely proportional
plate, temperature, and others. Therefore compound to the number of oxygen and nitrogen atoms. This is
identification is made by running the test solution on the the most commonly used detector. An electron capture
same plate as known compounds, not by comparing the detector uses a radioactive beta emitter to ionize the
rate of flow to published data. When more than one carrier gas. An electron capturing compound will
elution is required, thin layer chromatography can be run remove some of the ions. The resulting decrease in the
in two dimensions. The plate is spotted near one of the current carrying capability of the gas indicates the
corners at the bottom. Then the plate is developed presence of one of these compounds. This method of
normally in a developing solvent that separates the detection is very sensitive to electronegative
mixture into groups rather than single compounds. The compounds, but is insensitive to compounds such as
plate is then dried, rotated 90° so that the separated hydrocarbons which do not capture electrons. The
groups are along the bottom, and placed in a second detector output is recorded as a function of time, as
solvent trough. The second solvent separates the shown in figure 13-1. Each peak corresponds to a
groups into single compounds. Thin layer compound in the mixture. There is a general correlation
chromatography is used extensively as a qualitative between the area under the peak and the content of the
analysis technique. The developing solvents and plate compound in the mixture. However, the area ratio for
material used vary according to the test material so no two compounds does not necessarily represent their
single combination of solvent and material can be used weight ratio in the sample. This could be due to several
for separating all the energetic materials. reasons: difference in the detector response for
different compounds, adsorption or decomposition of a
d. Gas Chromatography. In gas chromatography compound before detection, or a faulty sampling
the vapor of the material to be tested is injected into a technique. Therefore, to use the recorder output
stream of inert gas such as nitrogen, and passed quantitatively a specific amount of a known compound
through a column. The carrier gas is the mobile phase, is added to the sample. The sample must react similarly
the material in the column is the stationary phase. The in the gas chromatographic unit to the unknown.
stationary phase can be either a solid or a liquid Relative weight percentages can then be computed by
supported on a solid. If the stationary phase is solid the comparing the area under the curve for the unknown
method is called gas-solid chromatography (GSC). If and known sample. Gas chromatography is used for
the stationary phase is a liquid supported on a solid then energetic materials, however, in some cases,
the method is called gas-liquid chromatography (GLC). application of this method is limited by the high
Two types of columns are used in GLC; packed temperature at which the test must be run.
columns, which contain an inert nonvolatile liquid, and Nitroaromatics are generally stable at their boiling point,
capillary columns, which are long, open tubes of small but nitramines and aliphatic nitrated esters are not. For
diameter that have a thin, liquid film on their inner the unstable compounds several techniques are
surface. Capillary columns offer a greater resolution of recommended to reduce decomposition; glass rather
mixture. As the carrier gas flows through the column than metal columns, short column length, lower
the components of the test mixture separate, each temperatures, low polarity liquid in the GLC stationary
traveling through the column material at a different rate. phase, and low loading percentage of the liquid. These
A detector at the end of the column detects when the precautions also minimize reaction between the
gas being tested emerges. Three types of detectors are compounds in the column. This is a consideration when
commonly used; thermal conductivity, flame ionization, analyzing the stabilizer content of propellants as the
and electron capture. A thermal conductivity detector higher temperature tends to drive off nitrogen oxides
detects changes in the thermal conductivity of the from the aliphatic nitrated ester and nitrate the stabilizer.
carrier gas. This type detector is simple and Gas chromatography can be run isothermally or with a
nondestructive but the sensitivity is low and the test programed temperature change.
results are highly dependent on gas temperature and
rate of flow. A flame
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e. High Performance Liquid Chromatography polar stationary phase and polar mobile phase. Another
(HPLC). HPLC is also known as high speed or high column material is the chemically bonded stationary
pressure liquid chromatography. Separation is done in a phase. Silica contains free hydroxyl groups. The
glass or stainless steel column that is packed with a fine hydrogen can be replaced by organic compounds,
powdered material, usually silica. Column dimensions although direct replacement with a carbon bond is less
are usually 15 to 30 centimeters in length and three to stable than bonding the oxygen to another silicon which
four millimeters in diameter. The packing material, or is bound to the organic compound. As the mobile phase
stationary phase, consists of particles in the 5 to 10 emerges from the column an ultraviolet
micrometer diameter range. A solvent, the mobile spectrophotometer is used to detect the test material in
phase, is pumped through the column under pressure in the eluent. The detector output is plotted as a function
the range of 1,379 to 6,895 kilopascals (200 to 1,000 of time. The graph obtained is very similar to the one
pounds per square inch). The test mixture to be shown in figure 13-1. The area under the peaks in the
separated is injected. Separation in the column is curve is proportional to the concentration of each
accomplished in the same manner as in the other forms component in the test material. A tentative identification
of chromatography: the various constituents diffuse of the compounds in the mixture can be made by
down the column at different rates. The composition of comparing the graph of the output of the unknown to the
the mobile phase can be held constant (isocratic elution) graph for known compounds run under the same
or varied (gradient elution) during the procedure to conditions. This identification, however, is not as
improve separation. When the column material is silica, specific as other methods and cannot be used in
surface adsorption is the mechanism of separation. forensic work, for example, where an exact identification
When the silica is coated with a liquid, partition between is required. The separated compounds can be collected
the two liquid phases is the separation mechanism. The and analyzed individually using one or a combination of
liquids of the stationary and mobile phase must be other methods for positive identification such as mass
immiscible. Normal HPLC is performed with a polar spectrometry, infrared spectrometry, and nuclear
stationary phase and a somewhat nonpolar mobile magnetic resonance.
phase. Reverse phase HPLC is performed with a non-
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f. Ion Chromatography. Ion chromatography is voltage is plotted against the current to obtain a
instrumentally very similar to HPLC, the difference polarogram. Single sweep polarography is more
between the methods being the column material. Ion accurate than DC polarography because the shorter
chromatography uses an ion exchange resin stationary time frame in which the measurement is made allows
phase which can be applied to glass microbeads for less change in the surface area of the mercury drop. In
packing. While HPLC is based on absorption and AC polarography, a small AC signal is placed on the DC
partiti6n phenomena, ion chromatography is based on waveform used in DC polarography. The effects of the
the exchange of ions between the resin and the mobile DC potential are electronically removed and a
phase. It is a very good technique for separating polarogram with peaks in the waveform is obtained. In
cations and anions from each other. differential pulse polarography, a pulse is applied just as
the mercury drop attains maximum size. The pulse has
13-4. Polarography. Polarography measures current an amplitude of 5 to 100 millivolts and a width of 50 to
in microamperes, generated through the 60 milliseconds. The current is measured twice, just
reduction/oxidation of chemical species in an electrolytic before the pulse and during the last 10 to 20
solution at an applied potential specific to the specie. A milliseconds of the pulse. The type and concentration of
reference electrode and polarizable electrode are used. species present is made by comparing polarograms.
The polarizable electrode normally used is the Dropping Polarography is a very sensitive method of detection.
Mercury Electrode (DME) which consists of a glass Applications include pollution control and analysis of
capillary filled with mercury. The mercury is allowed to sensitive material such as primary explosives, in which
drip from the capillary at a controlled rate. As a droplet sample sizes are held to a minimum because of safety
forms at the end of the tube the surface area of mercury considerations.
exposed to the solution increases. This causes an
increase in the current conducted through the solution at 13-5. Spectroscopy and Spectrometry.
any given voltage. There is a sharp decrease in the
current when the drop falls. The current then increases a. Ultraviolet and Visible Spectroscopy. In
during the formation of the next drop. Several forms of ultraviolet and visible spectroscopic techniques, a
polarography are used: DC, single sweep, AC, and solution of the sample to be analyzed is irradiated with
differential pulse. These four forms differ only in the discreet frequencies from the entire range of either the
manner in which voltage is applied between the ultraviolet or visible spectrum. To obtain a spectrum of
electrodes. In DC polarography, a DC potential, which the component, the absorbance, which is defined as the
is increasing linearly at the rate of 1 to 10 millivolts per log of quotient of the intensity of the incident and
second, is applied between the electrodes. At low transmitted radiation, is measured and plotted as a
voltages a small current, called the residual current, function of the frequency of the incident radiation.
flows. This current is due to charging the capacitance Usually a blank sample, which consists of only the
between the DME and the solution and miscellaneous solvent, is run at the same time so the absorbance of
impurities in solution. At a critical voltage depending on the solvent can be subtracted from the total absorbance
the chemical specie the current begins to increase with of the solution. Ultraviolet and visible spectra are not
increasing voltage. The current continues to increase generally used to identify energetic materials because
until a maximum current is attained, at which point they are not distinctive. However, the methods may be
further increases in voltage do not increase the current. used for quantitative analysis. The concentration of the
The plot of the applied voltage versus the current is compound in solution is determined by measuring the
called a polarogram. The difference between the absorbance of the material under test and comparing
residual current and maximum current is called the the value obtained to the value obtained for a solution of
diffusion current. The diffusion current is proportional to the same compound with a known concentration. The
the concentration of the chemical specie. In single same solvent, temperature, and optical path length
sweep polarography, a DC potential increasing at the through the solution must be used. With a limited
rate of 100 to 500 millivolts is applied between the number of exceptions, the concentration is a linear
electrodes. The voltage is applied at a specific time function of the absorbance.
during the formation of the mercury drop. The applied
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b. Infrared Spectroscopy. Infrared spectroscopy is and classified in terms of groups present in the molecule
one of the most widely used methods of identification. (OH; NH; C =0; N-NO2; aromatic NO2; C-O-C; C-O-NO 2;
The technique can be used with gases, solids, or liquids. etc.) and then compared with the standard spectra that
Gases or liquids are contained in cells containing salt contain the same groups. Table 13-2, which gives
windows, such as sodium chloride or potassium spectral correlations of aromatic nitro compounds,
bromide, that are transparent to infrared radiation over a nitramines, and nitrates, is useful for this purpose.
certain wavelength range. Solids may be in solution in Using infrared spectroscopy for identification depends
which case a blank cell that contains only the solvent is on having a library of spectra for comparison to the
tested in tandum with the material under test to spectra of unknowns. The spectra can be digitized and
compensate for the effects of the solvent. Solids may a computer used to search rapidly among known
also be prepared for testing by grinding with mineral oil spectrum. Usually the programs do not identify the
and placing between two sodium chloride plates or compound completely, but narrow the possibilities to
grinding with potassium bromide and pressing into a about 10 compounds. Infrared spectroscopy is most
pellet. The mineral oil interferes with the spectra over a effective when the sample is a pure compound, so
small wavelength range, but the potassium bromide separation techniques such as solvent extraction or
does not. In the identification of an explosive chromatography may be used on a sample before
ingredient, the spectrum of the unknown is examined irradiation.
Table 13-2. Spectral Correlations of Aromatic Nitro Compounds, Nitramines, and Nitrates
Band
assignments,
Structure µm Comments
sym-trinitro 9.25 Found in all sym-trinitro compounds examined which have the following addi-
tional groups: OC2H5, CH3, OH, C2H5, COOH, OCH3, NH2. The band
appears to shift to about 9.35 im in the presence of acidic groups such as
COOH or OH.
m-dinitro 10.85-10.95 Found in all m-dinitro compounds examined which have contained the follow-
ing additional groups: CH3, C2H5, OH, N =NH2, COOH, CHO, OCH3,
CH3NH, C2H5NH, NO2 (trinitro). In the trinitro compounds the position of the
band has been found from 10.75 to 11.0 µm.
11.90-12.05 Found in m-dinitro compounds examined where other additional groups, if
any, were ortho to the nitro. Not found in sym-trinitro compounds but present
in 2,3,4- and 2,4,5-trinitrotoluene. Absent in 3,5-dinitrobenzoic acid and
4,6-dinitro-o-cresol. It appears that a group meta to the nitro inhibits the
band.
o-mononitro 12.7-12.8 Found in all mononitro compounds containing any one of the following groups
ortho to the nitro: CH3, C2H5, CHO, NH2, COOH. Not usually found in dinitro
or trinitro compounds.
p-mononitro 9.0 Found in all mononitro compounds containing any one of the following groups
ortho to the nitro: CH3, C2H5, CHO, NH2, COOH. Not usually found in dinitro
or trinitro compounds.
nitramines 7.8 Found in all nitramines examined. Presumed to be caused by the N-N vibra-
tion.
nitrates 6.0 Found in all organic nitrates examined. From the analysis made of methyl
nitrate it is presumed that this band is caused by the symmetrical stretching
vibration of the N02.
7.8 Found in all organic nitrates examined. From the analysis made of methyl
nitrate it is presumed that this band is caused by the symmetrical deforma-
tion vibration of the NO2.
12.0 Found in all organic and inorganic nitrates.
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c. Magnetic Resonance. Two forms of magnetic per second is defined as the coupling constant, J. The
resonance are used; nuclear magnetic resonance and value of J yields useful information concerning the
electron spin resonance. positions of the protons in the molecule. The area under
the spectra peak is proportional to the number of
(1) Nuclear Magnetic Resonance (NMR). hydrogen nuclei in a given state. Chemical shift, J, and
When a charged particle spins, a magnetic field or the area under the peaks provide useful analytical
dipole is produced in a manner analogous to the information. Multiple peaks in the spectrum on a single
magnetic field produced by current flowing in a loop of compound are caused by hydrogen nuclei which are in
wire. An external magnetic field aligns the dipoles, different states. The spectrum of PETN shows one
either with the field or 180 degrees out of phase with the sharp peak because all the protons are in the same
field. The out of phase position, in which the north and chemical state. TNT, however, shows two peaks, one
south poles are reversed, is referred to as against the due to the protons in the methyl group and one due to
field. Alignment with the field is more stable than the protons in the ring. The solvent has a considerable
alignment against the field so the application of suitable effect on the NMR spectrum of a sample, so standard
frequency electromagnetic radiation will cause the procedures must be used. An exchange takes place
dipoles which are against the field to flip into alignment between the deuteriums used in the solvent and the
with the field. The frequency at which this occurs is active hydrogens in the material under test. This can
called the resonant frequency. Any nucleus which has a cause changes in the spectrum: line shifts, intensity
net spin can flip, but the hydrogen nucleus is the most shifts, and the creation of new multiplet lines. Stabilized
commonly used in NMR. The hydrogen nucleus spectra are obtained after the solution has been given
consists of a single proton, so this method is referred to enough time to come to equilibrium. This is called the
as proton magnetic resonance. The frequency at which development time. Careful attention must be paid to
resonance occurs depends on the nucleus and the ensure that the proper development time specified in the
surrounding medium. The magnetic field that is used to specific procedure is used. NMR spectra of unknown
align the protons also changes the configurations of the compounds can be compared to those of known
electrons around the nucleus in such a way that they compounds for identification purposes, or identification
produce a magnetic field in the opposite direction of the can be made on the basis of the analytical information
externally applied field. This field shields the nucleus obtained.
and must be overcome before any of the protons can be
flipped. The strength of the field depends on the (2) Electron Spin Resonance (ESR). This
structure of the electrons around the nucleus. If the test is sometimes referred to as electron paramagnetic
atom is bound into a compound and valence electrons resonance (EPR). ESR can only be performed on
are missing, added, or being shared, the effectiveness samples which contain unpaired electrons. An electron
of the shielding is changed. This alters the resonant has an intrinsic spin which creates a magnetic dipole
frequency for a given magnetic field strength or alters along the axis of rotation. In an external magnetic field,
the magnetic field strength required to flip the protons at the dipoles will align either with or against the field. By
a given frequency. Either method of scanning, varying applying high frequency energy at right angles to the
the magnetic field strength at fixed frequency or varying aligning magnetic field, the magnetic moment, and thus
the frequency at fixed magnetic field strength, can the direction of the electron spin, can be reversed or
produce an NMR spectrum. In an NMR spectrum, the flipped. Alignment with the field is the preferred
resonance of tetramethlylsilane (TMS) is taken as the direction. Flipping occurs when the frequency of the
standard and defined as zero. All twelve of the protons incident energy is equal to the frequency of precession
(hydrogen atom nuculei) in the methyl groups are in the of the electrons. Flipping does not occur in paired
same chemical state, so the spectra of TMS consists of electrons because the opposite spin quantum state is
one very sharp peak. The resonance peaks in the already occupied. Scanning is done by either varying
spectra of other compounds are defined in units of the magnetic field strength at fixed frequency or varying
chemical shift, ppm's. The chemical shift of a resonant the frequency at fixed magnetic field strength. The
peak is the frequency of resonance of TMS divided by former method is preferred. ESR, while of limited
the spectrometer frequency in megahertz at which the applicability to the energetic material field, can be used
analysis is being performed. Dipoles in close proximity to identify paramagnetic compounds, transition metal
can cause peaks to split into doublets, triplets, etc. The ions, and free radicals of organic compounds. Free
difference between the lines of the multiplet in cycles radical detection has been used in pyrolysis studies.
