3.4. Glasses

Glasses
3.4. Glasses
3.4.1 Properties of Glasses –

This chapter has been conceived as a source
General Comments ............................. 526
of information for scientists, engineers, and
technicians who need data and commercial- 3.4.2 Composition and Properties of Glasses . 527
product information to solve their technical task
3.4.3 Flat Glass and Hollowware .................. 528
by using glasses as engineering materials. It is not 3.4.3.1 Flat Glass ............................... 528
intended to replace the comprehensive scientific 3.4.3.2 Container Glass ....................... 529
literature. The fundamentals are merely sketched,
to provide a feeling for the unique behavior of this 3.4.4 Technical Specialty Glasses .................. 530
widely used class of materials. 3.4.4.1 Chemical Stability of Glasses ..... 530
The properties of glasses are as versatile as 3.4.4.2 Mechanical
their composition. Therefore only a selection of and Thermal Properties............ 533
3.4.4.3 Electrical Properties ................. 537
data can be listed, but their are intended to cover
3.4.4.4 Optical Properties .................... 539
the preferred glass types of practical importance.
Part 3 4
Wherever possible, formulas, for example for the 3.4.5 Optical Glasses ................................... 543
optical and thermal properties, are given with 3.4.5.1 Optical Properties .................... 543
their correct constants, which should enable the 3.4.5.2 Chemical Properties ................. 549
reader to calculate the data needed for a specific 3.4.5.3 Mechanical Properties.............. 550
situation by him/herself. 3.4.5.4 Thermal Properties .................. 556
For selected applications, the suitable glass 3.4.6 Vitreous Silica..................................... 556
types and the main instructions for their processing 3.4.6.1 Properties of Synthetic Silica..... 556
are presented. Owing to the availability of the 3.4.6.2 Gas Solubility
information, the products of Schott AG have and Molecular Diffusion ........... 557
a certain preponderance here. The properties of
3.4.7 Glass-Ceramics ................................... 558
glass types from other manufacturers have been
included whenever available. 3.4.8 Glasses for Miscellaneous Applications . 559
3.4.8.1 Sealing Glasses ....................... 559
3.4.8.2 Solder and Passivation Glasses.. 562
3.4.8.3 Colored Glasses ....................... 565
3.4.8.4 Infrared-Transmitting Glasses... 568
References .................................................. 572
Glasses are very special materials that are formed general, generic expression in comparison with the
only under suitable thermodynamic conditions; these term “glass”. Many different technological routes are
conditions may be natural or man-made. Most glass described in [4.1].
products manufactured on a commercial scale are made Glasses are also very universal engineering mater-
by quenching a mixture of oxides from the melt ials. Variation of the composition results in a huge
(Fig. 3.4-1). variety of glass types, families, or groups, and a cor-
For some particular applications, glasses are also responding variety of properties. In large compositional
made by other technologies, for example by chemical areas, the properties depend continuously on compos-
vapor deposition to achieve extreme purity, as required ition, thus allowing one to design a set of properties to
in optical fibers for communication, or by roller chilling fit a specific application. In narrow ranges, the prop-
in the case of amorphous metals, which need extremely erties depend linearly on composition; in wide ranges,
high quenching rates. The term “amorphous” is a more nonlinearity and step-function behavior have to be con-
524 Part 3 Classes of Materials
Volume
1
Q[2]
2
Glass formation
[3]
curve Q[2]
Q[3/432]
3
Q[3] Q[3]
Q[4/433] [3/432]
4 Crystallization
curve
Q[4/4333]
[4]
Tg Ts
Temperature Q[4]
Q[3] Q[4]
Fig. 3.4-1 Schematic volume–temperature curves for glass
formation along path 1–2–3 and crystallization along
path 1–4. Ts , melting temperature; Tg , transformation
temperature. 1, liquid; 2, supercooled liquid; 3, glass;
4, crystal Fig. 3.4-2 Fragment of a sodium silicate glass structure.
Part 3 4
The SiO2 tetrahedra are interconnected by the bridging

sidered. The most important engineering glasses are oxygen atoms, thus forming a three-dimensional network.
mixtures of oxide compounds. For some special require- Na2 O units form nonbridging oxygen atoms and act as
ments, for example a particular optical transmission network modifiers which break the network. The Q [i/klmn]
window or coloration, fluorides, chalcogenides, and col- nomenclature describes the connectivity of different atom
loidal (metal or semiconductor) components are also shells around a selected central atom (after [4.2])
used.
A very special glass is single-component silica, properties change with time and temperature, but in
SiO2 ,which is a technological material with extraordin- most cases at an extremely low rate which cannot be
ary properties and many important applications. observed under the conditions of classical applications
On a quasi-macroscopic scale (> 100 nm), glasses (in the range of ppm, ppb, or ppt per year at room
seem to be homogeneous and isotropic; this means that temperature). However, if the material is exposed to
all structural effects are, by definition, seen only as a higher temperature during processing or in the final
average properties. This is a consequence of the manu- application, the resulting relaxation may result in unac-
facturing process. If a melt is rapidly cooled down, there ceptable deformation or internal stresses that then limit
is not sufficient time for it to solidify into an ideal, its use.
crystalline structure. A structure with a well-defined If a glass is reheated, the quasi-solid material
short-range order (on a scale of less than 0.5 nm, to ful- softens and transforms into a liquid of medium vis-
fill the energy-driven bonding requirements of structural cosity in a continuous way. No well-defined melting
elements made up of specific atoms) [4.2] and a highly point exists. The temperature range of softening is
disturbed long-range order (on a scale of more than 2 nm, called the “transition range”. By use of standardized
disturbed by misconnecting lattice defects and a mixture measurement techniques, this imprecise characteriza-
of different structural elements) (Fig. 3.4-2). tion can be replaced by a quasi-materials constant, the
Crystallization is bypassed. We speak of a frozen-in, “transformation temperature” or “glass temperature” Tg ,
supercooled, liquid-like structure. This type of quasi- which depends on the specification of the procedure
static solid structure is thermodynamically controlled (Fig. 3.4-3).
but not in thermal equilibrium and thus is not absolutely As illustrated in Fig. 3.4-4, the continuous variation
stable; it tends to relax and slowly approach an “equi- of viscosity with temperature allows various technolo-
librium” structure (whatever this may be in a complex gies for hot forming to be applied, for example casting,
multicomponent composition, it represents a minimum floating, rolling, blowing, drawing, and pressing, all of
of the Gibbs free enthalpy). This also means that all which have a specific working point.
Glasses 525
Relative contraction ∆ l/l Nucleation rate (N) or crystal growth rate (C)
Cmax
A B C
C
Tg Nmax
0 200 400 600 800 1000

Temperature (K) Temperature
Fig. 3.4-3 Definition of the glass transition temperature Tg Fig. 3.4-5 Nucleation rate (N) and crystal growth rate (C)
by a diagram of length versus temperature during a meas- of glass as a function of temperature
urement, as the intersection of the tangents to the elastic
region B and to the liquid region to the right of C. In the Temperature (°C)
transformation range C, the glass softens 1800
Part 3 4
a
1600
lg (η /dPa s) 1400
15 10 14.5
dPa s Strain 1200 d
b
Transforma- point 1000
1013 dPa s
13 tion range Annealing
800 c
point
600 e
11 400
200
9
0
Sintering, 107.6 dPa s Softening Time
sagging point
7 Fig. 3.4-6 Temperature–time schedule for glass-ceramic
Blowing production: a, melting; b, working; c, nucleation; d, crys-
5 tallization; e, cooling to room temperature
104 dPa s Working
Pressing, point
3 drawing colored glasses with colloidal inclusions, porous glasses,
Melting, and glass-ceramics, to name just a few.
casting The commercially important glass-ceramics consist
1
0 200 600 1000 1400 1800 of a mixture of 30–90% crystallites (< 50 nm in diam-
Temperature (°C)
eter) and a residual glass phase, without any voids. The
Fig. 3.4-4 Typical viscosity–temperature curve: viscosity material is melted and hot-formed as a glass, cooled
ranges for the important processing technologies, and def- down, then annealed for nucleation, and finally tempered
initions of fixed viscosity points to allow crystal growth to a percentage that depends
on the desired properties [4.3, 4]. Some characteris-
The liquid-like situation results in thermodynam- tic features of the manufacturing process are shown in
ically induced density and concentration fluctuations, Figs. 3.4-5 and 3.4-6. As the melt is cooled, a region of
with a tendency toward phase separation and crystal- high velocity of crystal growth has to be passed through,
lization, which starts via a nucleation step. This can also but no nuclei exist in that region. The nuclei are formed
be used as a technological route to produce unconven- at a much lower temperature, where the crystallization is
tional, i. e. inhomogeneous, glasses. Some examples are slow again. Thus the material solidifies as a glass in the
first process step. In a second process step, the glass is overall bulk properties are the averages of the proper-
reheated, annealed in the range of maximum nucleation ties of the components. One of the major properties of
rate Nmax , and then annealed at a higher temperature in commercially important glass-ceramics is a near-zero
the range of maximum crystal growth rate Cmax . The coefficient of thermal expansion.
3.4.1 Properties of Glasses – General Comments

As for all materials, there are many properties for every 4. Vitreous silica, as a single-component material, has
type of glass described in the literature. In this section some extraordinary properties: high transparency
only a limited selection can be given. We also restrict from 160 nm to 1800 nm wavelength, high elec-
the presentation to commercially important glasses and trical insulation if it is of low hydrogen content,
glass-ceramics. For the huge variety of glasses that have high chemical and corrosion resistance, and quite
been manufactured for scientific purposes only, the orig- low thermal expansion with high thermal-shock re-
inal literature must be consulted. Extensive compilations sistance. A technological handicap is the high glass
of data of all kind may be found in books, e.g. [4.5–7], temperature Tg ≈ 1250 ◦ C, depending on the water
and in software packages [4.8, 9], which are based upon content.
these books and/or additional original data from lit- 5. Glass-ceramics are glassy in the first production
erature, patents, and information from manufacturers step. An important property is the final (after cer-
Part 3 4.1
worldwide. amization) coefficient of thermal expansion, often

Almost all commercially important glasses are in combination with a high elastic modulus and low
silicate-based. For practical reasons, these glasses are specific weight. High thermal stability and thermal-
subdivided into five major groups which focus on special shock resistance are a prerequisite for the major
properties. These groups are: applications. This group has the potential for many
other applications which require different property
1. Mass-production glasses, such as window and con-
combinations [4.3].
tainer glasses, which are soda–lime–silicate glasses.
Besides the application-dependant properties such as This separation into groups seems to be somewhat
transparency, chemical resistance, and mechanical artificial, in view of the material properties alone, and
strength, the main concern is cost. is justified only by the very different technological
2. Technical specialty glasses, such as display or tele- conditions used for manufacturing and processing. It
vision glasses, glasses for tubes for pharmaceutical corresponds to the specialization of the industry and to
packaging, glasses for industrial ware and labware, a traditional structuring in the literature.
glasses for metal-to-glass sealing and soldering, and For all these groups, various classes of product de-
glasses for glassware for consumers. The dominant fects exist, and these defects may occur in varying
properties are chemical inertness and corrosion re- concentration. Among these defects may be bubbles,
sistance, electrical insulation, mechanical strength, striations, crystalline inclusions, and metal particles,
shielding of X-ray or UV radiation, and others. To which are relics of a nonideal manufacturing process.
fulfill these specifications, the glass composition There may also be inclusions of foreign components
may be complex and even contain rare components. which were introduced with the raw materials as impur-
3. Optical glasses have the greatest variety of chem- ities or contamination. If a three-dimensional volume
ical components and do not exclude even the most of glass is cooled down, the finite heat conductivity
exotic materials, such as rare earth and non-oxide causes the volume elements to have nonidentical his-
compounds. The dominant properties are of optical tories in time and temperature. As a consequence, the
origin: refraction and dispersion with extremely time- and temperature-dependent relaxation processes
high homogeneity, combined with low absorption produce internal mechanical stress, which results in
and light scattering within an extended transmission optical birefringence. These “technical” properties are
range, including the infrared and ultraviolet parts of often very important for the suitability of a piece of
the electromagnetic spectrum. They are produced in glass for a specific application, but they are not “intrin-
comparably small volumes but with raw materials of sic” properties of the material, and are not considered in
high purity, and are thus quite expensive. this section.
Glasses 4.2 Composition and Properties of Glasses 527
3.4.2 Composition and Properties of Glasses