13-9
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d. Mass Spectrometry (MS). In mass ammonia, hydrogen, isobutane, methane, or water. The
spectrometry, molecules of the sample to be analyzed ionizing compounds produce positively charged
are ionized. These ions are then accelerated by an molecules. The molecules do not fragment as much as
electromagnetic field. The acceleration acquired by in electron impact mass spectrometry. In negative ion
each ion in a field of given strength will depend on the mass spectrometry, electrons are absorbed by the
fragment's mass and charge. Most of the ions will have sample molecules. Absorption may be accompanied by
a charge of plus one electron unit so separation is on decomposition of the molecule into charged ions. Field
the basis of mass; the more massive of the ions are ionization and field desorption mass spectrometry use
accelerated less than the fragments having less mass. high voltage electrostatic fields to produce ions. In field
Two types of electromagnetic fields are generally used ionization mass spectrometry the sample in gas form is
for separation: the magnetic selector and the passed over a point or edge on which a potential of 107
quadrupole. In the magnetic selector, a stream of ions or 108 volts per centimeter is maintained. Quantum
is accelerated to a potential at several kilovolts and tunneling by electrons in the gas to the high potential
introduced into a magnetic field. The direction of the forms ions. In field desorption the sample molecules
stream is at a right angle to the direction of the field. are absorbed, or deposited,on a surface. A strong
The magnetic field deflects the path of the ions into a electromagnetic field is applied to desorb the molecules
semicircle. The radius of the semicircular path for any as ions.
fragment for a given magnetic field strength is
proportional to the initial or tangential velocity and 13-6. Detection and Identification of Residues.
inversely proportional to the magnetic field strength. A
detector is placed at a point in a chosen semicircular a. Detecting and collecting the residue of
trajectory that the ion fragments can travel. For a given explosives left after detonation is a difficult task.
initial accelerating potential and magnetic field strength, Detonation is a relatively complete reaction and the
fragments of a particular mass to charge ratio will strike small amount of explosive left is scattered over a large
the detector. The spectra, plotted as a function of the area. The general destruction of the area also hampers
mass to charge ratio, is obtained by scanning the the collection effort. The most likely places for the
magnetic field strength or the initial accelerating residue to be found is in the soil and other debris in the
voltage. The former technique is the preferred method blast seat; wood, plastic, and other materials which can
in low resolution mass spectrometry. High resolution catch and hold the flying residue particles; and metal
mass spectrometers use both methods simultaneously objects which were close to the point of detonation such
to improve separation. In the quadrupole the field as a part of the bomb. The debris from the explosion
produced by a combination of DC and radio frequency site is first microscopically examined. Many times black
power applied to four parallel rods is used to focus the and smokeless powders can be identified by the shape
ion fragments rather than a magnetic field. A and color of the residue. A vapor trace analyzer can be
quadrupole unit is less sensitive than a magnetic used on the debris to identify volatile explosives such as
selection unit. The ions can be produced by several nitroglycerin. The vapor trace analyzer consists of a
methods. In electron impact mass spectrometry, the vapor preconcentrator and a gas chromatograph with an
sample is bombarded by electrons boiled off a hot electron capture detector. The residue in the post
filament. When the sample is ionized in this way detonation debris is of little chemical integrity. Solvent
organic molecules break up into fragments of various extraction is used to dissolve the residue for analysis.
masses. The spectra obtained can be compared with a Solvent selection is important. Extraction of substances
spectral library to identify unknown compounds, or that could interfere with the subsequent analysis of the
analytical information from the spectra can be used to explosive is undesirable. Large amounts of solvent are
identify groups within a molecule. Electron impact of used to extract even small amounts of explosive
organic compounds produces many products from bond residue, so only analytical techniques which can handle
cleavage fragments to complex fragments which have trace amounts are used. The methods described in
undergone significant rearrangement. In chemical paragraphs 13-2 through 13-5 can be used. In addition
ionization mass spectrometry, the sample reacts with an X-ray diffraction patterns can be compared to patterns of
ionizing compound to produce a positive ion. The known compounds for identification. Residues on hands
ionizing compounds are produced by electron impact of and clothes are extracted and tested similarly.
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b. Detection and identification can be made easier the presence of explosive vapors are used. For
by adding a taggant to explosives. One taggant system improved detection, two microorganisms may be used,
which has been proposed consists of small layered one which gets brighter in the presence of the vapor
particles which are laminated to increase the probability while the other gets dimmer. In laser optoacoustic
of surviving detonation. Each layer can be one of a spectroscopy a modulated laser beam is tuned to the
number of colors. The sequence of colors can be proper frequency to excite the vapors of explosives in a
decoded to determine the explosive and manufacturer. closed cell. The energy of the excited state is changed
Magnetic particles and fluorescent indicators which to translational energy through collisions with
respond to ultraviolet radiation are added to make the surrounding molecules. The translational energy is
taggant particle easier to find after a detonation. detected acoustically.
Another taggant system which has been proposed uses
layers of magnetic material with different Curie points. b. Animals, such as dogs, can also be used to
The Curie point is the temperature at which detect explosive vapors. Vapor detection can be
ferrimagnetism ceases. defeated with hermetic sealing. However, several
methods are considered practical for detection of bulk
13-7. Detection of Hidden Explosives. explosives. The nuclear magnetic resonance
a. Explosives can be detected using a variety of techniques can be used. X-ray contrast can also be
techniques. Many of the methods depend on vapor used. In this method gamma rays are passed through
detection. Two methods, gas chromatography and the material under test. The attenuation through the
mass spectrometry, have already been described. material is measured, then analyzed by a computer.
Electron capture detectors work on the same principle Thermal neutron-activation can be used to detect bulk
as the electron capture detector in gas chromatography explosives. In this method a thermal neutron is
which is discussed in paragraph 13-3d. In plasma absorbed by a nitrogen-14 nucleus to produce a
chromatography the vapors are ionized at atmospheric nitrogen-1i 5 nucleus in an excited state. The nitrogen-1
pressure. An electrostatic field is applied to cause the 5 nucleus will go to ground level by emission of a
ions to drift. Heavier ions will drift slower than lighter gamma ray. Neutron-nitrogen reactions can be
ones due to collisions with the inert gas at atmospheric differentiated from the neutron-other element reactions
pressure. In chemiluminescence, the reaction between by the energy of the gamma rays produced. A system
ozone and NO, which produces luminescence, is used. to make explosives easier to detect is to add a vapor
In bioluminescence, microorganisms that luminesce in taggant to the explosive material.
13-11(13-12 blank)
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CHAPTER 14
PACKING, MARKING, STORAGE, AND SHIPMENT
OF ENERGETIC MATERIALS
14-1. Introduction. The regulations governing the a. Items containing small quantities of explosive
marking, packing, and shipping of military supplies are and constructed or packaged so that their explosive
set forth in applicable Army regulations. These forces will be self-contained if they function.
operations will also comply with Department of b. Explosive items which both the testing agency
Transportation regulations. This chapter contains and the project manager or appropriate major
general regulations applying to the marking, packing, subordinate command agree in writing can be safely
and shipping of explosives and ammunition. No live transported.
ammunition component that has been subjected to
undue or abnormal forces for test purposes shall be 14-2. Packing.
offered for surface shipment by commercial carrier or be a. General. Explosives are packaged to safely
transported over public transportation systems by meet a wide variety of shipping and storage situations.
government conveyance except: Storage conditions may vary from the best possible
coverage to no cover at all and from extremes in
climatic conditions. Figures 14-1 through 14-7 area
representative sample of explosives packaging.
Figure 14-1. Steel box for packing solid propellants, including marking.
14-1
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Figure 14-2. Metal lined wood box for packing solid propellants, including markings.
14-2
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Figure 14-4. Palletized large caliber high explosive projectiles, including marking.
14-3
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14-4
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Figure 14-7. Wood box for packing high explosives, including marking.
14-5
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(3) Salvaged or deteriorated solid propellants loading projectiles. For future use, they should be
should be shipped water wet. restricted to the storage of Classes (04) 1.2, (08) 1.2,
e. Containers for Ammunition and Bulk High (12) 1.2, 1.3, and 1.4 materials (excluding rockets and
Explosives. rocket motors). The magazines measure 15.7 by 66.6
(1) Ammunition (fig 14-3, 14-4, and 14-5) and meters (51 feet 7 inches by 218 feet 8 inches), are
bulk high explosives (fig 14-6 and 14-7) shall be packed usually spaced 91.5 meters (300 feet) apart, and have
in accordance with approved DARCOM drawings that concrete foundation walls and piers, hollow-tile walls,
comply with DOT regulations. steel frames, and concrete floors. The storage capacity
of the magazines is not stated in definite figures since
(2) Containers used for packing bulk high the number of items which can be stored is regulated by
explosives should be lined with strong cloth or paper the appropriate quantity-distance tables.
bags or liners with cemented seams to prevent sifting.
(3) High explosives and black powder
magazines, classed as above ground magazines.
14-3. Marking.
These magazines were designed for the storage of bulk
a. Each package of explosives is marked in explosives such as black powder, TNT, tetryl, and
accordance with pertinent drawings to provide positive explosive D and may be used for this purpose where
identification (NSN, DODAC, nomenclature, lot number, more desirable storage space cannot be obtained. They
and ICC marking as a minimum). are 8.4 meters (27 feet 6 inches) wide and 13.2 meters
b. Whenever explosives or ammunition containers (43 feet 4 inches) long and are usually spaced 243.8
or ammunition and ammunition components are meters (800 feet) apart. They have concrete foundation
repainted, the new painting or marking shall correctly walls and piers, hollow tile walls filled with sand, steel
identify contents of items. The marking of empty or frames, and concrete floors covered with sparkproof
inert loaded ammunition items for display purposes is mastic or the equivalent. The magazines were originally
governed by the provisions of AR 385-65. designed for the storage of 1 13,400 kilograms (250,000
c. Explosives, ammunition, and loaded pounds) of explosives, but in order to assure adequate
ammunition components obtained from salvage aisle space for inspection and shipping and convenient
operations and material which has lost its identification height of piles, the amount of storage is usually limited
markings shall be clearly marked to show the explosive to approximately 45,360 kilograms (100,000 pounds).
nature of the material. Explosive material or items
which cannot be definitely identified as to their explosive (4) Primer and fuze magazines, classed as
nature should be disposed of by technically trained above ground magazines. These magazines were
personnel in accordance with the provisions of designed for storing primers, primer detonators,
DARCOM-R 385-100. adapters and boosters, and fuzes of all types. In the
d. See figures 14-1 through 14-7 for a future when it is necessary to use magazines of this
representative sample of markings required on type, they should be restricted to the storage of Classes
explosives packaging. (04) 1.2, 1.3 (except rockets and rocket motors), and 1.4
ammunition and explosives. The magazines are 8.4
14-4. Storage of Explosives and Ammunition. meters (27 feet 6 inches) wide, 13.2 meters (43 feet 4
a. General. The types of existing magazines listed inches) long and are usually spaced 91.5 to 121.9
below are considered standard for the storage of the meters (300 to 400 feet) apart. With respect to
types of items specified. New storage magazines construction details, they are similar to high explosive
should be of the earth covered, corrugated steel, or and black powder magazines except the hollow tile walls
reinforced concrete arch type. are not sand filled and the floor is not covered with
spark proof mastic.
b. Magazines.
(1) Earth covered magazines. These include (5) Service magazines and service storage
igloo, steel arch, Stradley, special type, hillside, and buildings. These buildings are used for intermediate
subsurface type magazines. Earth covered magazines storage of the minimum amount of explosives
are preferred for the storage of all items of ammunition necessary for safe and efficient manufacturing or
or explosives. processing operations. Construction details of such
(2) Standard ammunition magazines magazines should specify the use of fire-resistant
(commonly called "standard magazines"), classed as materials and/or fire-resistive construction.
above ground magazines. These magazines were
designed for the storage of fixed rounds or separate
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(6) Other structures. Structures not of storable liquid propellant, shall not be stored in
approved magazine type shall not be used for the magazines containing explosives.
storage of explosives and ammunition except when (6) Except when required for security
authorized by the Commander, HQ DARCOM, Attn: purposes, service magazines within an operating line
DRCSF. need not be locked during shift operations. These
magazines must be locked whenever the operating line
c. Temperature Control. is shut down; i.e., nights, weekends, and holidays.
(1) Sudden changes in temperature may
damage airtight containers or may result in excessive e. Stacking.
condensation of moisture. If the temperature in a (1) Ammunition and explosives shall be
magazine exceeds 37.80C (100°F) for a period of more stored in containers as prescribed by approved
than 24 hours, the magazine should be cooled by DARCOM drawings and specifications and shall be
wetting the exterior of the building with water or by stacked and arranged in a magazine in accordance with
opening the doors and ventilators after sunset and instructions set forth in Army regulations and approved
closing them in the morning. If these methods do not DARCOM drawings and directives. Explosives or
prove effective in lowering the temperature, the ammunition in stacks shall be grouped and identified
Commander shall decide whether the materials should according to lots. When military explosives or
be removed to some other magazine. ammunition are not packed in accordance with
(2) Storage magazines, in general, should not approved drawings and specifications, they must be
be provided with heat. Exception is made in the case of stored in accordance with special instructions from the
magazines where heating may be necessary to prevent Commander DARCOM, ATTN: DRCSF. General rules
condensation of moisture, to maintain constant set forth in paragraphs (2). and (3) below should be
temperature, or other reasons. If steam or hot water followed in the absence of applicable storage drawings.
coils are used to heat a magazine, they must be so (2) Methods used for stacking must provide
arranged that explosives material cannot come in for good ventilation to all parts of the stack. Adequate
contact with the coils. The coils must be kept clean. dunnage shall be used for this purpose.
(3) Aisles shall be maintained so that units in
d. Magazine Operational Regulations. The each stack may be inspected, inventoried, and removed
for shipment or surveillance tests. Block storage is
following regulations shall be complied with where
permitted, provided adequate ventilation of stacks
ammunition and explosives are stored:
exists. Unobstructed aisles shall be maintained to
(1) Instructions as printed on magazine permit rapid egress of personnel.
placards, DA Label 85, must be posted on or near each
(4) Only one light box, pallet, or unit should
door of the magazine so that they are visible when work
be allowed per lot in storage. A light box, pallet, or unit
is being done in the magazine.
is defined as a box, pallet, or unit which contains less
(2) Loose components of ammunition, than the normal quantity or count. Packaging and
packing materials, conveyors, skids, dunnage, empty marking shall be in accordance with approved drawings
boxes, and other similar material shall not be stored in and regulations. Light units shall be readily visible and
magazines containing ammunition or explosives. immediately accessible when stacked in storage. Light
(3) Vegetation around all ammunition and units might be painted white.
explosives storage locations shall be controlled.
(4) Doors and locks must be kept in good f. Permitted Open Storage.
working order. Magazines shall be locked at all times (1) Open storage of ammunition/explosives
except when permitted operations are in progress in the and limited material will not be used in lieu of covered
magazine and as provided for in paragraph 14-4c(1). A storage employing standard facilities and/or methods.
crew must not be permitted to work in a position in a (2) When circumstances dictate that open
magazine which requires passing the work aisle or storage must be utilized for storage of Army owned
position of a second crew to reach an exit. The number material, the storing installation will submit a request for
of crews shall not exceed the number of exits. Two or waiver in accordance with DARCOM-R 385-100.
more doors must be unlocked and open when personnel Requests involving material owned by another service
work in magazines having more than one door. will be forwarded through the same channel (through
(5) Flammable liquids, except when used as HQ DARCOM, ATTN: DRCSF-E) to the owning service.
the chemical filler of a munition or as a prepackaged
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(3) Bulk solid propellants, bagged propelling (4) If revetments are to be provided around
charges, pyrotechnics, bulk high explosives, and critical open storage sites, they must comply with the
items shall not be placed in open storage. requirements of Chapter 12. Stacks of ammunition
must be kept at least 0.61 meter (two feet) from the
g. Open Storage Sites. base of the revetment and at least 0.31 meter (one foot)
(1) Sites for open storage shall be separated below the top of the revetment.
from magazines, other facilities, and each other in (5) Excess dunnage should not be stored
accordance with the requirements of Chapter 12. between open sites and magazines nor between
(2) The storage sites shall be level, well magazines. Excess dunnage storage sites should
drained, and free from readily ignitable and flammable comply with applicable quantity-distance requirements
materials. The supporting timbers or platform upon except that during open storage operations, service
which the ammunition is stored shall be well constructed supplies of dunnage may be located not closer than 15.3
to prevent falling, sagging, and shifting of the meters (50 feet) from the stack being processed.
ammunition. In order to assure stack stability and free (6) Suitable types of firefighting equipment
circulation of air, not less than three inches of dunnage and fire symbols should be provided.
should be used between the bottom of the stack and the h. Special Requirements for Open Storage.
earth floor. Provisions should also be made for (1) Sites between earth covered magazines.
circulation of air through stacks. Non-flammable or fire- Sites may be located midway between adjacent earth
resistant, waterproof, overhead covers should be covered magazines which are 121.9 meters (400 feet)
provided for all ammunition containing solid propellants, apart, provided the sites are barricaded and are
torpex, tritonal, minol, or chemical agents since each of separated from the barricaded sides of the nearest
these materials may be adversely affected by exposure magazine by 56.4 meters (185 feet). Ammunition in
to the elements. An air space of not less than .45 meter such sites should not be stored beyond lines drawn
(18 inches) should be maintained between the top of the through the fronts and backs of magazines in the same
stack and the cover. If adequate ventilation is assured, row. Barricading does not reduce the required inhabited
overhead covers are also desirable for outdoor stacks of building or public traffic route distances. The storage of
bombs and shells. Sides of covered stacks also may be Class 1.2 between earth covered magazines is not
protected by non-flammable or fire-resistant, waterproof desirable and should be resorted to only when
covers provided air space is maintained between the necessary. Sites containing Class 1.2 may not be
cover and the ammunition. located closer than the fragment distance from other
(3) Frequent inspections shall be made to open sites. The limitations of the quantity-distances
detect sagging piles and accumulations of trash between listed in table 14-1 also are applicable.
or under stacks.
Table 14-1. Special Requirements for Open Storage Between Earth Cover Magazines
14-8
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(2) Sites not between earth covered No open storage site shall be located within 365.7
magazines. Sites containing Class 1.2 shall not be meters (1,200 feet) of above ground magazines. The
stored closer than fragment distance from other sites. limitations of the quantity-distances listed in table 14-2
also are applicable.
Table 14-2. Special Requirements for Open Storage Between Magazines That Are Not Earth Covered
(3) General. Inhabited building distance k. Small Arms Ammunition. Boxed small arms
and public traffic route distance shall be maintained ammunition shall not be used as barricades or dividing
around open storage sites as specified in Chapter 12. walls between stacks of other types of ammunition.
i. Storage of Bulk Initiating Explosives. Bulk I. Separate-Loading Ammunition, HE Loaded
initiating explosives must not be stored dry and shall not Except Explosive D.
be exposed to the direct rays of the sun. Glazed (1) Separate-loading projectiles must be
earthenware crocks of ample size to hold the double bag handled with care. They shall not be stored without
of material with covers of the plastic cap type to prevent fuze-well closing plugs. Metal dunnage should be used
evaporation and eliminate friction or abrasion when where practicable.
removed are used for normal storage. Proper selection (2) Class (18) 1.2 quantity-distances are the
and use of covers is required to prevent friction and minimum acceptable for Class (18) 1.2 items,
pinch points. If long term storage in shipping containers regardless of the quantities of the HE involved. For
is contemplated, the container must be equipped with a Class (18) 1.2 separate-loading projectiles, storage must
cover having a port for observation of the level of liquid comply with DARCOM Drawing 19-48-4102-1-2-
therein. The viewing port must be covered with a 14PE1001 in order to limit distance requirements to
transparent plastic which is known to be compatible with those prescribed by the Class (18) 1.2 quantity-distance
the initiating explosives being stored. As an expedient table. If those projectiles are equipped with core-
only, bulk initiating explosives may be stored in shipping recessed lifting plugs, the Class 1.1 quantity-distance
containers that are not so equipped, provided they are table applies when the total quantity of HE involved
stored in frostproof, earth covered magazines, with exceeds 6,804 kilograms (15,000 pounds) in above
containers on end, only one tier high, and with ground magazines, even if storage complies with
passageways for inspection and handling. Bags of DARCOM Drawing 19-48-4102-1-2-14PE1001.
initiating explosives in storage containers must be under
m. Separate-Loading Ammunition Explosive D
distilled water. Alcohol may be added to the distilled
Loaded, Class (12) 1.2. Except where permanent block
water to prevent freezing.
type storage methods are used, this type of projectile
j. Solid Propellants. Propellants shall not be may be stored with distances between stacks not more
stored or shipped in damaged containers. When leaking than that required to permit inspections.
containers are discovered, an examination of the
n. Fixed and Semi-Fixed Ammunition. Boxed
contents shall be made for the nitrous odor of
fixed and semi-fixed ammunition shall not be used as
decomposing propellant. If any such condition is
barricades or dividing walls between stacks of other
observed, the propellant shall be segregated or properly
types of ammunition.
disposed of. Propellants and propelling charges in
containers should be stored so that they can be readily
inspected. They shall not be exposed to the direct rays
of the sun.
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o. Rockets and Rocket Motors. (b) When cars containing explosives or other
hazardous materials are received at the installation or
(1) Whenever practicable, rockets and rocket held in yards, precautions must be taken to prevent
motors that are in a propulsive state should be stored accidents, particularly at night. These precautions must
nose down. Small rockets and missiles may be stored include provisions for quickly removing and isolating the
in standard earth covered magazines without regard to cars in case of fire.
direction in which they are pointed except that they will (c) Cars loaded with hazardous materials
not be pointed toward the door of the magazine. If not must be loaded and placarded as prescribed by
in a propulsive state, any rocket, rocket motor, or Department of Transportation regulations before being
missile may be stored in any magazine without regard to offered for transportation. The carrying of hazardous
the direction in which they are pointed. materials on locomotives or other self-propelled rail
(2) In above ground magazines where nose vehicles is prohibited.
down storage is not practicable, items (in a propulsive (d) Before cars are moved by a locomotive,
state) shall be pointed in the direction which offers the the air brake hose must be coupled and tested to assure
least exposure to personnel and property in the event of that the air brakes are in proper working condition and
fire or explosion. the car doors shall be closed.
(3) Rockets should be stored in a dry, cool (e) Empty cars shall not be removed from
magazine out of the direct rays of the sun. They should warehouses, magazines, buildings, or loading docks
not be stored in locations where temperatures exceed until all warning placards have been removed.
49°C (120°F). Prolonged exposure of rocket (f) Special care must be taken to avoid rough
ammunition to either high or low temperatures may handling of cars. Cars must not be "cut off" while in
increase the normal rate of deterioration or render the motion and must be coupled carefully to avoid
motors more susceptible to ignition if subsequently unnecessary shocks. Other cars must not be "cut off"
handled improperly. and allowed to strike a car containing explosives. Cars
must be so placed in yards or on sidings that they will be
14-5. Shipment of Explosives and Ammunition. subject to a minimum of handling and be readily
a. General. Explosives and ammunition are removed from danger of fire. Such cars must not be
routinely shipped via all common modes of placed under bridges or in or alongside passenger sheds
transportation, i.e., railroad, truck, ships, and aircraft. of station, and where avoidable, engines on parallel
However, due to the commodities hazardous nature tracks should not be allowed to stand opposite or near
each of the transportation modes rigidly adheres to its them.
own specific set of regulations. (g) "Dropping," "humping," "kicking," or the
b. Railroad Transportation. The operation of use of the flying switch is prohibited.
railroads within a DARCOM establishment shall be in (h) Adequate measures such as guarding,
accordance with applicable current directives, patrolling, and safety inspection must be provided at all
particularly TM 55-200, Railroad Operating Rules and times. All such activity should be under positive
this regulation. administrative controls.
(1) Specifications for equipment. The (i) Fire symbols or DOT placards shall be
regulations of the Department of Transportation, the placed on each railroad car while transporting
Federal Railroad Administration, and the Association of explosives or ammunition within a DARCOM
American Railroads pertaining to safety devices, safety establishment in order to provide a ready means of
guards, design of equipment, etc. are mandatory for identifying the potential hazard should a fire occur.
railway equipment involved in transporting materials (3) Placarded railcars. Placards shall be
between establishments. The same regulations should applied in accordance with DOT regulations to railcars
be followed for inspection, maintenance, and operation transporting hazardous materials. Ammunition and
of railroad equipment within an installation. explosives shall be loaded and braced in accordance
(2) Transportation of hazardous materials. with approved drawings.
(a) In addition to the requirements of
other parts of this section, the rules in subparagraphs (b)
through (i) below shall be followed.
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(4) Car inspection. A car must not be (8) Sealing cars containing explosives and
loaded with any DOT Class A explosives unless it has ammunition. In addition to any other seals which may
been thoroughly inspected by a qualified employee of be used, cars containing explosives or ammunition shall
the carrier who shall certify that its condition conforms to be sealed. A cable seal lock will be used to secure car
DOT regulations. After a certified car has been doors plus an upper rail lock. Serial numbers of seals
furnished by the carrier, the shipper or his authorized will be placed on GBL (DOD 5100.76M and AR 55-355,
employee must, before commencing the loading of any Chapter 13). If the seal is not in place when the car is
such car, inspect the interior thereof and after loading, received, the car shall be treated as suspicious and shall
certify to its proper condition. A certificate will be be inspected. See AR 55-38 for instructions on
completed and signed where applicable. Shipments of recording details when shortage, pilferage, or apparent
Class B explosives may be loaded in a closed car or theft is involved.
container car which is in good condition, into which (9) Inspection of cars before unloading.
sparks cannot enter, and with roof not in danger of (a) Rail cars containing explosives and ammunition
taking fire through unprotected decayed wood. Wood entering a DARCOM establishment must be inspected.
floored cars must be equipped with spark shields. Such This inspection comprises the examination of the
cars do not require a car certificate but must be outside and under side of each car for damage such as
placarded in accordance with paragraph 14-5b(3) above. defective brakes, couplings, wheel flanges, etc; to
(5) Car certificates. The car certificate detect unauthorized and suspicious articles; to check
printed on strong tag board measuring 177.8 millimeters correctness of individual car numbers and seal numbers
x 177.8 millimeters (7 by 7 inches) or 152.4 by 203.2 against bills of lading. When the probability of sabotage
millimeters (6 by 8 inches) must be duly executed in is remote, such inspections may be accomplished from
triplicate. The original copy must be filed by the carrier ground level without the aid of an inspection pit to
at the forwarding station in a separate file and the other discover unsafe structural and mechanical deficiencies
two must be attached to the car, one to each outer side of the car. During periods of emergency when sabotage
on a fixed placard board or as otherwise provided. may be attempted, and also to aid in the rapid
(6) Leaking packages. Constant alertness inspection and movement of cars, an inspection pit
must be maintained to detect, through characteristic should be provided.
odors, the leakage of hazardous materials from faulty (b) Cars of ammunition or explosives on
packages. Leaking packages should be removed from which foreign and suspicious articles have been
cases and repaired, or if in tank cars, the contents secreted or attached outside or underneath the car, or
should be transferred. If artificial light is necessary, only cars which show a defect that might affect the
electric lights approved for the hazard involved shall be installation or contents of the car, shall be removed to
used. Leaking tank cars containing compressed gases the suspect car siding for additional inspection. In
shall be switched to a location distant from habitation addition, during the times of national emergency, cars
and highways and proper action taken for transferring on which the seal numbers do not correspond to those
contents under competent supervision. Cars containing shown on the bill of lading shall be treated as suspect
leaking packages or leaking tank cars must be protected cars and should be removed to the suspect car siding
to prevent ignition of liquid or vapors by flame from for additional inspection.
inspectors' lanterns or torches, burning fuses, switch (c) Cars which satisfactorily pass the
lights, switch thawing flames, fires on side of track, or inspection outlined above may be considered
from other sources. All unnecessary movement of a reasonably safe but care must be exercised in breaking
leaking car discovered in transit must cease until the car seals and opening car doors because of the
unsafe condition is remedied. possibility of damage or shifting lading, leaking
(7) Car loading of items containing containers, etc. When the quantity and class of
ammunition and explosives. Loading methods ammunition present in the classification yard does not
prescribed by DARCOM drawings shall be followed for exceed that permitted by the appropriate quantity-
the loading and bracing of railway car shipments of distance table, based on distance to adjacent targets,
military explosives and ammunition. The packages cars may be opened for inspection at that point,
should be placed in position with no more force than is otherwise interior inspection should be accomplished
needed to secure a compact load and to prevent shifting after the cars have been spotted at the unloading point.
and damage en route. Excessive or violent use of
mauls shall not be permitted when positioning packages.
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(10) Inspection of cars after unloading. Cars in (3) Motor vehicle for explosives shipment.
which explosives or ammunition are received shall be Cargo type trucks and truck-tractor drawn semitrailer
inspected after unloading to see that they are clean and vans are the preferred means for transporting
free from loose explosives or other flammable ammunition, explosives, and other hazardous material.
materials, and that the placards and car certificates are Other types of trailers should not be used by DARCOM
removed. installations for this purpose except where the material
Explosives sweepings shall be destroyed. is sufficiently large to make handling by vans impractical
(11) Damaged shipment. Any shipment (this restriction need not apply to licensed common
received in a damaged condition as a result of carriers and contract equipment). Equipment used for
inadequate or improper blocking and bracing or not transporting ammunition, explosives, and other
loaded in accordance with appropriate DARCOM hazardous material must meet the following
drawings shall be reported on Discrepancy Shipment requirements and these should be supplemented by
Report (SF 361) in accordance with AR 55-38. If the local regulations as deemed necessary by the
damage was due to improper preservation, packaging, commander.
or packing, SF 364 (Report of Discrepancy) will be (a) Loading methods prescribed by DARCOM
prepared in accordance with AR 735-11-2. drawings shall be followed for the loading and bracing of
c. Motor Vehicle Transportation. The operation of motor vehicle shipments of military explosives and
motor vehicles within a DARCOM installation shall be in ammunition. The packages should be placed in position
accordance with this and other applicable current with no more force than is needed to secure a compact
regulations. load and to prevent shifting and damage en route.
Excessive or violent use of mauls shall not be permitted
(1) Motor vehicle safety program. Current
when positioning packages.
regulations, particularly AR 385-10, Army Safety
Program, require the institution of a motor vehicle safety (b) Special precautions must be taken to
program as part of the overall safety program of a avoid ignition of the material by the exhausts of
DARCOM installation. AR 385-55, Prevention of Army automotive vehicles.
Motor Vehicle Accidents, contains detailed information (c) The lighting system shall be electric.
for inclusion in such a program. Oth,r pertinent Batteries and wiring shall be so located that they will not
regulations are AR 55-162, AR 55-203, AR 55-355, AR come into contact with containers of explosives,
55-357, AR 735-11-2, and AR 55-38. ammunition, or other hazardous material. If exposed
(2) Motor vehicle shipment regulations. explosives or flammable vapors are encountered in a
Motor vehicle shipments on public highways are vehicle, only approved type portable lights should be
governed by the Department of Transportation permitted (certified by a nationally recognized testing
regulations. All motor vehicle shipments from a organization for the specific hazardous location as
DARCOM installation shall comply in full with the defined by the National Electric Code).
applicable portions of DOT, state, and municipal (d) The interior of the truck body shall have
regulations except as provided for in these regulations. all exposed ferrous metal covered with nonsparking
Before any motor vehicle designated for movement material when transporting scrap and bulk explosives in
over public highways may be loaded with ammunition or containers which may be damaged and explosives
explosives (DOT Class A or B) and other dangerous become exposed. If the explosives transported consist
articles, as specified in chapter 216, Section II, AR 55- of ammunition or explosives packaged for shipment in
355, the vehicle must be inspected and approved by a accordance with DOT specifications, it will not be
qualified inspector for compliance with AR 55-355 (DD necessary to cover the ferrous metal. Open body
Form 626) Motor Vehicle Inspection. After loading, vehicles other than the flatbed trailer type used to
lading must be inspected and approved. Driver transport large items such as rockets or missiles must
selection, training, etc., for intraplant shipping and for have sides that are strongly made and securely fastened
operation of government owned trucks on public so that the items are safely retained. Where a top is
highways shall be in accordance with pertinent required, it should be of a noncombustible or flame-
requirements of 49 C.F.R. Parts 390-397, Federal proof material. Whenever tarpaulins are used for
Motor Carrier Safety Regulations, FM 55-30, Army covering explosives, they will be secured by means of
Transportation, Units and Operations, and FM 21-305, rope or tiedowns. Nails will not be used to fasten
Manual for the Wheeled Vehicle Driver. protective tarpaulins.
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(e) All trucks (government and commercial) Fire Fighting Procedures, shall be applied, when
destined for offpost shipment over public highways shall applicable.
be equipped with one (1) Class 1 O-BC rated portable (7) Inspection and movement of incoming
fire extinguisher when transporting DOT Class A, B, or shipments.
C explosives. Government motor vehicles involved (a) Motor vehicles loaded with explosives,
only in on-post shipments shall be equipped, as a ammunition, or other hazardous materiel shall be
minimum, with two (2) Class 1-BC rated portable fire carefully inspected by a competent person at a
extinguishers; one mounted outside the cab on the designated inspection station in accordance with AR 55-
driver's side of the vehicle and the other inside the cab. 355 using DD Form 626. The inspection station should
If government vehicles are equipped with an interior be located remotely from hazardous and populated
carbon dioxide or dry powder flooding device, only one areas.
extinguisher is required and should be mounted on the
outside of the cab on the driver's side. (b) When inspection reveals that an incoming
tractor is in an unsatisfactory condition, it should be
(f) Red lights are not permitted on the front disconnected from the trailer (at the inspection station)
of vehicles transporting explosives and ammunition. and moved to a position where it will not endanger any
(g) Trucks fueled with LP gas shall not be explosives.
used to transport ammunition and explosives in (c) When inspection reveals that the trailer or
ammunition areas. its load is in an unsatisfactory condition, it shall be
(4) Inspection of vehicles. Government owned removed to a location which is at least inhabited building
motor vehicles used for transportation of hazardous distance (not less than fragment distance for fragment
materials shall be inspected at frequent intervals by a producing items) for the material involved from inert and
competent person to see that mechanical condition and administration areas, hazardous locations, and the
safety devices are in good working order and that oil installation boundary. At this location, correction of
and motor pans under engines are clean. Because of unsatisfactory conditions shall be accomplished prior to
vehicle usage, this requirement is over and above the movement to the destination of the vehicle within the
inspection requirements of TM 38-750. Daily inspection installation. The route when moving from the inspection
shall be made by operators to determine that: (a) Fire station to the isolated locations, insofar as possible,
extinguishers are serviceable. should be removed from built-up areas and areas where
(b) Electric wiring is in good condition and personnel concentrations are high.
properly attached. (d) Vehicles which cannot be dispatched
(c) Fuel tank and piping are secure and not immediately to points where they are to be unloaded
leaking. may be moved to a holding yard which shall be sited in
(d) Brakes, steering, and other equipment are accordance with paragraph 12-111.
in good condition. (e) Incoming or outgoing ammunition and
(e) The exhaust system is not exposed to explosives loaded trailers that cannot be exchanged
accumulations of grease, oil, gasoline, or other fuels, directly between the carrier and the DARCOM
and has ample clearance from fuel lines and other installation may be moved in to interchange yard.
combustible materials. Quantity-distance provisions do not apply provided the
(5) Mixed loading. The types of hazardous trailers are moved expeditiously from the interchange
materials that may be loaded and transported together yard. At least 3.048 meters (10 feet) separation should
over public highways are established in 49 CFR be maintained between trailers in an interchange yard.
177.835(c) and 177.848. These DOT requirements shall (8) Damaged shipments. Any shipments
be complied with for shipments over public highways. received in a damaged condition as a result of
(6) Instruction to drivers. Before motor vehicles inadequate or improper blocking and bracing or not
loaded with hazardous materials leave a DARCOM being loaded in accordance with appropriate DARCOM
establishment, drivers shall be informed of the nature of drawings shall be reported on Discrepancy Shipment
their cargo and methods of fighting fires involving the Report (SF 361) in accordance with AR 55-38. If the
truck or its cargo. DD Form 836 (Special Instructions for damage was due to improper preservation, packaging,
Motor Vehicle Drivers) will be completed in accordance or packing SF 364 (Report of Discrepancy) will be
with the requirements of AR 55-355 and furnished such prepared in accordance with AR 735-11-2.
drivers. The provisions of TB 38572, Nuclear Weapons
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d. Air Transportation. The carriage of ammunition, (2) Permissible air shipments. Hazardous
explosives, and other hazardous materials by civil materials that may be shipped by civil air are identified
aircraft is regulated by the DOT. See 49 CFR 106-178, in 49 CFR 172.101 along with the maximum net
particularly Part 175. Criteria for the preparation and quantities per package and in Chapter 4 of TM 38-250
carriage of hazardous materials on military aircraft and for shipments by military aircraft. External or internal
certain Department of Defense contract airlift operations transportation of electrically initiated explosive loaded
conducted under DOT Exemption 7573 are contained in items or components by helicopter will not be permitted
TM 38-250. without prior approval from the Commander, DARCOM.
(1) Military aircraft operating regulations. Packages must conform to the requirements of DOT
(a) Operation of military aircraft shall regulations. Dangerous articles and other cargo must
be in accordance with requirements outlined in the be firmly lashed to the aircraft structure or otherwise
applicable flight envelope, Army and/or Air Force secured to prevent shifting in flight. Signaling devices,
regulations, and as further required by locally equipment necessary to promote safety in operations,
established regulations. small arms equipment in moderate quantities for
personal use, and other items as permitted in Title 49
(b) If an aircraft carrying dangerous articles
CFR part 175.10 may be carried without complying with
makes a forced landing and only minor repairs are
the above requirements. Dangerous articles must be
necessary, the cargo need not be unloaded but repairs
placed in a baggage compartment inaccessible to
should be accomplished at a location separated from
passengers during flight.
dissimilar exposures and other aircraft by the
appropriate inhabited building distance for the cargo (3) Loading and unloading aircraft.
aboard. For major repairs, the plane shall be unloaded (a) Prior to loading or unloading ammunition,
and the cargo stored in accordance with appropriate explosives, and other hazardous materials, the aircraft
quantity-distance requirements. Appropriate protection shall be electrically grounded so that the resistance to
should be afforded the cargo during inclement weather. ground does not exceed 10,000 ohms.
If a landing is made for refueling purposes only, the (b) When loading or unloading aircraft
cargo need not be unloaded. Refueling shall be containing ammunition or explosives, placards and fire
accomplished at a location suitable for the performance symbols will be displayed as indicated in paragraph 14-
of minor repairs as described above. 5d(1 )(d).