A very common method for describing the composition If components other than oxides are used, it is
of a glass is to quote the content of each component advantageous to define fictitious components, for ex-
(oxide) by weight fraction (wi in wt%) or mole fraction ample the component F2 −O ( = fluorine–oxygen,
(m i in mol%). If Mi is the molar mass of the compo- with M = 2 × 19 − 16 = 22); this can be used to
nent i, the relationship between the two quantities is replace a fluoride with an oxide and this hypothet-
given by ical oxide component, for example CaF2 = CaO +
100wi F2 −O. This reduces the amount of data required
mi = n , 1≤i ≤n, (4.1)
Mi j=1 w j /M j
Table 3.4-1 Factors wi for the calculation of glass dens-
and ities [4.10]
100m i Mi Component i wi (g/cm3 )
wi = n , 1≤i ≤n, (4.2)
j=1 m j M j Na2 O 3.47
with the side conditions MgO 3.38
n
n
CaO 5.0
m i = 1 and wi = 1 . (4.3)
Al2 O3 2.75
i=1 i=1
SiO2 2.20
Part 3 4.2
a) 1a 2a 3b 4b 5b 6b 7b 8 1b 2b 3a 4a 5a 6a 7a 0 b) 1a 2a 3b 4b 5b 6b 7b 8 1b 2b 3a 4a 5a 6a 7a 0
H He H He
Li Be B C N O F Ne Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co N Cu Zn Ga Ge As Se Br Kr K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Rb Rb Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Te Pb Bi Po At Rn Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Te Pb Bi Po At Rn
Fig. 3.4-7 (a) Elements whose oxides act as glass-formers (gray) and conditional glass-formers (brown) in oxide systems (af-
ter [4.11]). (b) Elements whose fluorides act as glass-formers (gray) and conditional glass-formers (brown) in fluoride glass
systems (after [4.12])
Table 3.4-2 Composition of selected technical glasses
Glass type Code a Main components (wt%) Minor components

SiO2 B2 O3 Al2 O3 Na2 O PbO < 10%
Lead glass S 8095 57 28 Al2 O3 , Na2 O, K2 O

Low dielectric loss glass S 8248 70 27 Al2 O3 , Li2 O, Na2 O, K2 O, BaO
Sealing glass S 8250 69 19 Al2 O3 , Li2 O, Na2 O, K2 O, ZnO
Duran® S 8330 80 13 Al2 O3 , Na2 O, K2 O
Supremax® S 8409 52 22 B2 O3 , CaO, MgO, BaO, P2 O5
Sealing glass S 8465 11 11 75 SiO2
Sealing glass S 8487 75 16.5 Al2 O3 , Na2 O, K2 O
VycorTM C 7900 96 Al2 O3 , B2 O3 , Na2 O
a Code prefix: S = Schott AG, Mainz; C = Corning, New York.
to handle the different cation–anion combinations The component-specific factors pi were first systemat-
(Fig. 3.4-7). ically determined by Winckelmann and Schott [4.13],
With given weight or mole fractions, a property P and are listed in detail in the standard literature,
can be calculated (or approximated) via a linear relation e.g. [4.14].
of the type As an example, the density can be calculated
via (4.4) from: P = 1/, pwi = 1/wi , and the data in
1 1
n n
P= pwi wi or P= pm i m i . Table 3.4-1.
100 100 The composition of selected technical glasses is
i=1 i=1
(4.4) given in Table 3.4-2.
3.4.3 Flat Glass and Hollowware

By far the highest glass volume produced is for windows 3.4.3.1 Flat Glass
and containers. The base glass is a soda–lime compos-
ition, which may be modified for special applications. Plate glass for windows is mainly produced by float-
Owing to the Fe content of the natural raw materials, ing the melt on a bath of molten tin. All manufacturers
a green tint is observed for thicknesses that are not too worldwide use a soda–lime-type glass, with the aver-
small. age composition given in Table 3.4-3. For some other
If the product is designed to have a brown or green applications, this base glass may be modified by added
Part 3 4.3
color (obtained by the use of reducing or oxidizing melt- coloring agents, for example Cr and Fe oxides.
ing conditions), up to 80% waste glass can be used as For architectural applications, the surface(s) may be
a raw material. modified by coatings or grinding to achieve specific
Table 3.4-3 Average composition in wt% and viscosity data, for soda–lime glass, container glass, and Borofloat glass
Soda–lime glass Container glass Borofloat® 33
Composition (wt%)
SiO2 71–73 71–75 81
CaO + MgO 9.5–13.5 10–15
Na2 O + K2 O 13–16 12–16 4
B2 O3 0–1.5 13
Al2 O3 0.5–3.5 2
Other 0–3 0–3
Temperature (◦ C)
at viscosity of 1014.5 dPa s 518
at viscosity of 1013 dPa s 525–545 560
at viscosity of 107.6 dPa s 717–735 820
at viscosity of 104 dPa s 1015–1045 1270
Density (g/cm3 ) 2.5 2.2
Young’s modulus (GPa) 72 64
Poisson’s ratio 0.2
Knoop hardness 480
Bending strength (MPa) 30 25
Thermal expansion coefficient α,
20–300 ◦ C (10−6 /K) 9.0 3.25
Specific heat capacity c p ,
20–100 ◦ C (kJ/kg K) 0.83
Glasses 4.3 Flat Glass and Hollowware 529
Table 3.4-3 Average composition in wt% and viscosity data for soda–lime glass, cont.
Soda–lime glass Container glass Borofloat® 33

Heat conductivity λ at 90 ◦ C
(W/m kg) 1.2
Chemical resistance
Water HGB1/HGA1
Acid 1
Alkali A2
Refractive index n d 1.47140
Abbe value νe 65.41
Stress-optical constant K
(10−6 mm2 /N) 4.0
Dielectric constant εr 4.6
Dielectric loss tan δ
at 25 ◦ C, 1 MHz 37 × 10−4
Volume resistivity ρ
Part 3 4.3
at 250 ◦ C (Ω cm) 108
at 350 ◦ C (Ω cm) 106.5
optical effects, such as decorative effects, a higher re- Windshields are preferably made of laminated com-
flectivity in certain spectral regions (e.g. the IR), or an pound glass. Here, two (or more) layers are joined under
opaque but translucent appearance. Some other applica- pressure with a tough plastic foil.
tions require antireflection coatings. The compound technique is also used for armor-
If steel wires are embedded as a web into rolled plate glass: here, at least four laminated glass layers
glass, the resulting product can be used as a window with a total thickness of at least 60 mm are used.
glass for areas where improved break-in protection is For plasma and LCD displays and photovoltaic sub-
required. strates, extremely smooth, planar, and thin sheets of
Fire-protecting glasses are designed to withstand glass are needed which fit the thermal expansion of the
open fire and smoke for well-defined temperature– electronic materials in direct contact with them. These
time programs, for example from 30 min to 180 min panes must remain stable in geometry (no shrinkage)
with a maximum temperature of more than 1000 ◦ C when they are processed to obtain the final product.
(test according to DIN 4102, Part 13). The main
goal is to avoid the glass breaking under thermal 3.4.3.2 Container Glass
load. There are various ways to achieve this, such as
mechanical wire reinforcement, prestressing the plate For packaging, transportation, storage of liquids, chem-
by thermal or surface-chemical means, or reducing icals, pharmaceuticals, etc., a high variety of hollowware
the thermal expansion by using other glass composi- is produced in the shape of bottles and tubes. Most of the
tions, for example the floated borosilicate glass Pyran® products are made from soda–lime glass (Table 3.4-3)
(Schott). directly from the glass melt. Vials and ampoules are
In automotive applications, flat glass is used for win- manufactured from tubes; for pharmaceuticals these are
dows and mirrors. Single-pane safety glass is produced made from chemically resistant borosilicate glass.
by generating a compressive stress near to the surface Clear glass products have to be made from relatively
by a special tempering program: a stress of 80–120 MPa pure raw materials. To protect the contents from light,
is usual. In the case of a breakage the window breaks especially UV radiation, the glass may be colored brown
into small pieces, which greatly reduces the danger of or green by the addition of Fe or Cr compounds. For
injuries. other colors, see Sect. 3.4.8.3.
3.4.4 Technical Specialty Glasses

Technical glasses are special glasses manufactured in 13–16% alkaline earths CaO + MgO, about 15% alkali
the form of tubes, rods, hollow vessels, and a variety of (usually Na2 O), and 0–2% Al2 O3 .
special shapes, as well as flat glass and granular form. Variants of the basic composition can contain sig-
Their main uses are in chemistry, pharmaceutical pack- nificant amounts of BaO with reduced alkali and
aging, electronics, and household appliances. A list of alkaline-earth oxides: these are used for X-ray shielding
typical applications of different glass types is given in of cathode-ray tube screens.
Table 3.4-10, and a list of their properties is given in
Table 3.4-11. 3.4.4.1 Chemical Stability of Glasses
The multitude of technical glasses can be roughly
arranged in the following four groups, according to their Characteristically, glasses are highly resistant to water,
oxide composition (in weight percent). However, certain salt solutions, acids, and organic substances. In this re-
glass types fall between these groups or even completely spect, they are superior to most metals and plastics.
outside. Glasses are attacked to a significant degree only by
hydrofluoric acid, strongly alkaline solutions, and con-
Borosilicate Glasses. The network formers are substan- centrated phosphoric acid; this occurs particularly at
tial amounts of silica (SiO2 ) and boric oxide (B2 O3 higher temperatures.
> 8%). The following subtypes can be differentiated: Chemical reactions with glass surfaces, induced by
exchange, erosion, or adsorption processes, can cause
•
Part 3 4.4
Non-alkaline-earth borosilicate glass: with SiO2

the most diverse effects, ranging from virtually invisible
> 80% and B2 O3 at 12–13%, these glasses show
surface modifications to opacity, staining, thin films with
high chemical durability and low thermal expansion
interference colors, crystallization, holes, and rough or
(about 3.3 × 10−6 K−1 ).
smooth ablation, to name but a few such effects. These
• Alkaline-earth-containing glasses: with SiO2 ≈
changes are often limited to the glass surface, but in
75%, B2 O3 at 8–12%, and alumina (Al2 O3 ) and
extreme cases they can completely destroy or dissolve
alkaline earths up to 5%, these glasses are softer in
the glass. The glass composition, stress medium, and
terms of viscosity, and have high chemical dura-
operating conditions will decide to what extent such
bility and a thermal expansion in the range of
chemical attacks are technically significant.
4.0–5.0 × 10−6 K−1 .
• High-borate glasses: with 65–70% SiO2 , 15–25%
Chemical Reaction Mechanisms
B2 O3 , and smaller amounts of Al2 O3 and alkalis,
with Water, Acid, and Alkaline Solutions
these glasses have a low softening point and a ther-
Chemical stability is understood as the resistance of
mal expansion which is suitable for glass-to-metal
a glass surface to chemical attack by defined agents;
seals.
here, temperature, exposure time, and the condition of
the glass surface play important roles.
Alkaline-Earth Aluminosilicate Glasses. These glasses Every chemical attack on glass involves water or one
are free from alkali oxides, and contain 52–60% SiO2 , of its dissociation products, i. e. H+ or OH− ions. For
15–25% Al2 O3 , and about 15% alkaline earths. A typ- this reason, we differentiate between hydrolytic (water),
ical feature is a very high transformation temperature. acid, and alkali resistance. In water or acid attack, small
amounts of (mostly monovalent or divalent) cations are
Alkali–Lead Silicate Glasses. These glasses contain leached out. In resistant glasses, a very thin layer of silica
over 10% lead oxide (PbO). Glasses with 20–30% PbO, gel then forms on the surface, which normally inhibits
54–58% SiO2 , and about 14% alkalis are highly insu- further attack (Fig. 3.4-8a,b). Hydrofluoric acid, alkaline
lating and provide good X-ray shielding. They are used solutions, and in some cases phosphoric acid, however,
in cathode-ray tube components. gradually destroy the silica framework and thus ablate
the glass surface in total (Fig. 3.4-8c). In contrast, water-
Alkali–Alkaline-Earth Silicate Glasses (Soda–Lime free (i. e. organic) solutions do not react with glass.
Glasses). This is the oldest glass type, which is pro- Chemical reactions are often increased or decreased
duced in large batches for windows and containers by the presence of other components. Alkali attack on
(see Sect. 3.4.3). Such glasses contain about 71% SiO2 , glass is thus hindered by certain ions, particularly those
Glasses 4.4 Technical Specialty Glasses 531
a) Release (mg Na2O/g) from glass grains Attacked layer thickness (µm)
0.04 1
c (HCl) = 6 mol/l
0.03 Exposure time: 16 h
0.02
0.1
0.01 Na2O
0 2 4 6 8
Time (h)
b) Weight loss (mg per 100 cm2) Si2O
0.60 0.01
0.40
0.001
0.20 0 50 100 150
Temperature (°C)
0.00
0 2 4 6 8 Fig. 3.4-9 Acid attack on Duran® 8330 as a function of
2 Time (h)
c) Weight loss (mg per 100 cm ) temperature, determined from leached amounts of Na2 O
240 and SiO2
Part 3 4.4
160
Attacked layer thickness (µm)
1.5
80 c (NaOH) = 1 mol/l
Exposure time: 1h
0 2 4 6 8 1.0
Time (h)
Fig. 3.4-8a–c Attack by (a) water, (b) acid, and (c) alka-
line solution on chemically resistant glass as a function of 0.5
time
of aluminium. On the other hand, complex-forming