(c) Prior to take off or landing, the pilot must (c) Loading and unloading shall be done in
contact the tower for taxi, take off, or landing and accordance with quantity-distance requirements (para
parking instructions. The pilot shall, when requesting 14-5d(1)(b).
instructions, make known the contents of the cargo and (d) All ignition switches must be in the off
shall request priority for his aircraft. position.
(d) When an aircraft containing ammunition (e) Front and rear wheel chocks shall be in
or explosives is parked on a DARCOM installation in a place.
designated, restricted, posted, and traffic controlled (f) Military aircraft shall be loaded in
explosives parking or loading and unloading area, fire accordance with AR 95-16, "Weight and Balance: Army
symbols will be posted at all normal approaches to the Aircraft". Nonmilitary aircraft shall be loaded to comply
designated area. If parked in an area on a DARCOM with Civil Air Regulations.
installation which is not a designated, restricted, posted,
(g) Nonmilitary airfields used for loading and
and traffic controlled explosives parking or loading and
unloading explosives will be provided with aircraft
unloading area, fire symbols will be placed at the nose,
firefighting service equal to Army standards.
tail, and each side of the aircraft. Where the height of
the aircraft does not readily permit attaching the fire (h) At nonmilitary airfields used by US Army
symbols to the aircraft, the fire symbols may be Flight Activities, aircraft rescue and fire protection is
mounted on stands approximately 1.5 meters (five feet) normally provided by the host. If protection provided by
in height positioned adjacent to the aircraft where they the host does not meet the standards established in AR
are visible at long range. At other DOD installations and 420-90, Fire Prevention and Protection, and the
at non-DOD installations, placarding will be in DARCOM supplement to AR 420-90, Army fire
accordance with the requirements of TM 38-250 and the department personnel and/or auxiliary firefighters will be
requirements of the host installation. used during periods of Army flight activities, including
loading and unloading of explosives.
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CHAPTER 15
DISPOSAL, DESTRUCTION, DECONTAMINATION, AND DEMILITARIZATION
OF ENERGETIC MATERIALS
15-1. Introduction. Most energetic materials cannot unserviceable property. Prior approval for destruction of
be safely disposed of by dissolving in solution and routine waste is not required. Compliance with
eliminating as sewage because they are insoluble in applicable federal, state, and local environmental
water, are generally toxic, and are hazardous to the restrictions and permits is mandatory. Review of all
environment. Disposal must be by burning, detonation, SOPs for destruction of energetic materials by the
or chemical decomposition. The instructions in this Installation Environmental Coordinator is mandatory.
chapter are for destroying limited quantities of
explosive, pyrotechnic, incendiary, and smoke materials 15-3. Destruction by Burning or Detonation.
normally encountered during daily operations in
laboratories, manufacturing plants, and storage a. Destruction Sites.
facilities. When larger quantities are destroyed or (1) Site selection, physical security, personnel
reclaimed, special instructions will be furnished by the training, emergency equipment, and procedures are
US Army Armament, Munitions, and Chemical governed by applicable federal, state, and local
Command (AMCCOM)/US Army Materiel Development environmental regulations, particularly applicable
and Readiness Command (DARCOM). When hazardous waste regulations, and by the safety
destruction is authorized, the provisions of all current considerations which follow. Open burning and open
applicable Army directives must be observed. detonation operations will be conducted in accordance
with applicable air, hazardous waste, and other
15-2. Disposal. Methods for destruction are generally environmental permits. The site selected for the
based on the quantity and nature of materials to be destruction of explosives and other energetic materials
destroyed, the facilities available, and the topography of shall be located at the maximum practicable distance
the land. Destruction of explosive materiel will be from all magazines, inhabited buildings, public traffic
accomplished by burning or detonation. The only routes, and operating buildings but not less than 732
exception to this policy is made in the case of small meters (2,400 feet) unless pits or similar aids are used
quantities of explosives which can be destroyed by to limit the range of fragments and debris. In all
chemical means as specified in paragraph 15-4. disposal and destruction activities, the quantity of
Burying energetic materials in the ground or dumping in explosives that may be destroyed safely at one time
waste places, pits, wells, marshes, shallow streams, shall be determined carefully by starting with a limited
rivers, inland waterways, or deep sea is absolutely quantity and then gradually increasing that quantity until
prohibited. Existing locations, if known, of buried the optimum amount consistent with safe and efficient
explosives and other energetic materials shall be operation is determined. When trials prove that
appropriately marked with permanent type signs and fragments and debris are limited to lesser ranges, the
measures shall be taken to prohibit unauthorized appropriate inhabited building distances may be used.
personnel from entering the area. Existing records Sites must also be located in relation to the direction of
identifying the type and quantity of energetic materials prevailing winds so that sparks will not be blown toward
buried shall be maintained and the burial area shall be explosives location. Where possible, natural barricades
noted on installation drawings. Explosives which are shall be utilized between the site and operating buildings
dangerously deteriorated or cannot be definitely or magazines. When destroying explosives by burning,
identified shall be destroyed by an approved method. the possibility that the mass may detonate must be
Destruction shall not be undertaken without prior recognized and appropriate protective barriers or
approval unless the organization or installation distance separation should be used to protect personnel
commander decides that immediate destruction of and property. Open air burning and detonation of
deteriorating explosives is necessary for the protection explosives and pyrotechnics for demilitarization is
of life and property. All deteriorated materials thus prohibited between sunset and dawn.
destroyed must be accounted for, since Army
regulations pertaining to the disposal of excess and
surplus property apply to the destruction of such
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(2) Dry grass, leaves, and other extraneous (2) During disposal and destruction
combustible material in amounts sufficient to spread fire operations, the number of people in the area exposed to
shall be removed from a 200 foot radius from the point the hazard must be kept to a minimum. Warning signs
of destruction. The grounds should be of well packed or road blocks shall be posted to restrict the area and to
earth and shall be free from large stones and deep ensure proper segregation of activities. At least two
cracks in which explosives might lodge. Explosive people are needed in disposal and destruction
materials shall not be burned or detonated on concrete operations and operations shall be arranged so that not
mats. all of the personnel are exposed to an incident.
(3) Fire-fighting facilities shall be readily Personnel engaged in burning explosives should be
available to extinguish brush or grass fires and, if provided with flame resistant clothing.
necessary, to wet down the ground between burnings
and at the close of each day's operations. d. Supervision and Training.
(4) Ordinary combustible rubbish, explosives, (1) The disposal area and its operations
and explosives contaminated material shall be shall be under the direct control of an experienced,
destroyed at separate locations. Where limited space trained supervisor responsible for all activities within the
does not permit separate burning areas, part of the area. The supervisor shall be present during all burning
explosives destruction ground may be reserved for and demolition ground operations. During the
burning rubbish provided the two areas are not operated supervisor's absence, a competent qualified person will
simultaneously, and the area where rubbish has been be in charge. The alternate shall have sole custody of
burned is wetted down and inspected before explosives all ignition devices. Prior to actual burning or detonation
burning is resumed. Combustible material should be of explosives, all personnel including the demolition
burned in an incinerator complying with National Fire ground supervisor will be evacuated to a safe distance
Protection Association Standard No. 82 or in a or protective structure affording adequate protection but
substantial, wire-mesh enclosure (not over three-fourths consistent with the need to monitor the total operation
inch openings). until it is complete.
(5) The demolition area or burning ground (2) Personnel employed at the destruction
shall be serviced with telephones or two-way radio area shall be thoroughly trained regarding the nature of
communication. A change house serviced with the materials handled, the hazards involved, and the
electricity is desirable. precautions necessary. The danger of using
unapproved, improvised methods and other deviations
b. Explosives Material Awaiting Destruction. must be thoroughly instilled in the minds of the
Explosives material awaiting destruction shall be stored employees. It is essential that thorough training and
at not less than intraline distance, based on the largest vigilant supervision be provided.
quantity involved, from explosives being destroyed. (3) In the absence of specific regulations
The material shall be protected against accidental covering any phase of the destruction of explosive
ignition or explosion from fragments, grass fires, burning material, complete information will be forwarded through
embers, or detonating impulse originating in materials command channels to the Commander, DARCOM,
being destroyed. ATTN: DRCSF, requesting instructions and guidance.
e. Containers for Waste Explosives. Explosives
c. Personnel Protection. destined for the burning ground shall be in original
(1) Operational shields with overhead and closed packages or in containers of fire-retardant
frontal protection will be provided to protect personnel. materials which will not contribute to the existing hazard
Where circumstances warrant their use, complete by readily producing sparks when contacting rocks,
personnel protection shall be provided. Such structures steel, or other containers. Bags or containers made
should preferably be located at the appropriate inhabited from easily ignited material shall not be used.
building distance for the quantity and type of materials Containers shall have closures that will prevent spilling
being detonated but in no case will this distance be less or leakage of contents when handled or if overturned.
than 300 feet. Employees must use such protection Closures shall be of a type that will not 'pinch or rub
when explosive materials are destroyed by detonation or explosives during closing and opening. The closures
when explosive materials which may detonate are being and surfaces of containers openings shall be thoroughly
burned. When Class 1.3 material is being destroyed by cleaned of explosive contamination to minimize the
burning, personnel must remain at the greatest hazard during closing or opening.
practicable distance from the burning site but in no case
shall personnel be permitted closer than the applicable
public traffic route distances.
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f. Servicing of Destruction Site. must be ignited by a safety fuse of a length which will
(1) Trucks transporting explosive material to permit personnel to withdraw safely to the protective
burning or demolition grounds shall meet the shelter, or by black powder squib initiated by an electric
requirements of Chapter 14. No more than two persons current controlled from a distance or structure which
shall ride in the cab. assures safety to personnel should the total quantity of
(2) Upon arriving at a burning or demolition explosives detonate. In some cases, it may be
ground, trucks may distribute explosives necessary to tie two or more squibs together to assure
containers or explosives items to be ignition of the combustible train. When a misfire occurs,
destroyed at sites where destruction is to personnel shall not return to the point of initiation for at
take place. As soon as all items have least 30 minutes. Not more than two qualified persons
been removed, trucks shall be withdrawn shall be permitted to examine the misfire.
from the burning or demolition area to a (a) Loose, dry explosives may be
safe location until destruction is completed. burned without being placed on combustible material if
Containers of explosives shall not be burning will be complete and the ground does not
opened until the truck has been withdrawn become unduly contaminated. The ground must be
(3) (3) 'Containers of energetic materials decontaminated as frequently as is necessary for the
items to 1!( destroyed at the destruction safety of personnel and operations. Qualified inspectors
site shall be spotted and opened at least shall examine the sites after each burning to determine
10 feet from each other and from if these requirements are met. Volatile flammable
explosives material previously laid for liquids shall not be poured over explosives or the
destruction to prevent rapid transmission underlying combustible material to accelerate burning,
of file in event of premature ignition. either before or during the burning of materials.
(4) Empty containers shall be closed and (b) Wet explosives shall not be burned
moved a sufficient distance away to prevent charring or without first preparing a bed of nonexplosive
damage during burning of the explosives. Empty combustible material upon which the explosives are
containers may be picked up by truck on the return trip placed to assure complete burning. It is usually
after delivery of the next quantity to be destroyed. necessary to burn RDX wet to prevent detonation.
(5) When materials being processed at (c) Pyrotechnic materials collected as
destruction sites are to be handled by gasoline or diesel described in paragraph 15-5h(3) may be burned, except
powered fork lift truck, the requirements of Chapter 12 as noted below, by emptying the containers or buckets
will be observed. All such material handled will be containing the oil and pyrotechnic mixture into a shallow
properly packaged and must not be contaminated with metal pan and igniting as described above. The opened
explosives. containers may be burned with the explosives. Burning
of colored smokes and WP and HC mixes requires
g. General Burning Requirements. specific authorization of the Commander, AMC, ATTN:
(1) Except in specific cases, energetic AMCSF.
materials shall not be burned in containers. (4) Parallel beds of explosives prepared for
(2) Bulk initiating explosives and others burning shall be separated by not less than 45.7 meters
used predominantly in detonators and photoflash (150 feet). In repeated burning operations, care must be
compositions shall be destroyed by detonation except taken to guard against material being ignited from
that small quantities (not exceeding 28 grams) may be smoldering residue or from heat retained in the ground.
decomposed chemically. Burnings shall not be repeated on previously burned-
(3) Loose explosives, other than initiating over plots for 24 hours unless the burning area has been
explosives, may be burned in beds not more than three thoroughly soaked with water and an inspection of the
inches deep. Wet explosives may require a thick bed of plot by competent personnel has been made to assure
readily combustible material such as excelsior the safety of personnel during a subsequent burning
underneath and beyond to assure that all the explosives operation.
will be consumed once the materials are ignited. From (5) Some types of explosives and tracer or
the end of the layer of explosives the combustible igniter compositions give off toxic fumes when burned
material should be extended in a train to serve as the Proper protective respiratory equipment, such as hose
ignition point. When an ignition train of combustible masks, airline masks, and self-contained breathing
material leading to the explosives is used, it must be apparatus shall be worn where such fumes are likely to
arranged so that both it and the explosives burn in the be encountered.
direction from which the wind is blowing. The
combustible train of the explosive, if ignited directly,
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h. Materials for Detonating Explosives. together and connected to ground at the power source
(1) Detonation of explosives should, where and the ends of the circuit wires where blasting cap
practicable, be initiated by electric blasting caps using wires are connected except when actually firing the
blasting machines or permanently installed electric charge or testing circuit continuity. The connection
circuits energized by storage batteries or conventional between blasting caps and circuit firing wires must not
power line. Improvised methods for exploding electric be made unless the power end of the circuit lead (firing
blasting caps shall not be used. When items to be wires) are shorted and grounded. The following
detonated are covered with earth, as specified in methods should be followed when connecting electric
paragraph 15-3i(1), blasting caps shall not be buried type blasting cap lead wires to the firing circuit wires:
beneath the ground level with the initiating charge. The 1 Check wires leading to the blasting
initiating explosives should be primed with primacord of machine for continuity and stray currents.
sufficient length to reach up through the covering to a 2 Test electric blasting cap wires for
point where the blasting cap may be connected above electrical continuity, and after the test, connect to wires
the ground level. leading to the blasting machines.
(2) Special requirements for using electric 3 Evacuate all but two, persons from
blasting caps and electric blasting circuits: the area. Place cap into charge to be detonated.
(a) Electric blasting caps, other electric 4 Unshort firing lead wire circuit and
initiators, electric blasting circuits and the like may be check for continuity.
energized to dangerous levels by extraneous electricity 5 Connect firing lead wire to blasting
such as: static electricity, galvanic action, induced machine and fire charges.
electric currents, high tension wires. and radio 6 After firing, remove lead wires from
frequency energy from radio, radar, and television blasting machine and twist the end to short them.
transmitters. Safety precautions shall be taken to
reduce the probability of a premature initiation of electric (e) Electric blasting or demolition operations
blasting caps and explosives charges. and unshielded electric blasting caps should be
separated from radio frequency energy transmitters by
(b) The shunt shall not be removed from the the minimum distances specified in tables 15-1, 2, and
lead wires of the blasting cap until the moment of 3. These distances apply to all parts of the operation,
connecting them to the blasting circuit, except during including the lead wires of the cap and the firing wires
electrical continuity testing of the blasting cap and lead circuit. Before connecting electric blasting caps to the
wires. The individual who removed the shunt should firing wires, the blasting circuit must be tested for the
ground himself or herself by grasping the firing wire prior presence of extraneous electricity by the following test:
to performing the operation in order to prevent
accumulated static electricity from firing the blasting 1 Arrange a dummy test circuit,
cap. essentially the same as the actual blasting circuit except
that a No. 47 radio pilot lamp of known good quality
NOTE
inserted in place of the blasting cap shall be used
After electrical continuity testing of without applying electric current to the circuit. Any glow
the blasting cap, the lead wires must is evidence of the presence of possible dangerous
be short-circuited by twisting the amounts of RF energy and blasting operations in such
bare ends of the wires together areas must be performed with non-electric blasting caps
immediately after testing. The wires and safety fuse.
shall remain short circuited until time 2 The Dupont Blaster's Multimeter,
to connect them to the blasting Model 101, may be substituted for the No. 47 radio pilot
circuit. lamp. If the exposure is to radar, television, or other
microwave transmitters, the actual blasting circuit, with
(c) When uncoiling the lead wires of blasting blasting cap included, but without other explosives shall
caps, the explosives end of the cap should not be held be used to test for extraneous electricity. Personnel
directly in the hand. The lead wires should be performing such tests must be provided protection from
straightened out as far as necessary by hand and shall the effects of an exploding blasting cap. Distances
not be thrown, waved through the air, or snapped as a prescribed in tables 15-1, 2, and 3 should be used as a
whip to unloosen the wire coils. Avoid loops by running guide in the selection of sites for electric blasting
lead wires parallel to each other and close together. If operations in the vicinity of radar and other microwave
loops are unavoidable, keep them small. Keep wires on transmitters.
the ground in blasting layouts.
(d) Firing wires shall be twisted pairs.
Blasting circuit firing wires shall at all times be twisted
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(f) Blasting or demolition operations shall not crimpers. Safety fuse which is too large in diameter to
be conducted during an electrical storm or when a storm enter the blasting cap without forcing shall not be used.
is approaching. All operations shall be suspended, cap Before igniting the safety fuse, all personnel except the
wires and lead wires shall be short-circuited, and all supervisor and not more than one assistant shall retire
personnel must be removed from the demolition area to to the personnel shelter or be evacuated from the
a safe location when an electrical storm approaches. demolition area.
(g) Prior to making connections to the (4) When using blasting caps involving the
blasting machine, the firing circuit shall be tested with a electric or non-electric system of destruction, the
galvanometer for electrical continuity. The individual explosives end of the blasting cap shall always be
assigned to make the connections shall not complete pointed away from the body.
the circuit at the blasting machine or at the panel, nor i. Detonation of Explosives.
shall he/she give the signal for detonation until he/she is (1) Explosives to be destroyed by detonation
satisfied that all persons in the vicinity are in a safe should be detonated in a pit not less than four feet deep
place. When used, the blasting machine or its actuating and covered with not less than two feet of earth. The
device shall be in this individual's possession at all components should be placed on their sides or in
times. When the individual uses a panel, the switch position to expose the largest area to the influence of
must be locked in the open position until ready to fire the initiating explosives with an adequate number of
and the single key or plug must be in his/her possession. demolition blocks placed in intimate contact on top of
(h) Electric blasting caps must be in closed the item to be detonated and held in place by earth
metal boxes when being transported by vehicles packed over the demolition blocks. Bulk explosives can
equipped with two-way radios and also when in areas be used as a substitute for demolition blocks. Where
where extraneous electricity is known to be present or is space permits and the demolition area is remotely
suspected of being present. located from inhabited buildings, boundaries, work
(3) Safety fuses may be used in the areas, and storage areas, detonation of shells and
detonation of explosives where methods described in explosives may be accomplished without the aid of a pit.