compounds such as EDTA, tartaric acid, and citric acid 0 20 40 60 80 100
Temperature (°C)
can increase the solubility. In general terms, the glass
surface reacts with solutions which induce small-scale Fig. 3.4-10 Alkali attack on Duran® 8330 as a function of
exchange reactions and/or adsorption. Such phenomena temperature, determined from weight loss
are observed, for example, in high-vacuum technol-
ogy when residual gases are removed, and in certain creases rapidly with increasing temperature (Figs. 3.4-9
inorganic-chemical operations, when small amounts and 3.4-10).
of adsorbed chromium, resulting from treatment with In the case of truly ablative solutions such as hydro-
chromic acid, are removed. fluoric acid, alkaline solutions, and hot concentrated
Because acid and alkali attacks on glass are fun- phosphoric acid, the rate of attack increases rapidly with
damentally different, silica-gel layers produced by acid increasing concentration (Fig. 3.4-11). As can be seen in
attack obviously are not necessarily effective against Fig. 3.4-12, this is not true for the other frequently used
alkali solutions and may be destroyed. Conversely, the acids.
presence of ions that inhibit alkali attack does not neces-
sarily represent protection against acids and water. The Determination of the Chemical Stability
most severe chemical exposure is therefore an alternat- In most cases, either is the glass surface is analyzed in its
ing treatment with acids and alkaline solutions. As in all “as delivered” condition (with the original fire-polished
chemical reactions, the intensity of the interaction in- surface), or the basic material is analyzed with its fire-
in [4.2, 15] and summarized in Tables 3.4-4–3.4-6. The

Weight loss after 3 h (mg/100 cm2)
50 DIN classes of hydrolytic, acid, and alkali resistance
of technical glasses are also listed Table 3.4-11, second
page, last three colums.
40
Significance of the Chemical Stability
Release of Glass Constituents. In various processes in
30
chemical technology, pharmaceutical manufacture, and
laboratory work, the glass material used is expected to
20 release no constituents (or a very minimal amnount) into
reacting solutions or stored specimens.
Because even highly resistant materials such as non-
10 alkaline-earth and alkaline-earth borosilicate glasses do
react to a very small degree with the surrounding me-
dia, the fulfillment of this requirement is a question
0 8 10 12 14 of quantity and of detection limits. Concentrations of
pH 10−6 –10−9 (i. e. trace amounts), which are measurable
Fig. 3.4-11 Alkali attack on Duran® 8330 at 100 ◦ C as today with highly sophisticated analytical instruments,
a function of pH value can be released even from borosilicate glasses in the
form of SiO2 , B2 O3 , and Na2 O, depending on the con-
Part 3 4.4
Attacked layer thickness (µm) ditions. However, solutions in contact with high-grade
0.03 colorless Duran® laboratory glass will not be contam-
Temperature: 100 °C inated by Fe, Cr, Mn, Zn, Pb, or other heavy-metal
HCl Time: 1 h ions.
0.02 Undesirable Glass Surface Modifications. When an ap-
preciable interaction between a glass surface and an
aqueous solution occurs, there is an ion exchange in
0.01 which the easily soluble glass components are replaced
H2SO4 by H+ or OH− ions. This depletion of certain glass
components in the surface leads to a corresponding en-
richment in silica, which is poorly soluble, and thus to
0.00 HNO3 the formation of a silica-gel layer. This layer proves,
CH3COOH in most cases, to be more resistant than the base glass.
When its thickness exceeds about 0.1–0.2 µm, interfer-
ence colors caused by the different refractive indices of
0 5 10 15 20
Acid concentration (molarity) the layer and the base glass make this silica-gel layer
visible to the unaided eye. With increasing layer thick-
Fig. 3.4-12 Acid attack on Duran® 8330 as a function of ness it becomes opaque and finally peels off, destroying
concentration the glass. Between these stages there is a wide range
of possible surface modifications, some of which, al-
polished surface removed by mechanical or chemical though optically visible, are of no practical significance,
ablation, or after crushing. whereas others must be considered.
The standardized DIN (Deutsches Institut für In the case of less resistant glasses, small amounts
Normung, German Institute for Standardization) test of water (from air humidity and condensation) in the
methods, which are universally and easily applicable, presence of other agents such as carbon dioxide or sul-
are the most reliable analysis methods. They include the fur oxides can lead to surface damage. In the case of
determination of hydrolytic resistance (by two grain- sensitive glasses, hand perspiration or impurities left
titration methods and one surface method), of acid by detergents can sometimes induce strongly adhering
resistance to hydrochloric acid, and of alkali resistance surface defects, mostly recognizable as stains. If a con-
to a mixture of alkaline solutions. Details are described taminated glass surface is reheated (> 350–400 ◦ C), the
Table 3.4-4 Hydrolytic classes according to DIN 12111 (ISO 719)
Hydrolytic Acid consumption of Base equivalent Possible designation

class 0.01 mol/l hydrolytic acid as Na2 O
per g glass grains per g glass grains
(ml/g) (µg/g)
1 Up to 0.10 Up to 31 Very high resistance
2 Above 0.10, up to 0.20 Above 31, up to 62 High resistance
3 Above 0.20, up to 0.85 Above 62, up to 264 Medium resistance
4 Above 0.85, up to 2.0 Above 264, up to 620 Low resistance
5 Above 2.0, up to 3.5 Above 620, up to 1085 Very low resistance
Table 3.4-5 Acid classes according to DIN 12116 Table 3.4-6 Alkali classes according to DIN ISO 695
Acid Designation Half loss in weight Alkali Designation Loss in weight

class after 6 h class after 3 h
(mg/100 cm2 ) (mg/100 cm2 )
1 High acid resistance Up to 0.7 1 Low alkali attack Up to 75
Part 3 4.4
2 Good acid resistance Above 0.7, up to 1.5 2 Medium alkali attack Above 75, up to 175
3 Medium acid attack Above 1.5, up to 15 3 High alkali attack Above 175
4 High acid attack Above 15
3.4.4.2 Mechanical and Thermal Properties
contaminants or some of their components may burn
in. Normal cleaning processes will then be ineffective Viscosity
and the whole surface layer has to be removed (e.g. by As described earlier, the viscosity of glasses increases
etching). by 15–20 orders of magnitude during cooling. Within
this viscosity range, glasses are subject to three different
Desirable Chemical Reactions with the Glass Surface thermodynamic states:
(Cleaning and Etching). Very strong reactions between
aqueous agents and glass can be used for the thorough
• the melting range, above the liquidus tempera-
ture Ts ;
cleaning of glass. The complete ablation of a glass layer
leads to the formation of a new surface.
• the range of the supercooled melt, between the
liquidus temperature Ts and the transformation tem-
Hydrofluoric acid reacts most strongly with glass.
perature Tg , which is defined by ISO 7884-8;
Because it forms poorly soluble fluorides with a great
number of glass constituents, it is mostly used only in
• the frozen-in, quasi-solid melt range (“glass range”),
below the transformation temperature Tg .
diluted form. The best etching effect is usually achieved
when another acid (e.g. hydrochloric or nitric acid) is The absence of any significant crystallization in
added. A mixture of seven parts by volume of water, two the range of the supercooled melt (see Fig. 3.4-1, line
parts of concentrated hydrochloric acid (c = 38%) and segment 2) is of the utmost importance for glass for-
one part of hydrofluoric acid (c = 40%) is recommended mation. Hence a basically steady, smooth variation in
for a moderate surface ablation of highly resistant the viscosity in all temperature regions is a fundamen-
borosilicate glasses. When chemically less resistant tal characteristic of glasses (Fig. 3.4-4) and a crucial
glasses (e.g. Schott 8245 and 8250) are exposed for property for glass production. Figure 3.4-13 shows
5 min to a stirred solution at room temperature, a surface the strongly differing temperature dependences of the
layer with a thickness of 1–10 µm is ablated, and a trans- viscosity for some glasses. The best mathematical ex-
parent, smooth, completely new surface is produced. pression for practical purposes is the VFT (Vogel,
Glasses can also be ablated with alkaline solu- Fulcher, and Tammann) equation,
tions, but the alkaline etching process is much less
effective. log η(T ) = A + B/(T − T0 ) , (4.5)
for many purposes, and its brittleness (susceptibility to

log η (dPa s) cracking) is almost fully developed.
14
The lower limit of the annealing range is indi-
3 2 1 cated by the “strain point”, at which the glass has
12
4 a viscosity of 1014.5 dPa s (determined by extrapola-
10 tion from the viscosity–temperature curve). For most
glasses, the strain point lies about 30–40 K below the
8 annealing point. Relaxation of internal stresses here
takes 3–5 h. The strain point marks the maximum value
7 6 for short-term heat load. Thermally prestressed glasses,
6
in contrast, show significant stress relaxation even at
5 200–300 K below Tg . For glass objects with precisely
4
defined dimensions (e.g. etalons and gauge blocks) and
2 in the case of extreme demands on the stability of cer-
tain properties of the glass, application temperatures of
0 100–200 ◦ C can be the upper limit.
200 400 600 800 1000 1200 1400 1600
Temperature (°C)
Strength
Fig. 3.4-13 Viscosity–temperature curves for some impor- The high structural (theoretical) strength of glasses
tant technical glasses. 1, fused silica; 2, 8405; 3, 8330; and glass-ceramics (> 104 N/mm2 = 10 GPa) is without
Part 3 4.4
4, 8248; 5, 8350; 6, 8095; 7, 8465. Glasses with steep gra- practical significance, because the strength of glass arti-
dients (such as 7) are called “short” glasses, and those with cles is determined by surface defects induced by wear,
relatively shallow gradients (such as 4) are called “long” such as tiny chips and cracks (Griffith flaws), at whose
glasses tips critical stress concentrations may be induced by
a mechanical load, especially if the load is applied per-
where A, B, and T0 are glass-specific constants pendicular to the plane of the flaw (fracture mode I).
(Table 3.4-7). Glasses and glass-ceramics, in contrast to ductile ma-
Somewhat above 1010 dPa s, the viscosity becomes terials such as metals, show no plastic flow and behave
increasingly time-dependent. With increasing viscosity under a tensile stress σ in as brittle a manner as ceram-
(i. e. with decreasing temperature), the delay in estab- ics. A flaw will result in a fracture if the “stress intensity
lishing structural equilibrium finally becomes so large factor”
that, under normal cooling conditions, the glass struc- √
K I = 2σ a > K Ic , (4.6)
ture at 1013 dPa s can be described as solidified or
“frozen-in”. This temperature (for which a method of where a is the depth of the flaw and K Ic is the “crit-
measurement is specified by ISO 7884-4) is called the ical stress intensity factor”, a material constant which is
“annealing point”. At this viscosity, internal stresses in temperature- and humidity-dependent:
√ see Table 3.4-8.
the glass are released after ≈15 min annealing time, For K Ic = 1 MPa m and a stress σ = 50 MPa, the
while the dimensional stability of the glass is sufficient critical flaw depth ac is 100 µm. Thus very small flaws
Table 3.4-7 Parameters of the VFT equation (4.5) for the glasses in Fig. 3.4-13
Glass A B (◦ C) T0 (◦ C)
8095 − 1.5384 4920.68 96.54
8248 − 0.2453 4810.78 126.79
8330 − 1.8500 6756.75 105.00
8350 − 1.5401 4523.85 218.10
8405 − 2.3000 5890.50 65.00
8465 − 1.6250 1873.73 256.88
Fused silica − 7.9250 31 282.9 − 415.00
Soda–lime glass − 1.97 4912.5 475.4
can cause cracking at a comparatively low stress level, value. In contrast to the rapid stress increase occurring
and the practical strength of a glass is not a materials in an impact, for example, a slowly increasing tensile
constant! stress or continuous stress above a certain critical limit
may – as a result of stress corrosion cracking – cause
Surface Condition. As a result of wear-induced surface the propagation of critical surface flaws and cracks and
defects, glass and glass-ceramic articles have practical thus enhance their effect. Hence the tensile strength is
tensile strengths of 20–200 N/mm2 = 20–200 MPa, time- and stress-rate-dependent (this is mainly important
depending on the surface condition and the atmos- for test loads), as shown in Fig. 3.4-15. Independent of
pheric-exposure condition. To characterize the strength, surface damage or the initial tensile strength, increasing
a Weibull distribution for the cumulative failure prob-
ability F is assumed:
F (%)
F(σ) = 1 − exp −(σ/σc )m , (4.7)
Nominal strength
dσ /dt = 0.01
2
0.1 1 10 100 1000 N/(mm s)
where 0 ≤ F(σ) ≤ 1 is the probability of a fracture if values for
99
the applied stress is less than σ; σc denotes the char- Chem.- Normal
techn. glass 95
acteristic value (approximately the mean value of the large- consruc-
scale tions 80
distribution), and m is the Weibull modulus of the dis- units 60
50
tribution (which determines the standard deviation). 40
To obtain reproducible measurements, the surface is 20
predamaged by grinding with a narrow grain-size distri-
Part 3 4.4
10
bution (Fig. 3.4-14). 6
Only a slight – as a rule with neglible – dependence 4
on the chemical composition is found for silicate glasses 2
(Table 3.4-8). 1
3 5 7 10 20 30 50 70 100 200 300
σ E (N/mm2)
Stress Rate. The rate of increase of the stress and the
size of the glass area exposed to the maximum stress Fig. 3.4-15 Failure probability F of a predamaged surface
have to be considered for the specification of a strength (100 mm2 ; grain size 600) for various rates of increase of
stress dσ/ dt. A, range of nominal strength for large-scale
units in chemical technology; B, range of nominal strength
F (%)
for normal glass structures
Nominal strength Without
values for Grain size 200 220 300 600 deliberate damage
Chem.- Normal
99 σ D (N/mm2)
techn. glass 95 100
large- construc- 80
scale tions
units 60
50 80
40 Lifetime
20 102 s (1.7 min)
60
10
6 105 s (1.2 d)
4 40
2 108 s (3.17 y)
1 1011 s (3170 y)
20
3 5 7 10 20 30 50 70 100 200 300
σ E (N/mm2)
Fig. 3.4-14 Failure probability F for samples abraded by 0 20 40 60 80 100 120 160
variously sized grains. Predamaged surface area 100 mm2 , σ E (N/mm2)
rate of stress increase dσ/ dt = 10 MPa s−1 . A, range of Fig. 3.4-16 Time-related strength σD (strength under con-
nominal strength for large-scale units in chemical tech- stant loading) of soda–lime glass compared with the
nology; B, range of nominal strength for normal glass experimental strength σE at dσ/ dt = 10 N/mm2 s for vari-
structures ous lifetimes, in a normal humid atmosphere
the rate of increase of the stress by a factor of 10 results

F (%)
in an increase in the strength level of about 15%.
Nominal strength
values for S = 10 000 1000 100 10 mm2
Constant Loading. Fracture analysis of the effect and 99
Chem.- Normal
behavior of cracks in glasses and glass-ceramics yield techn. glass 95
large- consruc-
further information about the relationship between the scale tions 80
60
experimentally determined tensile strength σE (usually units
50
measured for a rapidly increasing load) and the tensile 40
strength σD expected under constant loading (= fatigue 20
strength), as shown in Fig. 3.4-16. Such analyses show 10
that, depending on the glass type, the tensile strength 6
4
under constant loading σD (for years of loading) may
2
amount to only about 1/2 to 1/3 of the experimental
1
tensile strength σE .
3 5 7 10 20 30 50 70 100 200 300
σ E (N/mm2)
Area Dependence. The larger the stressed area, the
higher is the probability of large defects (large crack Fig. 3.4-17 Failure probability F for differently sized
depths) within this area. This relationship is important stressed areas S. All samples abraded with 600 mesh
for the transfer of experimental tensile strengths, which grit, stress rate dσ/ dt = 10 N/mm2 s. A, range of nomi-
are mostly determined with relatively small test samples, nal strength for large-scale units in chemical technology;
Part 3 4.4
to practical glass applications such as pipelines, where B, range of nominal strength for normal glass structures
many square meters of glass can be uniformly stressed
(Fig. 3.4-17).
∆l/l × 103
700
Elasticity 600
4210
The ideal brittleness of glasses and glass-ceramics is
500
matched by an equally ideal elastic behavior up to break- 8095
ing point. The elastic moduli for most technical glasses 400
lie within a range of 50–90 kN/mm2 . The mean value 300 8250
of 70 kN/mm2 is about equal to the Young’s modulus of 200 8330
aluminium (see Table 3.4-11, first page, column 7).
100
Fused silica
Coefficient of Linear Thermal Expansion 0 100 200 300 400 500 600 700
With few exceptions, the length and the volume of Temperature (°C)
glasses increase with increasing temperature (positive
coefficient). Fig. 3.4-18 Linear thermal expansion coefficients of vari-
The typical curve begins with a zero gradient at ab- ous technical glasses and of fused silica
solute zero (Fig. 3.4-3) and increases slowly. At about
room temperature (section A in Fig. 3.4-3), the curve α(20 ◦ C/300 ◦ C) = 3.3–12.0 × 10−6 /K (see Table 3.4-11,
shows a distinct bend and then gradually increases first page, third column).
(section B, the quasi-linear region) up to the begin- The linear thermal expansion is an essential vari-
ning of the experimentally detectable plastic behavior. able in determining the sealability of glasses to other
Another distinct bend in the expansion curve charac- materials and in determining thermally induced stress
terizes the transition from a predominantly elastic to formation, and is therefore of prime importance for
a more plastic behavior of the glass (section C, the applications of glasses.
transformation range). As a result of increasing struc-
tural mobility, the temperature dependence of almost all Thermal Stresses. Owing to the low thermal conduc-
glass properties changes distinctly in this range. Fig- tivity of glasses (typically 0.9–1.2 W/m K at 90 ◦ C,
ure 3.4-18 shows the linear thermal expansion curves of and a minimum of 0.6 W/m K for high-lead-content
five glasses; 8330 and 4210 roughly define the normal glasses), temperature changes produce relatively high
range of technical glasses, with expansion coefficients temperature differences ∆T between the surface and
the interior, which, depending on the elastic proper- log ρ (Ω cm) Temperature (°C)
ties E (Young’s modulus) and µ (Poisson’s ratio) and on 200 300 400 500 700
13
the coefficient of linear thermal expansion α, can result
in stresses 12
8409
∆T αE 11
σ= N/mm2 . (4.8) 8250
(1 − µ) 10
In addition to the geometric factors (shape and wall 9
thickness), the material properties α, E, and µ decisively 8
8095
influence the thermal strength of glasses subjected to
temperature variations and/or thermal shock. Thermal 7
N16B Fused silica
loads in similar articles made from different glasses are 6
easily compared by means of the characteristic material 5
value
4
σ αE
ϕ= = N/(mm2 K) , (4.9) 3
∆T (1 − µ) 2.5 2.0 1.5 1.0
T –1/ (103 K–1)
which indicates the maximum thermally induced stress
to be expected in a flexure-resistant piece of glass for Fig. 3.4-19 Electrical volume resistivity of various tech-
a local temperature difference of 1 K. Because cracking nical glasses and fused silica as a function of reciprocal
originates almost exclusively from the glass surface and absolute temperature
Part 3 4.4
is caused there by tensile stress alone, cooling processes
are usually much more critical than the continuous rapid A plot of log ρ = f(1/T ) thus yields straight lines
heating of glass articles. (Fig. 3.4-19). Because of the relatively small differences
in slope for most glasses, the electrical insulation of
3.4.4.3 Electrical Properties glasses is often defined only by the temperature at
which the resistivity is 108 Ω cm. According to DIN
Glasses are used as electrically highly insulating ma- 52326, this temperature is denoted by Tk100 . The in-
terials in electrical engineering and electronics, in the ternational convention is to quote volume resistivities
production of high-vacuum tubes, lamps, electrode at 250 ◦ C and 350 ◦ C (Table 3.4-11, second page,
seals, hermetically encapsulated components, high- second column), from which the constants A and B
voltage insulators, etc. Moreover, glasses may be used as
insulating substrates for electrically conducting surface Table 3.4-8 Fracture toughness of some glasses
layers (in surface heating elements and data displays). √
Glass K Ic (MPa m)
Volume Resistivity BK7 1.08
Electrical conductivity in technical silicate glasses is, in F5 0.86
general, a result of the migration of ions – mostly alkali SF6 0.74
ions. At room temperature, the mobility of these ions is K50 0.77
usually so small that the volume resistivity, with values Duran® 0.85
above 1015 Ω cm, is beyond the range of measurement.
The ion mobility increases with increasing temperature.
Besides the number and nature of the charge carriers, the Table 3.4-9 Parameters of the volume resistivity (4.10) of
structural effects of other components also influence the the glasses in Fig. 3.4-19
volume resistivity and its relationship to temperature. Glass A B (K)
The Rasch and Hinrichsen law applies to this relation-
ship at temperatures below the transformation range: 8095 − 2.863 − 6520.0
8250 − 0.594 − 5542.0
log ρ = A − B/T , (4.10)
8409 − 0.463 − 6520.0
where ρ is the electrical volume resistivity in Ω cm, A, B N16B − 1.457 − 3832.4
are constants specific to the particular glass, and T is the Fused silica − 0.394 − 6222.4
absolute temperature in K.
(Table 3.4-9) and various other values below Tg can be

tan δ
calculated.
Surface Resistivity
The generally very high volume resistivity of glasses at
room temperature has superimposed on it in a normal 3
2
atmosphere a surface resistivity which is several orders
of magnitude lower. The all-important factor is the ad-
sorption of water on the glass surface. Depending on the
glass composition, surface resistivities of 1013 –1015 Ω
occur at low relative humidities, and 108 –1010 Ω at high 1 4
relative humidities. Above 100 ◦ C, the effect of this hy-
drated layer disappears almost completely. (Treatment 0 2 4 6 8 10 12 14
with silicones also considerably reduces this effect.) log f (Hz)
Fig. 3.4-21 Schematic representation of the frequency
Dielectric Properties spectrum of dielectric losses in glasses at room tempera-
With dielectric constants generally between 4.5 and 8, ture. The solid curve gives the total losses, made up of
technical glasses behave like other electrically insulat- (1) conduction loss, (2) relaxation loss, (3) vibration loss,
ing materials. The highest values are obtained for lead and (4) deformation loss
glasses such as 8531 (εr = 9.5) and for ultra-high-lead-
Part 3 4.4
content solder glasses (εr ∼ 20). The dependence of the At 106 Hz, the dissipation factors tan δ for most
dielectric constants εr on frequency and temperature is glasses lie between 10−2 and 10−3 ; fused silica, with
relatively small (Fig. 3.4-20). For a frequency range of a value of 10−5 , has the lowest dissipation factor of
50–109 Hz, εr values generally do not vary by more all glasses. The special glass 8248 has relatively low
than 10%. losses, and in this cases tan δ increases only slightly up
The dielectric dissipation factor tan δ is frequency- to 5.5 GHz (where tan δ = 3 × 10−3 ).
and temperature-dependent. Owing to the diverse mech- The steep increase in dielectric losses with increas-
anisms which cause dielectric losses in glasses, there ing temperature (Fig. 3.4-22) can lead to instability, i. e.
is a minimum of tan δ in the region of 106 –108 Hz, overheating of the glass due to dielectric loss energy in
and increasing values at lower and higher frequencies the case of restricted heat dissipation and corresponding
(Fig. 3.4-21). electrical power.
Dielectric constant ε r Dissipation factor tan δ