15-3h(1) above cannot be accomplished. Safety fuse, In either event, however, the total quantity to be
when used, must be tested for burning rate at the destroyed at one time, dependent on local conditions,
beginning of each day's operation and whenever a new should be established by trial methods to assure that
coil is used. Sufficient length of fuse shall be used to adjacent and nearby structures and personnel are safe
allow personnel to retire to a safe distance, but under no from the blast effect or missiles resulting from the
circumstances should a length be less than three feet or explosion Rocket solid propellants should not be
have less than 120 second burning time. Crimping of destroyed by detonation (paragraph 153Pt-.
fuse to detonators must be accomplished with approved
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(2) After each detonation, a search shall be against possible projection of the charges and
made of the surrounding area for unexploded materials. explosion. Propelling charges must not be piled one on
Lumps of explosives may be picked up and prepared for the other but shall be burned in single layer of charges
the next detonation. laid side by side. Core igniter type charges in the single
(3) In case of misfires, personnel shall not layer should be separated by a distance equal to one
return to the point of detonation for at least 30 minutes caliber.
after which not more than two qualified persons shall be n. Black Powder.
permitted to examine misfire. (1) Black powder is best disposed of by
(4) AR 95-50 outlines the organization and dissolving out the potassium nitrate in a closed system
functions of Regional Airspace Subcommittees and and disposing of the solid wastes separately. It may
establishes uniform procedures for the handling of also be burned as described below. Upon drying, wet
airspace problems. DARCOM installations will request, black powder may retain some of its explosive
through channels, airspace clearance for demolition properties since the nitrate may not have been removed
ground activities in accordance with these regulations. completely.
j. Dynamite. Unopened boxes of exuding (2) Only tools of wood or spark-resistant
dynamite to be destroyed should be burned on a bed of metal will be used in opening the containers. The
combustible material without being opened. contents of only one container will be burned at one
Precautions must be taken to protect personnel and time; no quantity should exceed 50 pounds. The
property from possible detonation. Individual cartridges powder must be removed from the container and spread
may be burned in a single layer not greater in width than on the ground in a train approximately two inches wide,
the length of one cartridge, on a bed of combustible so that no part of the train comes closer than 10 feet to
material. Dynamite awaiting destruction shall be another part. To ignite the powder bed, use a train of
shielded from the sun. Frozen dynamite is more likely flammable material approximately 25 feet in length
to detonate during burning than normal cartridges. placed so that the train and the bed of powder burn into
Destruction of dynamite by detonation may be the direction from which the wind is blowing. Emptied
accomplished where the location will permit this method black powder containers will be thoroughly washed with
of destruction. Care in priming to assure complete water. Serious explosions have occurred during
detonation of the quantity must be taken. handling of supposedly empty black powder cans.
k. Initiating Explosives. When relatively large Safety precautions shall be observed.
quantities of initiating explosives such as lead azide or o. Pyrotechnic Materials. Loose pyrotechnic
mercury fulminate are to be destroyed, detonation is the materials should be burned under the same conditions
best method. The bags containing the explosives as black powder. Water-wet pyrotechnic materials may
should be kept wet while being transported to the be burned in small quantities in furnaces designed and
demolition area. A predetermined number of bags approved for that purpose.
should be removed from the containers, carried to the p. Rocket Solid Propellants.
destruction pit, placed in intimate contact with each (1) Wherever practicable, propellant must be
other and blasting caps used to initiate the explosives. removed from rocket motors and destroyed by burning.
The remaining explosives shall be kept behind a In the event removal of the propellant is not practicable,
barricade with overhead protection during the the rocket motor should be positioned or restricted to
destruction operations and located at a distance that will prevent movement and propellant in the units shall be
assure safety. destroyed by static firing. When units are to be
I. RDX and PETN. RDX and PETN may be destroyed by static firing, complete details of the
burned as described in paragraph 15-3g. Since RDX procedures must be submitted to the Commander,
and PETN are usually collected wet, they should be DARCOM, ATTN: DRCSF for approval.
spread out and partially dried prior to burning. If the wet (2) Rocket or missile propellants (solid) may
material will burn incompletely and with difficulty on the weigh as much as several thousand pounds per grain
combustible bed, before any preparation for initiation is and the polymer-oxidizer type may be extremely difficult
attempted fuel oil may be sprinkled over the bed of to ignite at atmospheric pressures. Large size rocket
combustible material upon which the explosive is motors for specific systems may be destroyed in
placed. accordance with instructions contained in technical
m. Propelling Charges. Propelling charges with manuals or technical bulletins applicable to such
igniters may be burned without slitting but in all cases systems.
igniter protector caps shall be removed from the
charges to be burned. Protection must also be provided
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15-4. Destruction by Chemical Means. The chemical Empty shipping bags should be turned inside out and
destruction of loose explosives, except as provided treated while still water-wet.
below, shall not be permitted unless approval is given (2) The preferred chemical method for
by the Commander, DARCOM. Chemical methods destroying lead azide is to use a 20 to 25 percent
must be supervised by qualified personnel having aqueous solution of ceric ammonium nitrate. When
knowledge of chemistry. Chemical methods shall not be small quantities of lead azide are destroyed in this
used in an attempt to destroy explosives which are manner the reaction is not violent. Since one of the
enclosed or pressed into components such as products of the reaction is a gas, the ending of the gas
detonators. The following procedures may be used evolution indicates completion of destruction.
under adequate supervision for 28 grams or less of the
explosives named. 15-5. Decontamination.
a. Decontamination Requirements.
a. Mercury Fulminate. Place a quantity of aqueous (1) The cleansing of equipment, buildings,
sodium thiosulfate (hypo) solution (20 percent by weight and grounds of explosive materials is a difficult, tedious,
of sodium thiosulfate) equal to 10 times the weight of and sometimes hazardous operation. Because of the
mercury fulminate to be destroyed in a wood or wide variety of materials, the existence of cracks,
earthenware container. While agitating the hypo crevices, and cavities, and the possibility of explosions
solution, add water-wet mercury fulminate. The mixture and the evolution of toxic or explosive gases, the
shall be agitated by air or mechanical means but not by operations and techniques must be made as simple as
hand. Agitation must be continued until all fulminate possible and various precautions taken to ensure safety
has been dissolved, usually within two hours. Operators of personnel and completeness of decontamination.
shall keep to the windward of the container or wear gas Serious accidents have occurred through the
masks to avoid inhaling any cynogen gas evolved. subsequent handling or heating of incompletely
b. Nitroglycerin. Small quantities of nitroglycerin decontaminated equipment.
may be neutralized or destroyed with a mixture of the DARCOM Safety Manual and DARCOM Regulations
following solutions: Solution A. Sodium sulfide 385-series provide detailed safety measures.
(pulverized) (nine parts by weight) and water (30 parts (2) Loading plants, because of the use of a
by weight). number of explosive materials, present particularly
Solution B. Denatured ethyl alcohol (70 parts by difficult problems of decontamination. The procedures
weight) and acetone (20 parts by weight). appropriate to several different explosives
manufacturing plants may be required for the
Do not combine the two solutions until immediately decontamination of different parts of an individual
before use since potency of the mixed solutions loading plant.
diminishes on storage. This mixture should be used (3) With the growing complexity of modern
only for very small quantities of nitroglycerin (e.g., the military explosives and propellants because of the
oily film that adheres to surfaces after the nitroglycerin introduction of new nonexplosive ingredients as well as
has been removed with sponges or absorbed in wood mixtures of explosives, the problem of decontamination
pulp or sawdust). Operators using this solution should is increased correspondingly. New and special
wear rubber gloves. compositions, therefore, should be given careful
c. Black Powder. Black powder may be technical consideration before decontamination
completely destroyed by leaching or washing with large operations are undertaken.
quantities of water and disposing of the washings (4) A necessary function of decontamination
separately from the residue. is the collection of industrial wastes for destruction or
d. Lead Azide. reclamation. Elaborate controls are required to assure
(1) Lead azide accumulated on surfaces that these collection efforts are performed safely and
should be taken up with water wet cloths. The cloths economically without causing down-time in essential
should then be washed out in one of the solutions operations.
named below after which the complete desensitizing
treatment is carried out in the solution. The cloths
should be thoroughly washed with water before reuse.
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b. Decontamination and Dismantling Explosives tanks, sanitary filter tanks, and unlined sumps, settling
Establishments. The decontamination and dismantling basins, or leaching pits is prohibited except as
procedures to be followed for explosives establishments specifically authorized by permit. Sumps should be
upon cessation of activity or upon conversion to other desensitized and cleaned at regular intervals. Cracks
uses shall be outlined in detail as prescribed in TB 700- and crevices may contain explosives residue. Such
4. Requirements shall be developed for cleaning and residue must not be subjected to impact or friction from
dismantling equipment preparatory to repair or such sources as high pressure water streams, scraping
maintenance. Any equipment used in an explosive tools or devices, etc., which may initiate the sensitive
operation which may subsequently be used in operations explosives. Quantities of initiating explosives in excess
with non-explosive material or explosives other than that of 28 grams shall be destroyed by burning or detonation
for which the equipment was used originally shall first be (see paragraph 15-3). Explosive materials to be
given whatever treatment is necessary to insure that no removed from a settling basin should be maintained wet
explosive material remains. Decontamination markings until removed. The more sensitive explosives should be
and the use of DA Form 3803, Materiel Inspection Tag, maintained wet until destroyed. Materials containing
should be included as a part of these requirements. powdered metals should be kept under water to prevent
c. Decontamination Operations. any dangerous rise in temperature which might
(1) Wherever practicable, decontamination is otherwise be developed in the reaction between the
affected by the physical operations of washing, metals and a small quantity of water.
steaming, and vacuuming. While washing operations
suffice for most pyrotechnic materials, some smoke and Table 15-4. Decontaminating Chemicals
incendiary compositions present explosion hazards Contaminant Decontaminating chemical
when wet with water. A small amount of water Lead azide Ceric ammonium nitrate
contacting hexachloroethane (HC) smoke mixture may Mercury fulminate Sodium thiosulfate
cause an explosion and release of toxic fumes. Metal Nitroglycerin Methanolic sodium sulfite
objects such as nitrators, centrifuges, tanks, piping, etc. Nitrocellulose Sodium hydroxide
are washed with water and steamed. Wooden objects Smokeless powder Sodium hydroxide and acetone
such as railings, paddles, etc. and buildings such as TNT Sodium carbonate and sellite
dry-houses, and packing materials, gaskets, etc., are Tetryl Sodium carbonate and sellite or
destroyed by removing and burning after preliminary acetone
cleaning. Earth that is so contaminated as to offer a fire Pentolite Acetone
or explosion hazard is wetted, scraped up, and burned White phosphorus Copper sulphate solution
at a burning ground.
(2) Free acid present in equipment requires e. Deposition from Waste Liquids. When sumps or
neutralization as well as washing and a five percent basins are properly designed, the wash water which
solution of sodium carbonate (soda ash) is used for this passes beyond filters and basins should be free from
purpose. Because of the uncertainty of complete significant amounts of explosive materials. If the
removal of explosives in all cases by the physical effluent is discharged into a public stream, river, etc, it
methods described, chemical methods are used also to must not contain more explosives than permitted by
supplement these. Standard decontamination local and state regulation. Consideration should be
procedures include the decontaminating chemical given to the possibility of deposition of explosive
shown by table 15-4. materials on the banks of streams or marshes during
d. Collection of Contaminated Industrial Wastes. periods of drought, as well as to any possible
Industrial wastes which may contain explosive materials subsequent precipitation of explosives with change of
and chemical agents shall be collected only in holding, temperature, acidity, or concentration of the waste
storage, or disposal facilities specifically designed and water. Where uncertainty exists regarding the
permitted (i.e., having environmental operating permits) composition of waste waters, competent technical
for that purpose. Disposal into sanitary sewers, septic advice and assistance should be obtained.
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f. Handling Water-Soluble Materials. Where throughout the plant, and by having individual oil
ammonium picrate, black powder, or other materials containers serve as collection points for multiple
which are appreciably soluble in water are handled, the operations. In the latter case, nominal quantities of dry
amount of dissolved material should be kept as low as scrap may accumulate at operating locations before
practicable. Floors should be swept before washing they are delivered to collection points and placed in
down to reduce the quantity of dissolved material in the containers of oil. The level of oil should be kept at least
wash water. 2.54 centimeters (one inch) above the level of any
g. Destruction of Collected Solid Wastes. pyrotechnic mixture in the containers. Containers in
Contaminated solid waste material should be taken in which scrap explosives and pyrotechnic materials have
closed containers, as soon as practicable, to buildings been collected should be removed from the operating
set apart for its treatment or to the burning ground to be buildings for burning at least once per shift. Where oil is
destroyed in an appropriate manner. Collected used, fire-fighting equipment satisfactory for Class B
explosive and chemical wastes must not be disposed of fires should be available. Carbon dioxide or foam
by being buried or thrown in any streams or tidewater extinguishers are recommended.
unless they are decomposed by water. Disposal of
decomposed wastes in streams or tidewater will be i. Location of Collection Chambers.
allowed only if permitted by federal, state, and local laws (1) Wherever practicable, dry type explosives
and regulations. dust collection chambers, except portable units as
h. Collection of Explosives Dusts. specifically provided for in paragraph 15-5j(3), should be
(1) Dust collecting systems may be used to located outside operating buildings in the open or in
aid cleaning, to lessen explosion hazards, and to buildings exclusively set aside for the purpose. In order
minimize industrial job-incurred poisoning and to protect operating personnel from an incident involving
dermatitis. the collection chamber, a protective barrier must be
provided between the operating building and the outside
(2) Examples of high explosives dusts which
location or separate building where the collection
may be removed by a vacuum system are TNT, tetryl,
chamber is placed. If the collection chamber contains
ammonium picrate, composition B, and pentolite. A wet
11.35 kilograms (25 pounds) of explosives or less, the
collector, which moistens the dust close to the point of
protective barrier may be a 30.5 centimeters (12 inch)
origin and keeps it wet until the dust is removed for
reinforced concrete wall located at least 2.44 meters
disposal, is preferred except for ammonium picrate
(eight feet) away from the operating building. The
which should be collected in a dry system.
collection chamber must be separated from cubicle
(3) More sensitive explosives such as black walls by at least three feet. If the collection chamber
powder, lead azide, mercury fulminate, tracer, igniter, contains more than 11.35 kilograms (25 pounds) of
incendiary compositions, and pyrotechnic materials may explosives and is separated from the operating building
be collected by vacuum in this manner, provided they by a 30.5 centimeters (12 inch) reinforced concrete wall,
are kept wet with the wetting agent, close to the point of the wall must be separated from the operating building
intake. The vacuum (aspirator) systems must be so by a minimum of unbarricaded intraline distance. The
arranged that the various types of explosives are cubicle may be placed at a minimum of barricaded
collected separately or in a manner to avoid mixture of intraline distance from the operating building if the
dissimilar hazards; i.e., black powder with lead azide. protective barrier meets the requirements of DARCOM
Provision should be made for the proper liberation of safety regulations for operational shields (including the
gases that may be formed. The use of vacuum systems required three foot distance between the barrier and the
for collecting these more sensitive materials should be explosives) and for the quantity of explosive in the
confined to operations involving small quantities of collection chamber, or if the barrier complies with the
explosives; for example, in operations involving fuzes, requirements of paragraph 12-11v for barricades.
detonators, small arms ammunition, and black powder Barricaded and unbarricaded intraline distances will be
igniters. Potential fire and explosion hazards can be based on the quantity of explosives in the collection
minimized by collecting scrap pyrotechnic, tracer, flare, chamber.
and similar mixtures in No. 10 mineral oil. Satisfactory
techniques include placing the oil in catch pans and
scrap transporting containers at the various operations
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(2) When it is not practicable to locate dry dust concentration which may produce a severe health
type collection chambers outside the operating building, hazard, manual operation of the suction hose to remove
a separate room within the building may be set aside for explosives dusts is preferred to a permanent attachment
the purpose. This room shall not contain other to the explosive dust producing machine. A permanent
operations nor shall it be used as a communicating attachment increases the likelihood of propagation
corridor or passageway between other operating through a collection system of a detonation occurring at
locations within the building when explosives are being the machine. Interconnection of manually operated
collected. Walls separating the room from other hose connections to explosives dust-producing
portions of the operating buildings must meet the machines should be avoided.
requirements specified in DARCOM safety regulations (2) Two collection chambers should be
for the quantity of explosives in the collecting chamber. installed in series ahead of the pump or exhauster to
If more than one collection chamber is to be located in prevent explosives dust from entering the vacuum
the room, the room must be subdivided into cubicles by producer in dry vacuum collection systems.
walls meeting the requirements of DARCOM safety (3) Dry type portable vacuum collectors shall
regulations and not more than one collection chamber not be located in a bay or cubicle where explosives are
shall be in a single cubicle. present or in inclosed ramps but may be positioned
(3) Stationary and portable wet type outside the building or in a separate cubicle having
collectors may be placed in the explosives operating substantial dividing walls for quantities of explosives not
bays or cubicles provided the quantity of explosives in exceeding five pounds. Wet type portable vacuum
the collectors does not exceed five pounds. If placed in collectors may be placed in explosives operating bays or
separate cubicles, the explosives limits for the collectors cubicles provided the quantity of explosives in the
may be increased to the amount reflecting the collector is limited in accordance with the requirements
capabilities of the cubicle walls as operational shields. of paragraph 15-5i. For dry collection of quantities in
For greater quantities, the location requirements set excess of 2.3 kilograms (five pounds) or wet collection
forth above are applicable. of quantities in excess of 6.8 kilograms (15 pounds), the
further provisions of paragraph 15-5i shall apply.
j. Design and Operation of Collection Systems. (4) The design of wet collectors shall provide
(1) Collection systems and chambers shall be for proper immersion of explosives, breaking up air
designed to prevent pinching explosives (especially dust bubbles to release airborne particles, and removal of
or thin layers) between metal parts. Pipes or tubes moisture from the air before it leaves the collector to
through which dusts are conveyed should have flanged, prevent moistened particles of explosives from entering
welded, or rubber connections. Threaded connections the small piping between the collector and the exhauster
are prohibited. The system shall be designed to or pump.
minimize accumulation of explosives dusts in parts (5) At least once every shift, explosives dust
other than the collection chamber. Accordingly, pipes or shall be removed from the collector chamber to
ducts through which high explosives are conveyed shall eliminate unnecessary and hazardous concentrations of
have long radius bends with a centerline radius at least explosives. The entire system should be cleaned
four times the diameter of ducts or pipes. Short radius weekly, dismantling the parts if necessary.
bends may be used in systems for propellant powder (6) The entire explosives dust collecting
provided they are stainless steel with polished interiors. system shall be electrically bonded and grounded. The
The number of points of application of vacuum should grounds must be tested frequently.
be kept to a minimum. So far as practicable, each room
(7) Slide valves for vacuum collection
requiring vacuum collection chambers, but not more
systems are permitted. There shall be no metal-to-
than two bays, shall be serviced by a common header to
metal contacts with the metal slide. An aluminum slide
the primary collection chamber. Wet primary collectors
operating between two ebonite spacer bars will not
are preferred. Not more than two primary collectors
constitute a hazard.