7 N16B
10–3
8095 8245
8412
8330
8245 8486
6 8487
10–2
8486
8095
8487
5
8330 10–1
–100 0 100 200

4 Temperature (°C)
–100 0 100 200
Temperature (°C) Fig. 3.4-22 Dissipation factor tan δ as a function of tem-
Fig. 3.4-20 Dielectric constant εr of electrotechnical perature in the range −100 ◦ C < T < +200 ◦ C, measured
glasses as a function of temperature, measured at 1 MHz at 1 MHz
Dielectric Strength of up to 4 × 10−6 mm2 /N. High-lead-content glasses can

Some approximate values for the dielectric strength of have values down to nil or even negative (Table 3.4-11,
glasses are a field strength of 20–40 kV/mm for a glass second page, fifth column).
thickness of 1 mm at 50 Hz at 20 ◦ C, and 10–20 kV/mm
for greater thicknesses. At higher temperatures and fre- Light Transmittance
quencies, decreasing values can be expected. The transmittance due to the refractive index can
be further reduced by coloring agents (oxides of
3.4.4.4 Optical Properties transition elements or colloids) or by fine particles
in the glass which have a different refractive in-
Refraction of Light dex (in this case light scattering occurs, giving opal
The refractive indices n d of technical glasses at a wave- glasses).
length of λd = 587.6 nm generally lie within the range Absorption caused by impurities such as Fe2 O3 and
1.47–1.57. The exceptions to this rule are lead glasses by some major glass components such as PbO strongly
with PbO contents of over 35% (e.g. glass 8531, which reduces transparency in the UV range. Particularly good
has n d = 1.7; see Table 3.4-11, second page, fourth col- UV-transmitting multicomponent glasses have a cutoff
umn). The principal dispersion n F − n C (λF = 486.1 nm,
λC = 656.3 nm) of technical glasses lies between 0.007
and 0.013. Transmission (%)
100
At perpendicular incidence, the reflectance Rd of
a glass–air interface is 3.6% to 4.9%.
Part 3 4.4
80 8337B
The transmittance τd and the reflectance ρd of a non-
absorbing, planar, parallel-sided glass plate with two 60
glass–air interfaces, with multiple reflections taken into
account, can be calculated from the refractive index as 40 8405
2n d
τd = 2 (4.11) 20
nd + 1
and 210 230 250 270 300 340
(n d − 1)2 Wavelength (nm)
ρd = . (4.12)
nd + 1 Fig. 3.4-23 UV transmission of highly UV-transparent
The transmittance τd at perpendicular incidence has glasses 8337B and 8405 for 1 mm glass thickness
values between 90.6% and 93.1%.
Transmission (%)
Stress Birefringence 100
Owing to its structure, glass is an isotropic material.
90
Mechanical stress causes anisotropy, which manifests 1mm
itself as stress-induced birefringence. A light beam, after 80
passing through a plate of thickness d which is subjected 70
8 mm
to a principal-stress difference ∆σ, shows an optical 60
path difference ∆s between the two relevant polarization
directions. This path difference can either be estimated 50
by means of the birefrigence colors or be measured with 40
a compensator, and is given by 30
2 mm
∆s = Kd∆σ nm , (4.13) 20
where K is the stress-optical coefficient of the glass 10
(determined according to DIN 52314),
0
∆s 1 200 500 1000 2000 5000 10 000
K= mm2 /N . (4.14) Wavelength (nm)
d ∆σ
Many glasses have stress-optical coefficients of about Fig. 3.4-24 Transmission of Duran® 8330 for thicknesses
3 × 10−6 mm2 /N, and borosilicate glasses have values of 1, 2, and 8 mm
(50% value) at a wavelength of 220 nm (Fig. 3.4-23); In the IR range, absorption caused by impurities such
normal technical glasses already absorb considerably at as H2 O and by lattice vibrations limits the transmittance
300 nm. (Fig. 3.4-24).
Table 3.4-10 Schott technical specialty glasses and their typical applications
8095 Lead glass (28% PbO), electrically highly insulating, for general electrotechnical applications
8245 Sealing glass for Fe–Ni–Co alloys and molybdenum, minimum X-ray absorption, chemically highly resistant
8248 Borosilicate glass (of high B2 O3 content), minimum dielectric losses up to the GHz range, electrically highly
insulating
8250 Sealing glass for Ni–Fe–Co alloys and molybdenum, electrically highly insulating
8252 Alkaline-earth aluminosilicate glass for high-temperature applications, for sealing to molybdenum
8253 Alkaline-earth aluminosilicate glass for high-temperature applications, for sealing to molybdenum
8321 Alumino-borosilicate glass for TFT displays
8326 SBW glass, chemically highly resistant
8330 Duran® , borosilicate glass, general-purpose glass for apparatus for the chemical industry, pipelines, and
laboratory glassware
8337B Borosilicate glass, highly UV-transmitting, for sealing to glasses and to metals of the Kovar and Vacon-10
ranges and tungsten
8350 AR glass® , soda–lime silicate glass tubing
Part 3 4.4
8405 Highly UV-transmitting soft glass

8409 Supremax® (black identification line), alkali-free, for high application temperatures in thermometry, apparatus
construction, and electrical engineering
8412 a Fiolax® , clear (blue identification line), neutral, glass tubing (chemically highly resistant) for pharmaceutical
packaging
8414 Fiolax® , amber (blue identification line), neutral, glass tubing (chemically highly resistant) for pharmaceutical
packaging
8415 Illax® , amber tubing glass for pharmaceutical packaging
8421 Sealing glass for seals to NiFe45 (DIN 17745) and compression seals
8422 Sealing glass for seals to NiFe47 or 49 (DIN 17745) and compression seals
8436 Particularly resistant to sodium vapor and alkaline solutions, suitable for sealing to sapphire
8486 Suprax® , borosilicate glass, chemically and thermally resistant, suitable for sealing to tungsten
8487 Sealing glass for tungsten, softer than 8486
8488 Borosilicate glass, chemically and thermally resistant
8490 Black glass, light-transmitting in the UV region, highly absorbing in the visible region
8512 IR-absorbing sealing glass for Fe–Ni, lead-free (reed switches)
8516 IR-absorbing sealing glass for NiFe, lead-free, slow-evaporating (reed switches)
8531 Soft glass, Na-free, high lead-content, for low temperature encapsulation of semiconductor components
(diodes)
8532 Soft glass, Na-free, high lead-content, for low-temperature encapsulation of semiconductor components
(diodes)
8533 IR-absorbing sealing glass for Ni–Fe, lead- and potassium-free, slow-evaporating (reed switches)
8625 IR-absorbing biocompatible glass for (implantable) transponders
8650 Alkali-free sealing glass for molybdenum, especially for implosion diodes; high lead content
8651 Tungsten sealing glass for power diodes
8652 Tungsten sealing glass, low-melting, for power diodes
8656 Borofloat® 40, borosilicate float glass adapted for prestressing
a Also known as 8258, Estax® , low-potassium glass tubing for the manufacture of counting vials.
Table 3.4-11 Characteristic data of technical specialty glasses
Glass Shapes Thermal Trans- Temperature Density Young’s Poisson’s Heat con-
No. produceda expansion formation at viscosity at 25 ◦ C modulus ratio µ ductivity
coefficient tempera- 1013 dPa s 107.6 dPa s 104 dPa s λ at 90 ◦ C
α(20/300) ture Tg
(10−6 /K) (◦ C) (◦ C) (◦ C) (◦ C) (g/cm3 ) (103 N/mm2 ) (W/m K)
8095 TP 9.2 435 435 635 985 3.01 60 0.22 0.9

8245 MTRP 5.1 505 515 720 1040 2.31 68 0.22 1.2
8248 BP 3.1 445 490 740 1260 2.12 44 0.22 1.0
8250 MTBPC 5.0 490 500 720 1055 2.28 64 0.21 1.2
8252 TP 4.6 725 725 935 1250 2.63 81 0.24 1.1
8253 TP 4.7 785 790 1000 1315 2.65 83 0.23 1.1
8261 SP 3.7 720 725 950 1255 2.57 79 0.24 1.1
8326 MTP 6.6 560 565 770 1135 2.46 75 0.20 1.2
8330 MSTRPC 3.3 525 560 820 1260 2.23 63 0.20 1.12
8337B TP 4.1 430 465 715 1090 2.21 51 0.22 1.0
Part 3 4.4
8350 TRP 9.1 525 530 715 1040 2.50 73 0.22 1.1
8405 MTP 9.8 460 450 660 1000 2.51 65 0.21 1.0
8409 MTRP 4.1 745 740 950 1230 2.57 85 0.24 1.2
8412 TP 4.9 565 565 780 1165 2.34 73 0.20 1.2
8414 TP 5.4 560 560 770 1155 2.42 71 0.19 1.2
8415 TP 7.8 535 530 720 1050 2.50 74 0.21 1.1
8421 P 9.7 525 535 705 1000 2.59 74 0.22 1.0
8422 P 8.7 540 535 715 1010 2.46 76 0.21 1.1
8436 TRP 6.7 630 630 830 1110 2.76 85 0.22 1.1
8486 MP 4.1 555 580 820 1220 2.32 66 0.20 1.1
8487 TRP 3.9 525 560 775 1135 2.25 66 0.20 1.2
8488 M 4.3 545 560 800 1250 2.30 67 0.20 1.2
8490 MP 9.6 475 480 660 1000 2.61 70 0.22 1.0
8512 TP 9.0 445 460 665 980 2.53 68 0.22 1.0
8516 TP 8.9 440 445 650 990 2.56 72 0.21 1.1
8531 TP 9.0 440 430 590 830 4.34 52 0.24 0.57
8532 TP 8.8 430 425 565 760 4.47 56 0.24 0.7
8533 TP 8.7 475 480 645 915 2.57 79 0.21 1.1
8625 TP 9.0 510 520 710 1030 2.53 73 0.22 1.1
8650 TP 5.2 475 475 620 880 3.57 62 0.23 0.5
8651 TP 4.5 540 540 735 1040 2.87 59 0.24 0.9
8652 TP 4.5 495 490 640 915 3.18 58 0.25 0.9
8656 SP 4.1 590 600 850 1270 2.35 − − −
a Shapes produced: B = block glass; C = capillaries; M = molded glass (blown or pressed); P = powder, spray granulates, or sintered parts;
R = rods; S = sheet glass; T = tubing
Table 3.4-11 Characteristic data of technical specialty glasses, cont.
Tk100 Logarithm of Dielectric properties Refractive Stress- Classes of chemical

electrical volume at 1 MHz index nd optical stability against
resistivity and 25 ◦ C (λd = 587.6 nm) coefficient K
( cm) at εr tan δ Alkaline
(◦ C) 250 ◦ C 350 ◦ C (10−4 ) (10−6 mm2 /N) Water Acid solution
330 9.6 7.6 6.6 11 1.556 3.1 3 2 3

215 7.4 5.9 5.7 80 1.488 3.8 3 4 3
− 12 10 4.3 10 1.466 5.2 3 3 3
375 10 8.3 4.9 22 1.487 3.6 3 4 3
660 − 12 6.1 11 1.538 3.3 1 3 2
630 − 11 6.6 15 1.547 2.7 1 2 2
585 − − 5.8 14 1.534 3.1 1 4 2
210 7.3 6.0 6.4 65 1.506 2.8 1 1 2
250 8.0 6.5 4.6 37 1.473 4.0 1 1 2
Part 3 4.4
315 9.2 7.5 4.7 22 1.476 4.1 3 4 3

200 7.1 5.7 7.2 70 1.514 2.7 3 1 2
280 8.5 6.9 6.5 45 1.505 2.8 5 3 2
530 12 10 6.1 23 1.543 2.9 1 4 3
215 7.4 6.0 5.7 80 1.492 3.4 1 1 2
200 7.1 5.6 6.3 107 1.523 2.2 1 2 2
180 6.7 5.3 7.1 113 1.521 3.2 2 2 2
255 8.1 6.4 7.4 43 1.526 2.7 3 3 2
205 7.3 5.8 7.3 60 1.509 2.9 2 3 3
245 7.9 6.5 7.9 75 1.564 2.9 1–2 1–2 1
230 7.5 6.1 5.1 40 1.487 3.8 1 1 2
300 8.3 6.9 4.9 36 1.479 3.6 4 3 3
200 7.1 5.8 5.4 96 1.484 3.2 1 1 2
235 7.7 6.1 6.7 32 1.52 − 3 2 2
320 9.5 7.5 6.5 21 1.510 3.0 3 1–2 2
250 8.1 6.4 6.5 25 1.516 3.0 3 1 2
450 11 9.8 9.5 9 1.700 2.2 1 4 3
440 11 9.4 10.2 9 1.724 1.7 1 4 3
200 7.0 5.5 6.9 55 1.527 3.0 1 2 2
210 7.2 5.8 7.1 68 1.525 − 3 1 2
− − − 7.6 33 1.618 2.8 1 4 3
− 11.2 10.0 6.0 31 1.552 3.6 1 4 3
− − − 6.9 35 1.589 3.4 1 4 3
265 8.3 6.8 5.5 51 1.493 3.6 1 1 1
Glasses 4.5 Optical Glasses 543
3.4.5 Optical Glasses

Historically, optical glasses were developed to optimize in the middle range of the visible spectrum, and the
imaging refractive optics in the visible part of the spec- Abbe value νd = (n d − 1)/(n F − n C ) as a measure of
trum. With new mathematical tools, new light sources, the dispersion. The difference n F − n C is called the
and new detectors, the resulting lens systems, which principal dispersion. The symbols have subscripts that
used a combination of different glasses (or even some- identify spectral lines that are generally used to deter-
times crystalline materials), changed the requirement mine refractive indices; these spectral lines are listed in
from high versatility in terms of material properties Table 3.4-12.
to homogeneity, precision, and reproducibility, and an The quantities n e and νe = (n e − 1)/(n F − n C )
extended spectral range in the ultraviolet and infrared based on the e-line are usually used for specifying optical
regions; environmental aspects also became important. components.
Consequently, the high number of glass types has been For the comparison of glass types from different
reduced. manufacturers, an abbreviated glass code is defined
in the following way: the first three digits correspond
3.4.5.1 Optical Properties to n d − 1, the second three digits represent the Abbe
value νd , and, after a dot, three more digits characterize
Refractive Index, Abbe Value, Dispersion, the density (see Table 3.4-13).
and Glass Designation Glasses can be grouped into families in an
The most common identifying features used for char- n d /νd Abbe diagram (Fig. 3.4-25). These glass families
Part 3 4.5
acterizing an optical glass are the refractive index n d differ in chemical composition as shown in Fig. 3.4-26.
Table 3.4-12 Wavelengths of a selection for frequently used spectral lines
Wavelength (nm) Designation Spectral line used Element
2325.42 Infrared mercury line Hg
1060.0 Neodymium glass laser Nd
1013.98 t Infrared mercury line Hg
852.11 s Infrared cesium line Cs
706.5188 r Red helium line He
656.2725 C Red hydrogen line H
643.8469 C Red cadmium line Cd
632.8 Helium–neon gas laser He–Ne
589.2938 D Yellow sodium line (center of the double line) Na D
587.5618 d Yellow helium line He
546.0740 e Green mercury line Hg
486.1327 F Blue hydrogen line H
479.9914 F Blue cadmium line Cd
435.8343 g Blue mercury line Hg
404.6561 h Violet mercury line Hg
365.0146 i Ultraviolet mercury line Hg
334.1478 Ultraviolet mercury line Hg
248.00 Excimer laser KrF
194.23
193.00 Excimer laser ArF
vd
90 85 80 75 70 65 60 55 55 45 40 35 30 25 20
nd nd
2.00 2.00
Description of symbols
Circles All glasses except short flint glasses (KZFS)
1.95 KZFS 1.95
Only N-type (lead-free and arsenic-free type) 66
1.90 N-type and conventional type 46 1.90

Conventional type 31
LASF
1.85 9 57 1.85
41 40
SF
43 45 6
44
1.80 32 36 11
1.80
21 33 56
34
14
33 A LAF 4
1.75 35 2
7 1.75
34 10
LAK 10 3 1
8
64 64
1.70 14 12 15 1.70
9 8
12 BASF 5
10 19
2
5 51 5
1.65 7 22 2 1.65
21 SSK BAF
11
53 15 10 2 2
16 8 4
4 4
Part 3 4.5
2 52
1.60 14
SK
4 5 1.60
5 BALF F
PSK 1 4 4 3 5
11 2 LF
1.55 3 BAK 5 1 1.55
2
LLF
51
5
KF9
PK 7 7
K 10
1.50 52 A 10 BK ZK7 1.50
51 5
FK
1.45 1.45
vd 90 85 80 75 70 65 60 55 55 45 40 35 30 25 20
Fig. 3.4-25 Abbe diagram of glass families
Table 3.4-13 Examples of glass codes

Refractive index nd
2.00 Glass nd νd Density Glass code Remarks
KzF glasses: SiO2-Sb2O3-B2O3
1.95 type
KzFS glasses: B2O3-PbO-Al2O2
(g cm−3 )
1.90
MmOn: ZrO2, Ta2O5, Nb2O5, ... B2O3-La2O3
1.85 -MmOn SiO2- N-SF6 1.80518 25.36 3.37 805 254.337 Lead- and ar-
MO: MgO, CaO, SrO, BaO, ZnO PbO-
M2O
senic-free glass
1.80 M2O: Li2O, Na2O, K2O, Cs2O
SF6 1.80518 25.43 5.18 805 254.518 Classical lead
1.75 (B2O3,SiO2)-
La2O3-MO silicate glass
1.70
(SiO2, B2O3)
1.65 SiO2- B2O3- -BaO-PbO
BaO SiO2-
1.60 P2O5- M2O- The designation of each glass type here is composed of
Al2O3- SiO2-
1.55
MO- BaO-M2O SiO
-PbO
2
TiO2- an abbreviated family designation and a number. The
B 2O 3 -M2O (F2-O)
P2O5-
Al2O3-
SO2- SiO2,B2O3-
B2O3- M2O-MO
glass families are arranged by decreasing Abbe value in
1.50 MO-
(F2-O)
M2O the data tables (Table 3.4-14).
1.45
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 Table 3.4-14 gives an overview of the preferred
Abbe number Ψ d optical glasses from Schott, Hoya, and Ohara. The
glass types are listed in order of increasing refractive
Fig. 3.4-26 Abbe diagram showing the chemical composition of index n d .
the glass families
Table 3.4-14 Comparison of the preferred optical glasses from different manufacturers
Schott Hoya Ohara Schott Hoya Ohara
Code Glass Code Glass Code Glass Code Glass Code Glass Code Glass
type type type type type type
434950 N-FK56 575415 S-TIL27
439950 S-FPL53 580537 N-BALF4
456903 S-FPL52 581409 N-LF5 581407 E-FL5 581407 S-TIL25
487704 N-FK5 487704 FC5 487702 S-FSL5 581409 LF5 581409 FL5
487845 N-FK51 583465 N-BAF3 583464 BAM3
497816 N-PK52 497816 FCD1 497816 S-FPL51 583594 BaCD12 583594 S-BAL42
498670 N-BK10 589613 N-SK5 589613 BaCD5 589612 S-BAL35
501564 K10 592683 N-PSK57
508612 N-ZK7 593353 S-FTM16
511604 K7 594355 FF5
517522 CF6 596392 E-F8 596392 S-TIM8
517524 E-CF6 517524 S-NSL36 596392 F8
517642 N-BK7 517642 BSC7 516641 S-BSL7 603380 E-F5 603380 S-TIM5
Part 3 4.5
517696 S-APL1 603380 F5 603380 F5
518590 E-C3 518590 S-NSL3 603606 N-SK14 603606 BaCD14 603607 S-BSM14
521526 SSL5 603655 S-PHM53
522595 N-K5 606439 N-BAF4 606437 S-BAM4
522598 S-NSL5 607567 N-SK2 607568 BaCD2 607568 S-BSM2
523515 N-KF9 609464 N-BAF52
529517 SSL2 613370 F3 613370 PBM3
529770 N-PK51 613443 KZFSN4 613443 ADF10 613443 BPM51
532488 N-LLF6 532488 FEL6 613445 N-KZFS4
532489 E-FEL6 532489 S-TIL6 613586 N-SK4 613587 BaCD4 613587 S-BSM4
540597 N-BAK2 540595 S-BAL12 614550 BSM9
541472 E-FEL2 541472 S-TIL2 617366 F4
541472 FEL2 617628 S-PHM51
547536 N-BALF5 618498 N-SSK8 618498 S-BSM28
548458 LLF1 548458 FEL1 618634 PCD4 618634 S-PHM52
548458 N-LLF1 548458 E-FEL1 548458 S-TIL1 620364 N-F2 620363 E-F2 620363 S-TIM2
551496 SbF1 620364 F2 620364 F2
552635 N-PSK3 620603 N-SK16 620603 BaCD16 620603 S-BSM16
558542 N-KZFS2 620622 ADC1
560612 S-BAL50 620635 N-PSK53
564608 N-SK11 564607 EBaCD11 564607 S-BAL41 621359 TIM11
567428 FL6 567428 PBL26 621603 SK51
569561 N-BAK4 569563 BaC4 569563 S-BAL14 622532 N-SSK2 622532 BSM22
569713 N-PSK58
571508 S-BAL2 623569 N-SK10 623570 EBaCD10 623570 S-BSM10
571530 S-BAL3 623580 N-SK15 623582 BaCD15 623582 S-BSM15
573576 N-BAK1 573578 S-BAL11 624470 BaF8
Table 3.4-14 Comparison of the preferred optical glasses from different manufacturers, cont.
Schott Hoya Ohara Schott Hoya Ohara
Code Glass Code Glass Code Glass Code Glass Code Glass Code Glass
type type type type type type
626357 F1 699301 N-SF15 699301 E-FD15 699301 S-TIM35
626357 E-F1 626357 S-TIM1 699301 SF15 699301 FD15
639421 N-KZFS11 700481 S-LAM51
639449 S-BAM12 702412 BaFD7 702412 S-BAH27
639554 N-SK18 639554 BaCD18 639554 S-BSM18 704394 NBASF64
640345 E-FD7 640345 S-TIM27 706303 N-SF64
640601 N-LAK21 640601 LaCL60 640601 S-BSM81 713538 N-LAK8 713539 LaC8 713539 S-LAL8
641569 S-BSM93 717295 N-SF1 717295 E-FD1
643584 S-BSM36 717295 SF1 717295 FD1 717295 PBH1
648339 SF2 648339 FD2 717480 N-LAF3 717480 LaF3 717479 S-LAM3
648338 E-FD2 648338 S-TIM22 720347 BPH8
649530 E-BaCED20 649530 S-BSM71 720420 LAM58
651559 N-LAK22 720437 S-LAM52
Part 3 4.5
651562 LaCL2 651562 S-LAL54 720460 LAM61