(wet or dry type) should be connected to a single
secondary collector. If an operation does not create a
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e. Propellants Reclamation. Solid ammunition also impervious to water making it impossible to remove
propellants are difficult to recycle because the a water-soluble oxidizer from the metal and binder. This
smokeless base(s) (nitrocellulose and/or nitroguanidine) impediment in recycling calls for chemical cleavage of
used in the ammunition will deteriorate with age. Solid the binder linkage or the use of binder molecular
rocket propellants in many instances can be recovered structures which can be thermally degraded. Liquid
as shown in table 15-6. However, the polymeric binder propellants, on the other hand, do not present much of a
used in solid rocket propellants is a cross-linked material recycling problem. They usually consist of a fuel and an
which is insoluble in solvents making it impossible to oxidizer which are both usually basic industrial
remove the binder simply by solvent extraction. chemicals that can be stored separately for an indefinite
Furthermore, the finely divided metal and oxidizer period of time. Hence, liquid propellants are always
particles are intimately coated with the binder which is essentially recovered before actual use.
f. Pyrotechnics Reclamation. As can be seen Current investigations consist of attempts to recover the
from the data in table 15-7, little work has been done on pyrotechnic materials from signal flares. However, the
recycling the majority of pyrotechnic basic materials with work to date can be considered as a pilot activity which
the exception of the magnesium and sodium nitrate in can be further developed and applied to other
illuminating flares and dyes in smoke components. pyrotechnic items and components.
15-14
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15-15(15-16 blank)
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APPENDIX A
CHARACTERISTICS AND DATA
Primary explosives
Lead azide (pure) 29 100 - - - 0.01
DLA 29 to 43 13 to 28 - 340
SLA 14 30 - 350
CLA 14 to 21 - - - - -
PVA-LA 29 to 35 13 to 16 - 344
RD-1333 36 15 - 340
DCLA 21 to 42 - - 345
Mercury fulminate 14 5 100 210 - - 0.025
Diazodinitrophenol 14 5 100 195 - - 0.25
Lead styphnate (normal) 21 8 - 282 - - 0.0009
Tetracene 14 7 160 - - 0.01
Aliphatic nitrate esters
BTN 7 16 - - 230 - - -
DEGN - - - - 237 - - -
Nitrocellulose
Pyrocellulose (12.750/o N) 21 8 - 100 170 - - -
Blended 21 8 - 100 200
Guncotton (13.3% N) 21 9 - 100 230 0.10
Nitroglycerin 7 16 100 100 222
Nitrostarch 36 - - - 217
PETN 43 17 5 100 215 0.03 0.17 0.036
TEGN 307 100 + 0 - 225
TMETN - - 100 - 235 - - -
Nitramines
HMX - 32 100 (steel - 327 0.30 - -
shoe)
0 (fiber
shoe)
RDX 57 33 20 100 260 0.05 0.19 -
EDDN 64 75 - - 445 - 2.0
Haleite - 48 0 - 190 0.21 0.13
Nitroguanidine - 47 0 0 275 0.20 - -
Tetryl 57 26 0 70 257 0.10 0.19 -
A-1
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Nitroaromatics
Ammonium picrate 121 100+ 0 30 318 0.85 -
DATB 200 - - - - - - -
HNS 50 - - - - - - -
TATB 79 - - - 520 0.30 - -
TNT - - - 0 0 475 0.26 0.24 0.06
Ammonium nitrate 221 100 + 0 0 no explosion - - -
Binary
Amatol 93 to 100 - 0 0 254 to 300 - - -
Composition A3 125 - 0 0 250 to 280 0.25 0.22 -
Composition B 100 75 - 20 278 0.20 0.22 -
Composition C3 100 100 + 0 40 280 - - -
Composition C4 > 100 - 0 20 263 to 290 0.20 - -
55/45 Ednatol - 95 0 0 190 0.22 0.22 -
75/25 Octol 170 0 - 350 0.30 - -
70/30 Octol 136 - 0 - 335 0.30 - -
50/50 Pentolite 86 34 0 80 220 0.13 0.19
Picratol 100 100 + 0 0 285 - - -
70/30 Tetrytol 78 28 0 - 320 0.22 0.23
Tritonal 71 73 0 60 470 0.30 - -
Ternary
Amatex 20 107 to 129 - - 6 240 - - -
HBX-1 75 - - 75 - - - -
HBX-2 80 - - 80 - - - -
HTA-3 121 - 0 90 370 - - -
Minol-2 93 35 - - 224 to 260 - - -
Torpex 50 75 - 100 260 - 0.18 -
Quanternary
DBX 71 - 49 200 0.20 - -
A-2
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Table A-2. Effects of Explosives
Primary explosives
Lead azide (pure) 40 - - - 4.68 5,400 - 40 - -
DLA 38
Mercury fulminate 27.3 to 59 - - - 4.17 5,400 - 37 to 50 - -
Diazodinitrophenol 94 to 105 - - - 1.63 7,100 - 110 - -
Lead styphnate (normal) 22 to 53 - - - 2.9 5,200 - 42
Tetracene 40 to 70 - - - - - 51 to 63 - -
Potassium dinitro-
benzofuroxane 93 - - - - - - - - -
Aliphatic nitrate esters
BTN 103 - - - - - - - -
DEGN 100 - - 1.38 6,760 127 144 to 150 - -
Nitrocellulose
Pyrocellulose (12.75% N) 94
Blended (13.30/o N) 99
Guncotton 102 - - 84 1.3 7,300 125 136 to 147 - -
High nitrogen 108-120
Nitroglycerin 120 - - - 1.6 7,700 140 185
Nitrostarch(13.4% N) - - - 83 0.90 6,190 145
PETN 129 to 141 127 - - 1.773 8,300 145 170 -
TEGN 30.6 - - - 1.33 2,000 - -
TMETN 91 - - - - - 140 - -
Nitramines
HMX 125 - - 1.89 1.89 9,110 170 159 to 165 - -
RDX 125 to 145 135 to 141 141 - 1.770 8,700 150 170 - -
EDDN 96 100 - - 1.50 6,915 120 125 - -
A-3
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Table A-2. Effects of Explosives (Cont.)
Haleite 109 to 119 113 to 122 117 to 147 1.55 7,883 136 122 to 143 - -
Nitroguanidine 73.5 to 84 95 1.70 8,100 104 78 to 101 - -
Tetryl 113 to 123 115 121 117 to 125 1.71 7,850 145 125 to 145 - -
Nitroaromatics
Ammonium picrate 78 to 82.591 99 1.63 7,154 98 - - --
DATB 120 - - 1.79 7,585
HNAB - - - 1.77 7,250 - 123 --
HNS - 120 - - 1.70 7,000 - - - --
TATB 90 - - - 1.937 8,000 - - - --
TNT - - - - 1.636 6,826 - - - --
Ammonium nitrate - - - 1.0 2,800 - 75
Binary
Amatol 74 to 94 - 81 - 1.6 5,300 to 6,550 122 116 to 126 97 87
Composition A3 107 to 115 126 150 - 1.6 8,200 132 144 -
Composition B 113 129 to 132 142 - 1.68 7,840 133 131 110 110
Composition C3 112 114 to 118 133 - 1.6 7,625 126 117 105 109
Composition C4 116 115 to 130 - - 1.59 8,040 130 -
CH6 128 - - - - 8,223
55/45 Ednatol 112 112 118 1.63 7,340 119 119 108 110
75/25 Octol - - - - 1.81 8,364 to 8,643 -
70/30 Octol - - - - 1.80 8,310 to 8,377 - - - -
50/50 Pentolite 114 126 131 113 1.62 7,402 126 121 105 107
Picratol 94 100 102 - 1.67 6,970 100 - 100 100
70/30 Tetrytol 111 118 119 1.61 7,350 - 120
80/20 Tritonal 114 93 91 1.76 6,770 124 153 113 118
A-4
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Table A-2. Effects of explosives (Cont)
Ternary
Amatex 20 - - - 1.61 6,944
HBX-1 102 129 1.75 7,222 - 121 116
HBX-3 93.5 - 68 - 1.86 6,920 - 121 125
HTA-3 128 - - - - 7,866 -
Minol-2 86 66 - - 1.77 6,200 143 165
Torpex 122 120 126 - 1.8 7,660 134 161 122 125
Quanternary
DBX 112 - - - 1.76 6,800
A-6
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Products of explosion
Heat of Heat of
combustion, formation Heat, Gas,
calories kilogram calories milliliters
per gram at calories per gram per gram
Material constant per mole (H2O gas)
Primary explosives
Lead azide - -112 to -126.3 367 308
Mercury fulminate 938 -221 to-226 427 315
Diazodinitrophenol - 956 820 -
Lead styphnate 1,251 92.3 460 440
Tetracene - 270 658 1,190
Aliphatic nitrate esters
BTN 2,167 368 1,458 -
DEGN 2,792 -99.4 1,161 -
Nitrocellulose
Pyroxlyn (12% N) - -216 1,020 -
Guncotton (13.350/o N) 2,313 -200 1,020 883.2
High nitrogen (14.14% N) - -191 1,810
Nitroglycerin 1,603 -90.8 1,486 715
PETN 1,957 -128.7 1,510 790
TEGN 3,428 -603.7 750 -
TMETN 2,642 -422
Nitramines
HMX 2,231 to 2,253 11.3 to 17.93 1,480
RDX 2,259 to 2,284 14.71 1,480 908
EDDN 2,013 156.1 128 to 159
Haleite 2,477 20.11 1,276 908
Nitroguanidine 2,021 20.29 880 1,077
Tetryl 2,914 4.67 to 7.6 1,450 760
Nitroaromatics
`Ammonium picrate 2,745 95.82 800 -
`DATB - -97.1 to-119 910 -
`HNAB - -58 to-67.9 1,420 -
`HNS 3,451 -13.9 to 1.87 1,360 -
`TATB 2,850 -33.46 to-36.85 1,018 -
`TNT 3,563 to 3,598 -10 to- 19.99 1,290 730
`Ammonium nitrate - 88.6 381 980
A-6
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Primary explosives
Lead azide
DLA 0.34 0.39 1 0.32 40 0.46 40 - -
SLA 0.08 0.16 - - - - - - -
PVA-LA- - 0.13 - 1 0.20 40 0.44 40 - -
RD1333- - 0.30 0.30 1 - - 0.43 40 - -
Mercury fulminate 0.18 ----------------------------------------------explodes----------------------------------------- -----
Diazodinitrophenol 0.24 2.10 2.20 5 7.6 40
Lead styphnate (normal) - 1.5 1.5 1 0.4 40 0.4 40
Tetracene 0.5 23.2 3.4
Potassium dinitrobenzofuroxane 0.03 0.05
Lead mononitroresorcinate - - - 2.3 - - 0.4 40 - -
Aliphatic nitrate esters
Nitrocellulose (12%N) - 0.3 0 1 - - 5.0 48 - -
Nitroglycerin 3.5 3.5 1 11 + 16
PETN 0.02 0.1 0.0 5 0.5 40 11 + 40 - -
TEGN - 1.8 1.6 1 -0.45 40 0.8 8
to 0.99
TMETN - 2.5 1.8 - - - - - - -
Nitramines
HMX - 0.05 0.03 5 0.37 40 0.45 40 0.62 40
RDX 0.03 0.04 0 5 - - 0.9 40 2.5 40
Haleite 0.01 0.2 0.3 5 0.5 48 1.5 48 11 +
to 2.4
Nitroguanidine 0.04 0.48 0.09 5 0.4 40 0.5 40 - -
Tetryl 0.01 0.1 0.0 5 0.3 40 1.0 40 11 + 12
Nitroaromatics
Ammonium picrate 0.12 0.1 0.1 5 0.2 40 0.4 40 0.4 40
DATB - - - 1 - - 0.03 48
HNS - >1 - - - - - - - -
TATB - 17 - - - - - - - -
TNT 0.04 0.1 0.1 5 0.1 40 0.4 40 0.7 40
A-7
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Binary
50/50 Amatol - - 5 0.3 40 1.0 40
Composition B - 0.2 0.2 5 0.7 48 0.9 48 11 + 48
Composition C3 - - - 1.21 48 11 + 48
Composition C4 - 0.13 0.0 - 0.20 40
55/45 Ednatol - 0.2 0.1 5 0.7 40 11 + 24 - -
75/25 Octol - - 5 - - 0.39 40 11 40
to 0.65
70/30 Octol - - - 5 - - 0.37 40 5.10 40
to 0.76
50/50 Pentolite - 0.0 0.2 5 2.5 40 11 + 16 -
Picratol 0.0 0.0 0.05 5 0.4 40 0.7 40 0.7 40
70/30 Tetrytol - 0.1 0.1 5 3.0 40 11 + 40
80/20 Tritonal - - 5 0.1 40 0.2 40 0.8 40
Ternary
HBX-1 - 0.058 0.0
HBX-2 - 0.70 0.0
Minol-2 - 5 0.0 48 2.1 40 - -
Torpex - 0.0 0.10 5 0.2 40 1.5 40 11 + 16
Material Crystal or 20,685 34,475 68,450 103,425 137,900 206,850 275,800 Cast
liquid (3,00) (5,000) (10,000) (15,000) (20,000) (30,000) (40,000)
Primary explosives
Lead azide (pure) 4.87
DLA - - - - 3.14 - - - -
SLA - - - - 3.31 - - - -
PVA-LA - - - - 3.81 - - - -
Mercury fulminate 4.43 3.0 3.2 3.6 3.82 4.0 4.1 - -
Diazodinitrophenol 1.63 to 1.65 1.14
Lead styphnate (normal) 3.02
Tetracene 1.7 1.05
A-8
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Material Crystal or 20,685 34,475 68,450 103,425 137,900 206,850 275,800 Cast
liquid (3,00) (5,000) (10,000) (15,000) (20,000) (30,000) (40,000)
Nitramines
HMX 1.905 - - - - - - - -
RDX 1.816 1.46 1.52 1.60 1.65 1.68 1.70 1.71
Haleite 1.66 to 1.77 - 1.28 1.38 1.44 1.49 - - -
Nitroguanidine 1.71 0.95 -
Tetryl 1.73 1.40 1.47 1.57 1.63 1.67 1.71 1.71 1.62
Nitroaromatics
Ammonium picrate 1.717 1.33 1.41 1.47 1.51 1.53 1.56 1.57
HNAB 1.79 - - - - - - - -
TNT 1.654 1.34 1.40 1.47 1.52 1.55 1.59 1.59 - -
Quanternary
DBX - - - - - - - - 1.61 to
- - - - - - - - 1.74
A-9
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A-10
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Nitramines
HMX MIL-H-45444
RDX MIL-R-398
EDDN no specification
Haleite no specification
NQ MIL-N-494
Tetryl MIL-T-339
Nitroaromatics
Ammonium picrate MIL-A-166
DATB no specification
HNAB no specification
HNS no specification
TATB no specification
TNT MIL-T-248
Ammonium nitrate MIL-A-50460
Binary
Amatol no specification
Composition A3 MIL-C-440
Composition A4 MIL-C-440
Composition A5 MIL-E-14970
Composition A6 MIL-C-60051
Composition B MIL-C-401
Composition B3 MIL-C-45113
Composition B4 MIL-C-46652
Cyclotol MIL-C-13477
Composition CH6 MIL-C-21723
A-11
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Ternary
Amatex no specification
Ammonal no specification
H6 MIL-E-22267
HBX MIL-E-22267
HTA-3 no specification
Minol-2 MIL-M-14745
Torpex no specification
PBX
Military specifications
LX-14-0 MIL-H-48358
PBX Type 1 MIL-P-14999
PBX Type 2
PBX 0280 MIL-R-48878
PBX 9010 MIL-P-45447
PBX 9407 MIL-R-63419
PBXN-203 MIL-E-85113
PBXN-4 MIL-P-23625
PBXN-5 MIL-E-81111
Navy specifications (ternary category)
PBXN-3 OS-11641
PBXN-6 WS-12604
PBXN-101 WS-3829
PBXN-102 WS-3823
PBXN-103 OS-12800D
PBXN-104 WS-11511
PBXN-201 WS-1 1498
PBXN-301 WS-12612
Dept. of energy specifications
(Lawrence Livermore Laboratory [LLNL])
LX-04 RM 252353
LX-07 RM 253379
LX-09 RM 253200
LX-10 RM 253511
LX-13 RM 253520
1
Currently, because of worker exposure hazards, benzene is being replaced by other solvents in all specifications.
A-12
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A-13(A-14 blank)
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APPENDIX B
BIBLIOGRAPHY
B-1
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TM 9-1300-214
Partington, J.R. A History of Greek Fire and Gunpowder. Cambridge, England: W. Heffer and
Sons, LTD, 1960.
Pollard, F.B. andJ.H. Arnold, ed. Aerospace Ordnance Handbook. Englewood Cliffs, New
Jersey: Prentiss Hall, 1966.
Prentiss, Agustin M. Chemicals in War. York, Pa: McGraw-Hill, Maple Press, 1937.
Pristera, F. Explosives. Encyclopedia of Industrial Chemical Analysis, vol 12. New York: John
Wiley and Sons, 1971.
Stiefel, Ludwig. GunPropellants. Progress in Astronautics and Aeronautics, vol 66, 1978.
The Encyclopedia of Explosives and Related Items. Springfield, Virginia: National Technical
Information Service (US Department of Commerce), 1960-1982.
Thompson, Harry C. and Lida Mayo.The Ordnance Department, Procurement and Supply. US
Army in World War II. Washington, DC: Office of Chief of Military History, Department of the
Army, 1956.
Wells, H.G. The Outline of History. New York: The Macmillan Co., 1923 (1920).
Yinon, J. and S. Zitrin. The Analysis of Explosives. Peragamon Series in Analytical Chemistry,
vol 3. New York: Peragamon Press, 1981.