652449 N-BAF51 720506 N-LAK10 720504 LaC10 720502 S-LAL10
652585 N-LAK7 652585 LaC7 652585 S-LAL7 722292 S-TIH18
654396 KZFSN5 654396 ADF50 654397 BPH5 724381 NBASF51 723380 S-BAH28
658509 N-SSK5 658509 BaCED5 658509 S-BSM25 724381 BASF51 724381 BaFD8
658573 S-LAL11 726536 S-LAL60
664360 N-BASF2 728284 SF10 728284 FD10
667330 S-TIM39 728285 N-SF10 728285 E-FD10 728285 S-TIH10
667484 BaF11 667483 S-BAH11 729547 N-LAK34 729547 TaC8 729547 S-LAL18
670393 BAH32 734515 TaC4 734515 S-LAL59
670471 N-BAF10 670473 BaF10 670473 S-BAH10 740283 PBH3W
741276 FD13 740283 PBH3
670573 S-LAL52 741278 E-FD13 741278 S-TIH13
673322 N-SF5 673321 E-FD5 673321 S-TIM25 741527 TaC2 741527 S-LAL61
673322 SF5 673322 FD5 743492 N-LAF35 743493 NbF1 743493 S-LAM60
678507 LaCL9 678507 S-LAL56 744447 N-LAF2 744447 LaF2 744448 S-LAM2
678549 LAKL12 750350 LaFN7 750353 LaF7 750353 LAM7
678552 N-LAK12 678553 LaC12 678553 S-LAL12 750350 N-LAF7
689312 N-SF8 689311 E-FD8 689311 S-TIM28 754524 N-LAK33 755523 TaC6 755523 S-YGH51
689312 FD8 755276 N-SF4 755275 E-FD4 755275 S-TIH4
691547 N-LAK9 691548 LaC9 691548 S-LAL9 755276 SF4 755276 FD4
694508 LaCL5 694508 LAL58 756251 TPH55
694533 LAKN13 694532 LaC13 694532 S-LAL13 757478 NbF2 757478 S-LAM54
695422 S-BAH54 762265 N-SF14 762265 FD140 762265 S-TIH14
697485 LaFL2 697485 LAM59 762265 SF14 762266 FD14
697554 N-LAK14 697555 LaC14 697555 S-LAL14 762401 S-LAM55
697565 S-LAL64 772496 N-LAF34 772496 TaF1 772496 S-LAH66
Table 3.4-14 Comparison of preferred optical glasses, cont. Relative Partial Dispersion. The relative partial disper-
sion Px,y for the wavelengths x and y based on the blue F
Schott Hoya Ohara
hydrogen line and red C hydrogen line is given by
Code Glass Code Glass Code Glass
type type type Px,y = (n x − n y )/(n F − n C ) . (4.15)
785258 SF11 785258 FD11 The corresponding value based on the blue F cadmium
785258 FD110 785257 S-TIH11 line and red C cadmium line is given by

785261 SF56A Px,y = (n x − n y )/(n F − n C ) . (4.16)
785261 N-SF56 785261 FDS30 785263 S-TIH23
Relationship Between the Abbe Value and the Rel-
786441 N-LAF33 786439 NBFD11 786442 S-LAH51
ative Partial Dispersion. A linear relationship exists
787500 S-YGH52
between the Abbe value and the relative partial disper-
788475 N-LAF21 788475 TAF4 788474 S-LAH64 sion for what are known as “normal glasses”:
794454 N-LAF32 795453 S-LAH67
Px,y ≈ axy + bxy νd . (4.17)
800423 N-LAF36 800423 NBFD12 800422 S-LAH52
801350 N-LASF45 801350 S-LAM66
804396 S-LAH63 Deviation from the “Normal Line”. All other glasses
804466 N-LASF44 804465 TAF3 804466 S-LAH65
deviate from the “normal line” defined by ∆Px,y . For the
selected wavelength pairs the ∆P-value are calculated
805254 N-SF6 805254 FD60 805254 S-TIH6
from the following equations:
Part 3 4.5
805254 SF6 805254 FD6
805396 NBFD3 Px,y = axy + bxy νd + ∆Px,y , (4.18)
806333 NBFD15 ∆PC,t = (n C − n t )/(n F − n C )
806407 N-LASF43 806407 NBFD13 806409 S-LAH53 − (0.5450 + 0.004743νd ) , (4.19)
808228 S-NPH1 ∆PC,s = (n C − n s )/(n F − n C )
816445 TAFD10 816444 S-LAH54 − (0.4029 + 0.002331νd ) , (4.20)
816466 TAF5 816466 S-LAH59
∆PF,e = (n F − n e )/(n F − n C )
834374 N-LASF40 834373 NBFD10 834372 S-LAH60
− (0.4884 − 0.000526νd ) , (4.21)
835430 N-LASF41 835430 TAFD5 835427 S-LAH55
∆Pg,F = (n g − n F )/(n F − n C )
847238 N-SF57 847238 FDS90 847238 S-TIH53
847236 SFL57 − (0.6438 − 0.001682νd ) , (4.22)
847238 SF57 847238 FDS9 847238 TIH53 ∆Pi,g = (n i − n g )/(n F − n C )

850322 LASFN9 − (1.7241 − 0.008382νd ) . (4.23)
874353 S-LAH75 The “normal line” has been determined based on value
881410 N-LASF31 pairs of glasses types K7 and F2. The term ∆Px,y quan-
883408 TAFD30 883408 S-LAH58 titatively describes the deviation of the behavior of the
901315 N-LASF46 901315 LAH78 dispersion from that of “normal glasses”.
923209 SF66 923209 E-FDS1 The Sellmeier dispersion formula for the refractive
923213 PBH71 index,
1003283 S-LAH79 n 2 (λ) − 1 = B1 λ2 /(λ2 − C1 ) + B2 λ2 /(λ2 − C2 )
1022291 N-LASF35 + B3 λ2 /(λ2 − C3 ) , (4.24)
can be derived from classical dispersion theory with

Formulas for Optical Characterization the assumption of three resonance wavelengths. It is
The characterization of optical glasses through the re- valid only for interpolation within a spectral region
fractive index and Abbe value alone is insufficient for in which the refractive index has been measured. The
high-quality optical systems. A more accurate descrip- vacuum wavelength λ in µm has to be used. The pre-
tion of the properties of a glass can be achieved with the cision of the calculation achievable is generally better
aid of the relative partial dispersion. than 1 × 10−5 .
Temperature Dependence of the Refractive Index. The Transmission. The transmittance of glasses is limited
refractive index is also dependent on temperature. This by electronic excitiations and light scattering in the UV,
temperature dependence is represented by ∆n rel /∆T for by vibronic excitations in the IR, and by reflections and
an air pressure of 1013.3 hPa and ∆n abs /∆T in vacuum. impurity absorptions within the transmission window
The following equation is derived from the Sellmeier (in the visible part of the spectrum): Fig. 3.4-27. The UV
formula and is valid with the given coefficients in the absorption edge is temperature dependent. An example
temperature range −40 ◦ C < T < +80 ◦ C and within the is shown in Fig. 3.4-28.
wavelength range 435.8 nm < λ < 643.8 nm:
Spectral Internal Transmittance. The spectral internal
dn abs (λ, T ) n 2 (λ, T0 ) − 1 transmittance is given by
=
dT 2n(λ, T0 ) τiλ = Φeλ /Φiλ ,
(4.30)
E 0 + 2E 1 ∆T where Φiλ is the incident light intensity and Φeλ is the
× D0 + 2D1 ∆T + 3D2 ∆T + 2
,
λ2 − λ2TK intensity at the exit.
(4.25)
Spectral Transmission. The spectral transmission is
where ∆T is the temperature difference in ◦C
from given by
20 ◦ C, and λTK is an effective resonance wavelength. τλ = τiλ Pλ , (4.31)
The changes in the refractive index and Abbe value
where Pλ is the reflection factor.
caused by a change in the annealing rate are given by
Part 3 4.5
n d (h x ) = n d (h 0 ) + m nd log(h x /h 0 ) , (4.26)
νd (h x ) = νd (h 0 ) + m νd log(h x /h 0 ) , (4.27)
Transmission (%)
m nd − νd (h 0 )m nF−nC 100
m νd = ,
(n F − n C ) + 2m nF−nC log(h x /h 0 ) 90
(4.28) 80
70
where h 0 is the original annealing rate in ◦ C/h, h x is 60
the new annealing rate in ◦ C/h, m nd is the annealing 50
coefficient for the refractive index (Table 3.4-15), m νd is 40
the annealing coefficient for the Abbe value and m nF−nC 30
is the annealing coefficient for the principal dispersion. 20
The last three quantities depend on the glass type. 10
The measurement accuracy of the Abbe value can 0
be calculated using 200 500 1000 5000
Wavelength (nm)
σ(νd ) ≈ σ(n F − n C )νd /(n F − n C ) . (4.29) Fig. 3.4-27 Transmission of three glasses for a thickness
of 5 mm: Brown line FK5; dashed line SF2; gray line SF11
The accuracy of precision measurements of the refrac-
tive indices is better than ±1 × 10−5 , and the accuracy
of the dispersion is ±3 × 10−6 . In the infrared wave- 100
Transmission (%)
length range above 2 µm, the corresponding accuracies
are ±2 × 10−5 and ±5 × 10−6 . 80
60 20 °C
Table 3.4-15 Annealing coefficients for selected glass 100 °C
types 40 200 °C
300 °C
Glass type mnd mnF−nC mνd 20 400 °C
500 °C
N-BK7 −0.00087 −0.000005 −0.0682
0
N-FK51 −0.00054 −0.000002 −0.0644 300 400 500 600 700 800
Wavelength (µm)
SF6 −0.00058 +0.000035 −0.0464
Fig. 3.4-28 Influence of temperature on the UV transmis-
N-SF6 −0.0025 −0.000212 +0.0904 sion of glass F2 for a thickness of 10 mm
Fresnel Reflectivity. For a light beam striking the surface glass type depends on the volume and the form of
perpendicularly, the Fresnel reflectivity is, independent the individual glass piece. Values of ±5 × 10−7 (class
of polarization, H5) cannot be achieved for all dimensions and glass
types.
R = (n − 1)2 /(n + 1)2 . (4.32) The properties of a selection of optical glasses are
collected together in Table 3.4-16.
Reflection Factor. The reflection factor, taking account
of multiple reflection, is given by Internal Transmittance and Color Code
The internal transmittance, i. e. the light transmission
P = (1 − R)2 /(1 − R2 ) = 2n/(n 2 + 1) , (4.33) excluding reflection losses, is closely related to the
optical position of the glass type, according to gen-
where n is the refractive index for the wavelength λ.
eral dispersion theory. This can be achieved, however,
only by using purest raw materials and costly melting
Conversion of Internal Transmittance to Another
technology.
Layer Thickness. The conversion of data for internal
The internal transmittance of lead- and arsenic-
transmittance to another sample thickness is accom-
free glasses, in which lead has been replaced by other
plished by the use of the equation
elements, is markedly less than in the lead-containing
log τi1 / log τi2 = d1 /d2 (4.34) predecessor glasses.
(d /d ) The limit of the transmission range of optical glasses
or τi2 = τi1 2 1 , (4.35)
towards the UV area is of special interest and is
Part 3 4.5
where τi1 and τi2 are the internal transmittances for the characterized by the position and slope of the UV ab-
thicknesses d1 and d2 , respectively. sorption curve, which is described by a color code.
The color code gives the wavelengths λ80 and λ5 , at
Stress Birefringence. The change in optical path length which the transmission (including reflection losses) is
for existing stress birefringence can be calculated from 0.80 and 0.05, respectively, at 10 mm thickness. The
color code 33/30 means, for example, λ80 = 330 nm
∆s = (n − n ⊥ )d = (K − K ⊥ )dσ = Kdσ , (4.36) and λ5 = 300 nm.
where K is the stress optical coefficient, dependent on
the glass type, d is the length of the light path in the sam- 3.4.5.2 Chemical Properties
ple, and σ is the mechanical stress (positive for tensile
stress). If K is given in 10−6 mm2 /N, d is given in mm, The composition of optical glasses includes elements
and σ is measured in MPa = N/mm2 , ∆s comes out in that reduce chemical resistance. For these glasses,
mm. five test methods are used to assess the chemical
For the Pockels glass SF57, the stress optical coeffi- behavior of polished glass surfaces in typical appli-
cient K is close to 0 in the visible wavelength range. cations. The test methods and classification numbers
take the place of those described for technical glasses
Homogeneity. The homogeneity of the refractive index in Sect. 3.4.4. Data for optical properties are found in
of a sample can be measured from the interferometrically Table 3.4-16c.
measured wavefront deformation using the equation
Climatic Resistance (ISO/WD 13384): Division
∆n = ∆W/2d into Climatic Resistance Classes CR 1–4
= ∆W(λ) × 633 × 10−6 /(2d[mm]) , (4.37)
Climatic resistance describes the behavior of optical
glasses at high relative humidity and high temperatures.
where the wavefront deformation is in units of the In the case of sensitive glasses, a cloudy film can appear
wavelength and is measured using a test wavelength that generally cannot be wiped off.
of 633 nm (He–Ne laser); ∆W is the wavefront de- The classifications are based on the increase in trans-
formation for double beam passage; and d is the mission haze ∆H after a 30 h test period. The glasses in
thickness of the test piece. With special effort during class CR 1 display no visible attack after being subjected
melting and careful annealing, it is possible to pro- to 30 h of climatic change.
duce pieces of glass having high homogeneity. The Under normal humidity conditions, no surface attack
refractive-index homogeneity achievable for a given should be expected during the fabrication and storage of
optical glasses in class CR 1. On the other hand, the in grinding and polishing processes. The phosphate re-
fabrication and storage of optical glasses in class CR 4 sistance describes the behavior of optical glasses during
should be done with caution because these glasses are cleaning with phosphate-containing washing solutions
very sensitive to climatic influences. (detergents).
The alkali resistance class AR is based on the time
Stain Resistance: Division into Stain Resistance required to remove a layer of glass of thickness 0.1 µm in
Classes FR 0–5 an alkaline solution (sodium hydroxide, c = 0.01 mol/l,
The test procedure gives information about possible pH = 12) at a temperature of 50 ◦ C.
changes in the glass surface (stain formation) under The phosphate resistance class PR is based on the
the influence of lightly acidic water (for example per- time required to remove a layer of glass of thickness
spiration and acidic condensates) without vaporization. 0.1 mm in an alkaline phosphate-containing solution
Two test solutions are used. Test solution I is a standard (pentasodium triphosphate, Na5 P3 O10 , c = 0.01 mol/l,
acetate solution with pH = 4.6, for classes FR 0 to 3. pH = 10) at a temperature of 50 ◦ C. The thickness is cal-
Test solution II is a sodium acetate buffer solution with culated from the weight loss per unit surface area and
pH = 5.6, for classes FR 4 and FR 5. the density of the glass.
Interference color stains develop as a result of de-
composition of the surface of the glass by the test 3.4.5.3 Mechanical Properties
solution. The measure used for classifying the glasses
is the time that elapses before the first brown–blue stain Young’s Modulus and Poisson’s Ratio
occurs at a temperature of 25 ◦ C. The adiabatic Young’s modulus E (in units of
Part 3 4.5
Stain resistance class FR 0 contains all glasses that 103 N/mm2 ) and Poisson’s ratio µ have been deter-
exhibit virtually no interference colors even after 100 h mined at room temperature and at a frequency of 1 kHz
of exposure to test solution I. using carefully annealed test samples. Data are listed in
Glasses in classification FR 5 must be handled with Table 3.4-16c. In most cases, the values decrease slightly
particular care during processing. with temperature.
The torsional modulus can be calculated from
Acid Resistance (ISO 8424: 1987): Division into
Acid Resistance Classes SR 1–4, 5, and 51–53 G = E/[2(1 + µ)] . (4.38)
Acid resistance classifies the behavior of optical glasses
that come into contact with large quantities of acidic
solutions (from a practical standpoint, these may be The longitudinal sound velocity is
perspiration, laminating substances, carbonated water,