B-2
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INDEX
Paragraph Page
Change 3 Index 1
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Index 3
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Composition A
Brisance ........................................................................................................................... 8-6 8-100
Characteristics.................................................................................................................. 8-6 8-100
Destruction ....................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-6 8-100
Packing............................................................................................................................. 14-2 14-1
Sensitivity ........................................................................................................................ 8-6 8-100
Shipment ......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-101
Composition B
Brisance ........................................................................................................................... 8-6 8-106
Characteristics.................................................................................................................. 8-6 8-105
Destruction ...................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-6 8-105
Packing ............................................................................................................................ 14-2 14-1
Reactivity ......................................................................................................................... 8-6 8-105
Sensitivity ........................................................................................................................ 8-6 8-105
Shipment.......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-106
Composition C
Brisance ........................................................................................................................... 8-6 8-111
Characteristics ................................................................................................................. 8-6 8-109
Destruction ....................................................................................................................... 15-3 15-1
History ............................................................................................................................. 15-3 15-3
Manufacture...................................................................................................................... 8-6 8-111
Packing............................................................................................................................. 14-2 14-1
Reactivity.......................................................................................................................... 8-6 8-111
Sensitivity ........................................................................................................................ 8-6 8-109,
......................................................................................................................................... 8-111
Shipment ......................................................................................................................... 14-5 14-10
Specification..................................................................................................................... 8-6 8-109,
......................................................................................................................................... 8-110
Stability ............................................................................................................................ 8-6 8-110,
......................................................................................................................................... 8-111
Composition CH6
Brisance ........................................................................................................................... 8-6 8-111
Characteristics .................................................................................................................. 8-6 8-111
Destruction ....................................................................................................................... 15-3 15-1
Packing............................................................................................................................. 14-2 14-1
Sensitivity ........................................................................................................................ 8-6 8-111
Shipment ......................................................................................................................... 14-5 14-10
Computer programs
Detonation........................................................................................................................ 4-5 4-10
Interior ballistics ............................................................................................................... 9-10 9-8
Propellants ....................................................................................................................... 9-3 9-2
Cook-off temperature test........................................................................................................ 5-6 5-5
Corning of black powder.......................................................................................................... 2-5 2-3
Couche ................................................................................................................................... 11-2 11-3
Covolume............................................................................................................................... 9-3 9-2
CSE ....................................................................................................................................... 11-2 11-3
Cyclotetramethylenetetranitramine
Brisance............................................................................................................................ 8-3 8-30
Characteristics.................................................................................................................. 8-3 8-27
Destruction ...................................................................................................................... 15-3 15-1
Index 4
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Cyclotetramethylenetetranitramine (Cont)
Manufacture...................................................................................................................... 8-3 8-29
Packing............................................................................................................................. 14-2 14-1
Reactivity ......................................................................................................................... 8-3 8-30
Sensitivity ........................................................................................................................ 8-3 8-30
Shipment.......................................................................................................................... 14-5 14-10
Specification..................................................................................................................... 8-3 8-29
Stability ............................................................................................................................ 8-3 8-30
Toxicity ............................................................................................................................ 12-2 12-1
Cyclotrimethylenetrinitramine
Brisance ........................................................................................................................... 8-3 8-35
Characteristics ................................................................................................................. 8-3 8-30
Destruction ...................................................................................................................... 15-3 15-1
History ............................................................................................................................. 2-6, 2-8 2-8, 2-14
Manufacture ..................................................................................................................... 8-3 8-34
Packing ............................................................................................................................ 14-2 14-1
Reactivity ......................................................................................................................... 8-3 8-33
Sensitivity ........................................................................................................................ 8-3 8-34
Shipment.......................................................................................................................... 14-5 14-10
Specification..................................................................................................................... 8-3 8-37
Stability ............................................................................................................................ 8-3 8-35
Toxicity ............................................................................................................................ 12-2 12-1
Cylinder expansion test.......................................................................................................... 5-21 5-9
Dainamaito ............................................................................................................................. 11-5 11-10
DATB (see diamino-trinitrobenzene)
DBX (see depth bomb explosive)
DCLA (see lead azide)
DDNP (see diazodinitrophenol)
Decontamination .................................................................................................................... 15-5 15-28
Deflagration ........................................................................................................................... 3-2, 4-3 3-1, 4-1
Deflagration to detonation transition propellant ....................................................................... 6-4 6-1
Deflagration to detonation transfer......................................................................................... 4-4 4-2
DEGN (see diethyleneglycol dinitrate)
Delays .................................................................................................................................... 3-4, 10-1 3-3, 10-15
Demilitarization ...................................................................................................................... 15-6 15-12
Depth bomb explosive
Brisance ........................................................................................................................... 8-6 8-129
Characteristics ................................................................................................................. 8-6 8-129
Destruction ...................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-6 8-129
Packing ............................................................................................................................ 14-2 14-1
Sensitivity ........................................................................................................................ 8-6 8-129
Shipment.......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-129
Toxicity ............................................................................................................................ 12-2 12-3
deSaint Roberts equation ...................................................................................................... 9-7 9-6
Destruction by burning and detonation................................................................................... 15-3 15-1
Destruction of waste ............................................................................................................... 15-5 15-8
Detection, hidden explosives.................................................................................................. 3-7 13-11
Detection, residues................................................................................................................. 13-6 13-10
Deterrent ................................................................................................................................ 9-7 9-7
Detonation ............................................................................................................................. 3-2, 4-5 3-1, 4-3
Detonation velocity
Definition ......................................................................................................................... 3-5 3-4
Test ................................................................................................................................. 5-5 5-3
Detonierande zundschnur........................................................................................................ 1-9 11-17
Detonity .................................................................................................................................. 11-6 11-12
Change 3 Index 5
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Index 6
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Index 7
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Index 8 Change 3
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Hexanitroazobenzene
Brisance............................................................................................................................ 8-4 8-62
Characteristics ................................................................................................................. 8-4 8-62
Destruction ....................................................................................................................... 15-3 15-1
Manufacture...................................................................................................................... 8-4 8-62
Packing............................................................................................................................. 14-2 14-1
Sensitivity......................................................................................................................... 8-4 8-62
Shipment.......................................................................................................................... 14-5 14-10
Stability............................................................................................................................. 8-4 8-62
Hexanitrostilbene
Brisance............................................................................................................................ 8-4 8-65
Characteristics ................................................................................................................. 8-4 8-62
Destruction ....................................................................................................................... 15-3 15-1
Manufacture...................................................................................................................... 8-4 8-65
Packing............................................................................................................................. 14-2 14-1
Sensitivity......................................................................................................................... 8-4 8-65
Shipment.......................................................................................................................... 14-5 14-10
Stability............................................................................................................................. 8-4 8-66
Hexgeno plastico..................................................................................................................... 11-7 11-14
Hexocire ................................................................................................................................. 11-4 11-8
Hexocire-aluminum................................................................................................................. 11-4 11-8
Hexonitas................................................................................................................................ 11-7 11-14
Hexonite................................................................................................................................. 11-9 11-17
Hexotol................................................................................................................................... 11-8 11-15
Hexotonal................................................................................................................................ 11-8 11-15
High blast explosives
Brisance............................................................................................................................ 8-6 8-125
Characteristics.................................................................................................................. 8-6 8 -125
Destruction ....................................................................................................................... 15-3 1-1
Manufacture...................................................................................................................... 8-6 8-126
Packing............................................................................................................................. 14-2 14-1
Sensitivity......................................................................................................................... 8-6 8-125
Shipment.......................................................................................................................... 14-5 14-10
Stability............................................................................................................................. 8-6 8-125
High loading rate compression test .......................................................................................... 6-14 6-2
High performance liquid chromatography............................................................................... 13-3 13-6
HMX (see cyclotetramethylenetetranitramine)
HNAB (see hexanitroazobenzene)
HNS (see hexanitrostilbene)
Hot spots................................................................................................................................. 4-2 4-1
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Index 10
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Illustrations (Cont)
8-8. Biazzi continuous method for manufacturing nitroglycerin ........................... 8-13
8-9. Structural formula of PETN......................................................................... 8-16
8-10. Thermal decomposition of PETN................................................................ 8-23
8-11. DTA curve for PETN................................................................................... 8-24
8-12. TGA curve for PETN................................................................................... 8-25
8-13. Structural formula for TEGN....................................................................... 8-25
8-14. Structural formula for TMETN..................................................................... 8-26
8-15. Structural formula for HMX......................................................................... 8-27
8-16. DTA curve for HMX..................................................................................... 8-31
8-17. TGA curve for HMX .................................................................................... 8-32
8-18. Structurdl formula for RDX.......................................................................... 8-32
8-19. DTA curve for RDX..................................................................................... 8-36
8-20. TGA curve for RDX..................................................................................... 8-37
8-21. Structural formula for EDDN....................................................................... 8-38
8-22. Structural formula for Haleite ..................................................................... 8-39
8-23. Production of ethyleneurea........................................................................ 8-40
8-24. Boiling of dinitroethyleneurea ..................................................................... 8-41
8-25. Production of Haleite.................................................................................. 8-41
8-26. Structural formula for nitroguanidine.......................................................... 8-43
8-27. DTA curve for nitroguanidine ..................................................................... 8-46
8-28. TGA curve for nitroguanidine ..................................................................... 8-47
8-29. Structural formula for tetryl ........................................................................ 8-47
8-30. Trinitrophenyl methylamine........................................................................ 8-48
8-31. Hydrolysis of tetryl ..................................................................................... 8-48
8-32. Reaction of tetryl with aniline..................................................................... 8-49
8-33. Homologs and analogs of tetryl.................................................................. 8-49
8-34. Nitration and hydrolysis LI methylaniline.................................................... 8-50
8-35. Benzidine derivatives during tetr yl manufacture ......................................... 8-51
8-36. Deflagration to detonation transfer apparatus ............................................. 8-53
8-37. Effects of compaction on predetonation column length in tetryl .................. 8-54
8-38. Kinetic gas-evolution curves in the decomposition of tetryl .......................... 8-54
8-39. DTA curve for tetryl .................................................................................... 8-56
8-40. TGA curve for tetryl ................................................................................... 8-57
8-41. Structural formula for ammonium picrate................................................... 8-57
8-42. DTA curve for ammonium picrale .............................................................. 8-60
8-43. Structural formula for DATB........................................................................ 8-61
8-44. DTA curve for DATB................................................................................... 8-63
8-45. Structural formula for HNAB ...................................................................... 8-64
8-46. DTA curve for HNAB................................................................................... 8-64
8-47. Structural formula for HNS.......................................................................... 8-65
8-48. DTA curve for HNS..................................................................................... 8-68
8-49. TGA curve for HNS..................................................................................... 8-69
8-50. Structural formula for TATB........................................................................ 8-69
8-51. Configuration of TATB molecule................................................................. 8-69
8-52. SUSAN lest results for TATB ..................................................................... 8-72
8-53. DTA curve for TATB ................................................................................... 8-73
8-54. Structural formula for TNT.......................................................................... 8-75
8-55. White compound ........................................................................................ 8-78
8-56. TNT and 2,4.5-TNT reaction....................................................................... 8-78
8-57. Reaction of TNT with nitrosylchloride......................................................... 8-79
8-58. Reaction between TNT andphthalic anhydride .......................................... 8-79
8-59. Reduction of TNT with sodium borohydride................................................. 8-79
Index 11
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Illustrations (Cont)
8-60. Seven member ring structure..................................................................... 8-80
8-61. Reaction of TNT with hydrogen.................................................................. 8-80
8-62. Production of TATB from TNT.................................................................... 8-80
8-63. Reaction of TNT with bases ....................................................................... 8-81
8-64. Reaction of TNT with potassium hydroxide................................................ 8-81
8-65. Reaction of TNT with phenylhydrazine........................................................ 8-82
8-66. Agitation versus MNT yield ........................................................................ 8-84
8-67. SUSAN test results for TNT ....................................................................... 8-88
8-68. DTA curve for TNT .................................................................................... 8-90
8-69. TGA curve for TNT ..................................................................................... 8-91
8-70. 4,6-Dinitroanthronil..................................................................................... 8-91
8-71. Explosive coke azoxy compound ................................................................ 8-91
8-72. Photoexcitation of TNT............................................................................... 8-92
8-73. Structural formula for ammonium nitrate.................................................... 8-93
8-74. DTA curve for ammonium nitrate............................................................... 8-96
8-75. TGA curve for ammonium nitrate............................................................... 8-97
8-76. DTA curve for 80/20 amatol ....................................................................... 8-99
8-77. DTA curve for composition A ..................................................................... 8-101
8-78. DTA curve for composition A3 ................................................................... 8-102
8-79. SUSAN test results for composition B3 ...................................................... 8-106
8-80. SUSAN test results for 75/25 cyclotol......................................................... 8-106
8-81. DTA curve for composition B ..................................................................... 8-107
8-82. DTA curve for 75/25 cyclotol...................................................................... 8-108
8-83. TGA curve for composition B ..................................................................... 8-109
8-84. DTA curve for composition C3 ................................................................... 8-110
8-85. SUSAN test results for LX-14...................................................................... 8-113
8-86. DTA curve for LX- 14 ................................................................................. 8-113
8-87. SUSAN test results for 75/25 octol ............................................................. 8-117
8-88. DTA curve for 75/25 octol .......................................................................... 8-118
8-89. DTA curve for pentolite .............................................................................. 8-120
8-90. DTA curve for H6........................................................................................ 8-127
8-91. Injection molding process........................................................................... 8-131
8-92. DTA curve for PBXN-5 ............................................................................... 8-132
9-1. Typical shapes of propellant grains ................................
. ........................... 9-5
9-2. Web thickness and direction of burning through a progressively
burning grain .............................................................................................. 9-6
9-3. Pressure travel curves for a projectile in a gun........................................... 9-9
9-4. Akardits ...................................................................................................... 9-12
12-1 Deleted
12-2. Deleted ......................................................................................................
12-3. Deleted ......................................................................................................
13-1. Gas chrornatograph output......................................................................... 13-6
14-1. Steel box for packing solid propellants, including marking ........................... 14-1
14-2. Metal lined wood box for packing solid propellants. including
markings..................................................................................................... 14-2
14-3. Metal containers for propelling charges, including marking.......................... 14-3
14-4. Palletized large caliber high explosive projectiles, including
marking ...................................................................................................... 14-3
14-5. Palletized wood boxes containing explosives .............................................. 14-4
14-6. Carton for packing high explosives, including marking ................................ 14-4
14-7. Wood box for packing high explosives, including marking ........................... 14-5
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Impact sensitivity ................................................................................................................... 3-5 3-4
Impact sensitivity test:
Explosives ....................................................................................................................... 5-3 5-2
Propellants ....................................................................................................................... 6-13 6-2
Impetus .................................................................................................................................. 9-10 9-10
Impulse, blast ......................................................................................................................... 4-6 4-12
Incendiaries ............................................................................................................................ 3-4,10-1 3-3,10-4
Infrared spectroscopy ............................................................................................................. 13-5 13-8
Infrared spectroscopy, pyrotechnics ....................................................................................... 10-4 10-12
Initiating explosives, destruction of......................................................................................... 15-3 15-7
Initiation ................................................................................................................................. 4-2 4-1
Initiator ................................................................................................................................... 3-4, 1-1 3-2, 10-6
Interior ballistics ..................................................................................................................... 9-10 9-8
Italian dynamites .................................................................................................................... 11-4 11-5
Italian energetic material........................................................................................................ 11-4 11-4
Japanese energetic materials................................................................................................. 11-5 11-9
Jolt test .................................................................................................................................. 5-12 5-7
Jurrmble test .......................................................................................................................... 5-13 5-7
Jump equations ...................................................................................................................... 4-5 4-6
KDNBF (see potassium dinitrobenzofuroxane)
Ki (potassium iodide) test ....................................................................................................... 3-5 3-5
Kokushokuyaku ...................................................................................................................... 11-5 11-9
LANL large scale gap test ...................................................................................................... 5-8 5-7
LANL small scale gap test ...................................................................................................... 5-8 5-7
Lead azide
Brisance ........................................................................................................................... 7-2 7-5
Characteristics ................................................................................................................. 7-2 7-1
Destruction ...................................................................................................................... 15-4 15-8
History ............................................................................................................................. 2-7 2-9
Manufacture ..................................................................................................................... 7-2 7-3
Packing ............................................................................................................................ 14-2 14-1
Sensitivity ........................................................................................................................ 7-2 7-4
Shipment ......................................................................................................................... 14-5 14-10
Specification .................................................................................................................... 7-2 7-4
Stability ............................................................................................................................ 7-2 7-5
Toxicity ............................................................................................................................ 12-2 12-1
Types ............................................................................................................................... 7-2 7-3
Lead mononitroresorcinate
Characteristics.................................................................................................................. 7-8 7-1,7
Destruction ....................................................................................................................... 15-3 15-1
Manufacture...................................................................................................................... 7-8 7-18
Packing ............................................................................................................................ 14-2 14-1
Shipment ......................................................................................................................... 14-5 14-10
Specification..................................................................................................................... 7-8 7-18
Lead styphnate
Brisance............................................................................................................................ 7-5 7-13
Characteristics.................................................................................................................. 7-5 7-11
Destruction ....................................................................................................................... 15-3 15-1
History ............................................................................................................................. 2-7 2-9
Manufacture...................................................................................................................... 7-5 7-12
Packing ............................................................................................................................ 14-2 14-1
Reactivity ......................................................................................................................... 7-5 7-1
Sensitivity......................................................................................................................... 7-5 7-13
Shipment ......................................................................................................................... 1 4-5 14-10
Specification..................................................................................................................... 7-5 7-12, 7-13
Stability............................................................................................................................. 7-5 7-13
Types ............................................................................................................................... 7-5 7-1
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Index 14 Change 3
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Change 3 Index 15
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Index 16 Change 3
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9-5 9-3
Single fragment impact test, propellant.................................................................................. 6-22 6-4
Skid tests................................................................................................................................ 5-18 5-9
SLA (see lead azide)
Slurry explosives, Russian ..................................................................................................... 11-6 11-13
Smoke .................................................................................................................................... 2-2, 2-7 2-1, 2-10
Smoke dyes............................................................................................................................ 10-1 10-1
Spanish 'energetic materials................................................................................................... 11-7 11-13
Spectrometry.......................................................................................................................... 13-5 13-7
Spectroscopy.......................................................................................................................... 13-5 13-7
Sprangdeg.............................................................................................................................. 11-8 11-16
Index 18 Change 3
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Change 3 Index 19
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Tables (Cont)
8-22. Haleite packing density..................................................................... 8-39
8-23. Solubility of nitroguanidine in sulfuric acid........................................ 8-42
8-24. Gap test results for nitroguanidine..................................................... 8-45
8-25. Density as a function of loading pressure for tetryl............................ 8-45
8-26. Dielectric constant of tetryl................................................................ 8-47
8-27. Solubility of tetryl in various solvents................................................ 8-48
8-28. Heat initiation of tetryl....................................................................... 8-51
8-29. Heat initiation of confined tetryl......................................................... 8-51
8-30. Gap test results for tetryl.................................................................... 8-52
8-31. Low velocity detonation in tetryl ......................................................... 8-53
8-32. Composition of gaseous products of tetryl decompositi on.................. 8-54
8-33. Composition of condensed phase tetryl............................................. 8-55
8-34. Density of ammonium picrate............................................................ 8-55
8-35. Solubility of ammonium picrate.......................................................... 8-57
8-36. Ammonium picrate explosion temperature ......................................... 8-58
8-37. Gap test results for DATB.................................................................. 8-60
8-38. Gap test results for HNAB.................................................................. 8-61
8-39. Properties of HNS.............................................................................. 8-65
8-40. Gap test results for HNS ................................................................... 8-66
8-41. Solubility of TATB in various solvents................................................ 8-66
8-42. Effects of gamma radiation on TATB................................................. 8-67
8-43. Small scale gap test results for TATB................................................ 8-71
8-44. Detonation characteristics of TATB.................................................... 8-72
8-45. Effects of moisture on the freezing point of TNT............................... 8-74
8-46. Removal of moisture from TNT......................................................... 8-74
8-47. Density as a function of loading pressure for TNT .............................. 8-74
8-48. Surface tension of liquid TNT............................................................ 8-75
8-49. Dielectric constant of TNT ................................................................ 8-75
8-50. Solubility of TNT ............................................................................... 8-75
8-51. Specific heat, enthalpy, and entropy of TNT..................................... 8-76
8-52. Thermal diffusivity of TNT ................................................................ 8-76
8-53. Isomers of TNT ................................................................................. 8-83
8-54. Nitrobody concentration for a six nitrator system ............................... 8-84
8-55. Impurities present in TNT.................................................................. 8-85
8-56. Impact sensitivity of TNT .................................................................. 8-87
8-57. Gap test results for TNT.................................................................... 8-87
8-58. Detonation pressure of TNT.............................................................. 8-88
8-59. Fragmentation effects of TNT............................................................ 8-88
8-60. Effects of confinement on TNT detonation products ........................... 8-89
8-61. Crystal modifications of ammonium nitrate....................................... 8-92
8-62. Specific heat of ammonium nitrate................................................... 8-93
8-63. Properties of amatols........................................................................ 8-97
8-64. Detonation characteristics of amatols............................................... 8-98
8-65. Composition A explosives................................................................. 8-100
8-66. Cyclotol properties ............................................................................ 8-103
8-67. Gap test results for composition B..................................................... 8-105
8-68. Detonation characteristics of composition C explosives ..................... 8-111
8-69. Properties of octols............................................................................ 8-114
8-70. Crater volume in mild steel targets................................................... 8-116
8-71. Gap tests for 75/25 octol.................................................................... 8-116
8-72. Gap test results for 50/50 pentolite................................................... 8-119
8-73. General characteristics of tetrytols.................................................... 8-122
8-74. High blast explosives........................................................................ 8-125
8-75. HTA-3 composition ........................................................................... 8-126
8-76. PBX compositions.............................................................................. 8-131
8-77. Compositions and characteristics of dynam ites ................................. 8-133
Index 20
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Tables (Cont)
9-1. Distribution of propellant energy....................................................... 9-1
9-2. Composition and properties of propellants ......................................... 9-1
9-3. Burning rate parameters for several standard gun propellants ........... 9-7
10-1. Infrared flare formulas ...................................................................... 10-2
10-2. Red-green flare s) item parts weight.................................................. 10-2
10-3. Amount of smoke agent per cubic meter of standard smoke .............. 10-3
10-4. Typical formulas for igniter and tracer compositions.......................... 10-4
10-5. Properties of pyrophoric metals........................................................ 10-5
10-6. Maximum volumetric heats of reaction for metals reacting with
fluorocarbons .................................................................................... 10-5
10-7. Delay compositions........................................................................... 10-6
10-8. Black powders used in pyrotechnics................................................... 10-7
10-9. Ignition mixtures ............................................................................... 10-7
11-1. French secondary explosives............................................................ 11-1
11-2. French chlorate cheddites.................................................................. 11-2
11-3. French perchlorate cheddites............................................................ 11-3
11-4. CSE silicon explosives ..................................................................... 11-3
11-5. German secondary explosives.......................................................... 11-4
11-6. Italian explosives .............................................................................. 11-4
11-7. Esplosivi da mina gelatinosi con nitroglicerina.................................. 11-6
11-8. Esplosivi da mina polverulenti con nilroglicerina............................... 11-7
11-9. Esplosivi da mina polverulenti senza nitroglicerina ............................ 11-7
11-10. Japanese explosives ........................................................................ 11-9
11-11. Russian explosives............................................................................ 11-10
11-12. Some ammonits formulations........................................................... 11-11
11-13. Russian brown powders .................................................................... 11-12
11-14. Russian black powders ..................................................................... 11-12
11-15. Detonity ............................................................................................ 11-12
11-16. Granulity ........................................................................................... 11-13
11-17. Spanish explosives............................................................................ 11-13
11-18. Spanish artigrisu explosives ............................................................. 11-14
11-19. Swedish explosives .......................................................................... 11-15
11-20. Hexotonal ......................................................................................... 11-15
11-21. Swiss explosives............................................................................... 11-16
11-22. Ammonpentrinits............................................................................... 11-16
11-23. Penthrinits ........................................................................................ 11-17
12-1. Toxicity of United States
Military Explosives.............................................................................. 12-1
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Tables (Cont)
12-15. Deleted
12-16. Deleted
12-17. Deleted
12-18. Deleted
12-19. Deleted
12-20. Deleted
12-21. Deleted
13-1. Colortests ......................................................................................... 13-1
13-2. Special correlations of aromatic nitro compounds, nitramines, and
nitrates ............................................................................................. 13-8
14-1. Special requirements for open storage between earth covered
magazines ........................................................................................ 14-8
14-2. Special requirements for open storage between magazines that are
not earth covered.............................................................................. 14-9
15-1. Minimum safe distance between RF transmitters and electric blasting
operations ......................................................................................... 15-5
15-2. Minimum safe distances between mobile RF transmitters and electric
blasting operations............................................................................ 15-5
15-3. Minimum safe distance between TV and FM broadcasting transmit-
ters and electric blasting operations.................................................. 15-6
15-4. Decontaminating chemicals.............................................................. 15-9
15-5. High explosive reclamation............................................................... 15-12
15-6. Propellant reclamation...................................................................... 15-14
15-7. Pyrotechnic reclamation ................................................................... 15-15
Taliani test ............................................................................................................................. 6-16 6-3
TATB (see triamino-trinilrobenzene)
TEGN (see triethylene glycoldinitrate)
Temperature and humidity test............................................................................................... 5-11 5-7
Territ ...................................................................................................................................... 11-8 11-16
Test
90°C Dulch weight loss .................................................................................................... 6-19 6-3
Adiabatic sensitivity ......................................................................................................... 5-19 5-9
Ballistic mortar ................................................................................................................. 3-5 3-4
Ballistic pendulum ............................................................................................................ 3-5 3-4
Cap test ........................................................................................................................... 6-10 6-2
Card gap test ................................................................................................................... 6-9 6-2
Closed bomb test, propellants.......................................................................................... 6-7 6-1
Compatibility, propellants................................................................................................. 6-2 6-1
Cook-off temperature test ................................................................................................ 5-6 5-5
Cylinder expansion lest.................................................................................................... 5-21 5-9
Dellagration to detonation transition, propellants .............................................................. 6-4 6-1
Detonation velocity test.................................................................................................... 5-5 5-3
Development ................................................................................................................... 10-3 10-9
Dilfferential thermal analysis............................................................................................ 3.5 3-5
Electrostatic sensitivity..................................................................................................... 3-5, 5-4, 3-4, 5-3,
......................................................................................................................................... 6-11 6-2
Evaluation ........................................................................................................................ 10-3 10-9
External heat test. propellants ........................................................................................... 6-3 6-1
Explosion temperature..................................................................................................... 6-17 6-3
Flying plate test ............................................................................................................... 5-9 5-7
Forty foot drop test........................................................................................................... 5-14 5-8
Fragmentation lest ........................................................................................................... 5-20 5-9
Friction sensitivity ............................................................................................................ 5-7, 6-12 5-5, 6-2
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Test (cont)
Gap tests.......................................................................................................................... 5-8 5-7
Growth and exudation test............................................................................................... 5-15 5-8
Heat, 100°C and 75°C....................................................................................................... 3-5 3-5
Heat tests, propellants, 134.5°C and 120°C..................................................................... 6-5 6-1
High loading rate compression test.................................................................................. 6-14 6-2
Impact sensitivity ............................................................................................................. 3-5 3-4, 5-2,
......................................................................................................................................... 6-13 6-2
Incendiary heat output....................................................................................................... 10-3 10-11
Jolt test............................................................................................................................. 512 5-7
Jumble test....................................................................................................................... 5-13 5-7
KI (potassium iodide)........................................................................................................ 3-5 3-5
LANL large scale gap test................................................................................................. 5-8 5-7
LANL small scale gap test................................................................................................. 5-8 5-7
LLNL reactivity ................................................................................................................. 3-5 3-5
Low loading ratecompression test ................................................................................... 6-15 6-2
Malfunction....................................................................................................................... 10-3 10-9
Multiple fragment impact test, propellant.......................................................................... 6-23 6-4
NATO ............................................................................................................................... 10-3 10-9
NSWC small scale gap test.............................................................................................. 5-8 5-7
PX gap test....................................................................................................................... 5-8 5-7
Pyrolysis........................................................................................................................... 3-5 3-5
Pyrotechnic light output..................................................................................................... 10-3 10-9
Pyrotechnic smoke output................................................................................................. 10-3 10-10
Rifle bullet impact test...................................................................................................... 5-16 5-3
Service............................................................................................................................. 10-3 1 0-9
Shaped charge jet impact test, propellant........................................................................ 6-20 6-4
Shaped charge jet spall test, propellant............................................................................ 6-21 6-4
Shock sensitivity............................................................................................................... 3-5 3-4
Single fragment impact test, propellant............................................................................ 6-22 6-4
Skid tests.......................................................................................................................... 5-18 5-9
Strand burner test............................................................................................................. 6-18 6-3
Surveillance...................................................................................................................... 10-3 10-9
Surveillance test............................................................................................................... 6-8 6-2
SUSAN test ...................................................................................................................... 5-17 5-8
Taliani test........................................................................................................................ 5-16 6-3
Temperature and humidity test .......................................................................................... 5-11 5-7
Thermal sensitivity............................................................................................................ 3-5, 5-8 3-4, 5-7
Thermal gravimetric analysis............................................................................................ 3-5 3-5
Transport vibration test .................................................................................................... 5-10 5-7
Trauzl lead block test........................................................................................................ 3-5 3-4
Vacuum stability............................................................................................................... 3-5, 5-2, 3-5, 5-2,
......................................................................................................................................... 6-6 6-1
Tetracene
Brisance ........................................................................................................................... 7-6 7-16
Characteristics ................................................................................................................. 7-6 7-15
Destruction ....................................................................................................................... 15-3 15-1
History ............................................................................................................................. 2-7 2-9
Manufacture ..................................................................................................................... 7-6 7-15
Packing ............................................................................................................................ 14-2 14-1
Reactivity ......................................................................................................................... 7-6 7-16
Sensitivity ........................................................................................................................ 7-6 7-16
Shipment ......................................................................................................................... 14-5 14-10
Specification .................................................................................................................... 7-6 7-16
Stability ............................................................................................................................ 7-6 7-16
Tetritol ................................................................................................................................... 11-7 11-14
Tetritoly................................................................................................................................... 11-6 11-13
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Tetryl (see trinitrophenylmelhylnilramine)
Tetrytols
Brisance ........................................................................................................................... 8-6 8-122
Characteristics ................................................................................................................. 8-6 8-121
Destruction ...................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-6 8-121
Packing ............................................................................................................................ 14-2 14-1
Reactivity ......................................................................................................................... 8-6 8-122
Sensitivity ........................................................................................................................ 8-6 8-122
Shipment ......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-122
Toxicity ............................................................................................................................ 12-2 12-3
Thermal conductimetric analysis ............................................................................................ 10-4 10-12
Thermal gravimetric analysis ................................................................................................. 3-5 3-5
Thermal sensitivity ................................................................................................................. 3-5 3-4
Thermochemistry, propellants ................................................................................................ 9-3 9-2
Thermogravimetry, pyrotechnics............................................................................................ 10-4 10-12
Thin layer chromatography..................................................................................................... 13-3 13-4
TMETN (see trimetholethane trinitrate)
TNT (see trinitrototuene)
Tontia ..................................................................................................................................... 11-7 11-14
Torpex
Brisance ........................................................................................................................... 8-6 8-129
Characteristics ................................................................................................................. 8-6 8-128
Destruction ...................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-6 8-128
Packing ............................................................................................................................ 14-2 14-1
Sensitivity ........................................................................................................................ 8-6 8-123
Shipment ......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-129
Toxicity ............................................................................................................................ 12-2 12-4
Totalit ..................................................................................................................................... 11-9 11-17
Toxicity .................................................................................................................................. 12-2 12-1
Tracers ................................................................................................................................... 3-4, 101 3-1, 10-4
Tramex .................................................................................................................................. 11-9 11-17
Transport vibration test .......................................................................................................... 5-10 5-7
Trauzl lead block test ............................................................................................................. 3-5 3-4
Triamino-trinitrobenzene
Brisance ........................................................................................................................... 8-4 8-72
Characteristics ................................................................................................................. 8-4 8-66
Destruction ...................................................................................................................... 15-3 15-1
Manufacture ..................................................................................................................... 8-4 8-70
Packing ............................................................................................................................ 14-2 14-1
Sensitivity ........................................................................................................................ 8-4 8-71
Shipment ......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-4 8-72
Triethylene glycoldinitrate
Brisance ........................................................................................................................... 8-2 8-26
Characteristics ................................................................................................................. 8-2 8-22
Index 24 Change 3
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Triethylene glycoldinitrate (Cont)
Destruction ....................................................................................................................... 15-3 15-1
Manufacture...................................................................................................................... 8-2 8-25
Packing............................................................................................................................. 14-2 14-1
Reactivity.......................................................................................................................... 8-2 8-22
Sensitivity......................................................................................................................... 8-2 8-26
Shipment.......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-2 8-26
Trimethylolethane trinitrate
Brisance............................................................................................................................ 8-2 8-26
Characteristics.................................................................................................................. 8-2 8-26
Destruction ....................................................................................................................... 15-3 15-1
Manufacture...................................................................................................................... 8-2 8-26
Packing............................................................................................................................. 14-2 14-1
Reactivity.......................................................................................................................... 8-2 8-26
Sensitivity......................................................................................................................... 8-2 8-26
Shipment.......................................................................................................................... 14-5 14-10
Stability............................................................................................................................. 8-2 8-27
Trinitrophenylmethylnitramine
Brisance............................................................................................................................ 8-3 8-52
Characteristics .................................................................................................................. 8-3 8-45
Destruction ....................................................................................................................... 15-3 15-1
History .............................................................................................................................. 2-6 2-7
Manufacture...................................................................................................................... 8-3 8-49
Packing............................................................................................................................. 14-2 14-1
Reactivity.......................................................................................................................... 8-3 8-48
Sensitivity......................................................................................................................... 8-3 8-51
Shipment.......................................................................................................................... 14-5 14-10
Stability............................................................................................................................. 8-3 8-55
Toxicity............................................................................................................................. 12-2 12-1
Trinitrotoluene
Brisance............................................................................................................................ 8-4 8-88
Characteristics.................................................................................................................. 8-4 8-72
Destruction ....................................................................................................................... 1-3 15-1
History .............................................................................................................................. 2-6, 2-7 2-6, 2-8
Manufacture...................................................................................................................... 8-4 8-83
Packing............................................................................................................................. 14-2 14-1
Reactivity.......................................................................................................................... 8-4 8-77
Sensitivity......................................................................................................................... 8-4 8-87
Shipment.......................................................................................................................... 14-5 14-10
Specification..................................................................................................................... 8-4 8-86
Stability............................................................................................................................. 8-4 8-89
Toxicity............................................................................................................................. 12-2 12-3
Triplastita................................................................................................................................ 11-7 11-14
Triple-base propellant.............................................................................................................. 3-4, 9-2, 3-2, 9-2,
......................................................................................................................................... 9-5 9-4
Tritolita.................................................................................................................................... 11-7 11-14
Tritolital .................................................................................................................................. 11-7 11-14
Tritonal
Brisance ........................................................................................................................... 8-6 8-123
Characteristics ................................................................................................................. 8-6 8-123
Destruction ...................................................................................................................... 5-3 15-1
Manufacture ..................................................................................................................... 8-6 8-123
Packing............................................................................................................................. 14-2 14-1
Reactivity ......................................................................................................................... 8-6 8-123
Sensitivity ........................................................................................................................ 8-6 8-123
Change 3 Index 25
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Tritonal (Cont)
Shipment.......................................................................................................................... 14-5 14-10
Stability ............................................................................................................................ 8-6 8-123
Toxicity ............................................................................................................................ 12-2 12-4
Uglenity ........................................................................................................................... 11-6 11-13
Ultraviolet spectroscopy.......................................................................................................... 13-5 13-7
Umbrite .................................................................................................................................. 11-4 11-9
Vacuum stability test
Definition ......................................................................................................................... 3-5 3-5
Explosives ....................................................................................................................... 5-2 5-2
Propellants ....................................................................................................................... 6-6 6-1
Visible spectroscopy ............................................................................................................... 13-5 13-7
Waste recycling ..................................................................................................................... 15-6 15-12
Water shipment of explosives and ammunition...................................................................... 14-5 14-15
Waterproofing agents, pyrotechnic.......................................................................................... 10-1 10-1
Web ....................................................................................................................................... 9-6 9-5
Wet chemical identification methods....................................................................................... 13-2 13-1
White smoke .......................................................................................................................... 3-4, 10-1 3-3, 10-2
Zemogranoolity ...................................................................................................................... 11-6 11-13
Index 26 Change 3
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ROBERT M. JOYCE
Major General, United States Army
The Adjutant General
Distribution:
To be distributed in accordance with DA Form 12-40, Requirements for Section IV, General Information Applicable
to All Organizations Which Have a Conventional Munitions Mission.
Temperature (Exact)
PIN: 027361-000