etc.). E(1 − µ)
The time t required to dissolve a layer with a thick- vlong = , (4.39)
ness of 0.1 µm serves as a measure of acid resistance. (1 + µ)(1 − 2µ)
Two aggressive solutions are used in determining acid
resistance. A strong acid (nitric acid, c = 0.5 mol/l, where is the density.
pH = 0.3) at 25 ◦ C is used for the more resistant glass
types. For glasses with less acid resistance, a weakly Knoop Hardness
acidic solution with a pH value of 4.6 (standard acetate) The Knoop hardness (HK) of a material is a measure
is used, also at 25 ◦ C. of the residual surface changes after the application of
pressure with a test diamond. The standard ISO 9385
Alkali Resistance (ISO 10629) and Phosphate describes the measurement procedure for glasses. In
Resistance (ISO 9689): Division into Alkali accordance with this standard, values for Knoop hard-
Resistance Classes AR 1–4 and Phosphate ness HK are listed in the data sheets for a test force of
Resistance Classes PR 1–4 0.9807 N (corresponds to 0.1 kp) and an effective test
These two test methods indicate the resistance to aque- period of 20 s. The test was performed on polished glass
ous alkaline solutions in excess and use the same surfaces at room temperature. The data for hardness val-
classification scheme. The alkali resistance indicates the ues are rounded to 10 HK 0.1/20. The microhardness
sensitivity of optical glasses when they are in contact is a function of the magnitude of the test force and
with warm, alkaline liquids, such as cooling liquids used decreases with increasing test force.
Table 3.4-16a Properties of optical glasses. Refractive index and Sellmeier constants
Glass Refractive index Abbe value Constants of the Sellmeier dispersion formula
type nd ne vd ve B1 B2 B3 C1 C2 C3
F2 1.62004 1.62408 36.37 36.11 1.34533359 × 10+00 2.09073176 × 10−01 9.37357162 × 10−01 9.97743871 × 10−03 4.70450767 × 10−02 1.11886764 × 10+02
K10 1.50137 1.50349 56.41 56.15 1.15687082 × 10+00 6.42625444 × 10−02 8.72376139 × 10−01 8.09424251 × 10−03 3.86051284 × 10−02 1.04747730 × 10+02
LASF35 2.02204 2.03035 29.06 28.84 2.45505861 × 10+00 4.53006077 × 10−01 2.38513080 × 10+00 1.35670404 × 10−02 5.45803020 × 10−02 1.67904715 × 10+02
LF5 1.58144 1.58482 40.85 40.57 1.28035628 × 10+00 1.63505973 × 10−01 8.93930112 × 10−01 9.29854416 × 10−03 4.49135769 × 10−02 1.10493685 × 10+02
LLF1 1.54814 1.55098 45.89 45.60 1.23326922 × 10+00 1.16923839 × 10−01 8.62645379 × 10−01 8.85396812 × 10−03 4.36875155 × 10−02 1.04992168 × 10+02
N-BAF10 1.67003 1.67341 47.11 46.83 1.58514950 × 10+00 1.43559385 × 10−01 1.08521269 × 10+00 9.26681282 × 10−03 4.24489805 × 10−02 1.05613573 × 10+02
N-BAF52 1.60863 1.61173 46.60 46.30 1.43903433 × 10+00 9.67046052 × 10−02 1.09875818 × 10+00 9.07800128 × 10−03 5.08212080 × 10−02 1.05691856 × 10+02
N-BAK4 1.56883 1.57125 55.98 55.70 1.28834642 × 10+00 1.32817724 × 10−01 9.45395373 × 10−01 7.79980626 × 10−03 3.15631177 × 10−02 1.05965875 × 10+02
N-BALF4 1.57956 1.58212 53.87 53.59 1.31004128 × 10+00 1.42038259 × 10−01 9.64929351 × 10−01 7.96596450 × 10−03 3.30672072 × 10−02 1.09197320 × 10+02
N-BASF64 1.70400 1.70824 39.38 39.12 1.65554268 × 10+00 1.71319770 × 10−01 1.33664448 × 10+00 1.04485644 × 10−02 4.99394756 × 10−02 1.18961472 × 10+02
N-BK7 1.51680 1.51872 64.17 63.96 1.03961212 × 10+00 2.31792344 × 10−01 1.01046945 × 10+00 6.00069867 × 10−03 2.00179144 × 10−02 1.03560653 × 10+02
N-FK56 1.43425 1.43534 94.95 94.53 9.11957171 × 10−01 1.28580417 × 10−01 9.83146162 × 10−01 4.50933489 × 10−03 1.53515963 × 10−02 2.23961126 × 10+02
N-KF9 1.52346 1.52588 51.54 51.26 1.19286778 × 10+00 8.93346571 × 10−02 9.20819805 × 10−01 8.39154696 × 10−03 4.04010786 × 10−02 1.12572446 × 10+02
N-KZFS2 1.55836 1.56082 54.01 53.83 1.23697554 × 10+00 1.53569376 × 10−01 9.03976272 × 10−01 7.47170505 × 10−03 3.08053556 × 10−02 7.01731084 × 10+01
N-LAF2 1.74397 1.74791 44.85 44.57 1.80984227 × 10+00 1.57295550 × 10−01 1.09300370 × 10+00 1.01711622 × 10−02 4.42431765 × 10−02 1.00687748 × 10+02
N-LAK33 1.75398 1.75740 52.43 52.20 1.45796869 × 10+00 5.55403936 × 10−01 1.19938794 × 10+00 6.80545280 × 10−03 2.25253283 × 10−02 8.27543327 × 10+01
N-LASF31 1.88067 1.88577 41.01 40.76 1.71317198 × 10+00 7.18575109 × 10−01 1.72332470 × 10+00 8.19172228 × 10−03 2.97801704 × 10−02 1.38461313 × 10+02
N-PK51 1.52855 1.53019 76.98 76.58 1.15610775 × 10+00 1.53229344 × 10−01 7.85618966 × 10−01 5.85597402 × 10−03 1.94072416 × 10−02 1.40537046 × 10+02
N-PSK57 1.59240 1.59447 68.40 68.01 9.88511414 × 10−01 5.10855261 × 10−01 7.58837122 × 10−01 4.78397680 × 10−03 1.58020289 × 10−02 1.29709222 × 10+02
N-SF1 1.71736 1.72308 29.62 29.39 1.60865158 × 10+00 2.37725916 × 10−01 1.51530653 × 10+00 1.19654879 × 10−02 5.90589722 × 10−02 1.35521676 × 10+02
N-SF56 1.78470 1.79179 26.10 25.89 1.73562085 × 10+00 3.17487012 × 10−01 1.95398203 × 10+00 1.29624742 × 10−02 6.12884288 × 10−02 1.61559441 × 10+02
N-SK16 1.62041 1.62286 60.32 60.08 1.34317774 × 10+00 2.41144399 × 10−01 9.94317969 × 10−01 7.04687339 × 10−03 2.29005000 × 10−02 9.27508526 × 10+01
N-SSK2 1.62229 1.62508 53.27 52.99 1.43060270 × 10+00 1.53150554 × 10−01 1.01390904 × 10+00 8.23982975 × 10−03 3.33736841 × 10−02 1.06870822 × 10+02
SF1 1.71736 1.72310 29.51 29.29 1.55912923 × 10+00 2.84246288 × 10−01 9.68842926 × 10−01 1.21481001 × 10−02 5.34549042 × 10−02 1.12174809 × 10+02
SF11 1.78472 1.79190 25.76 25.55 1.73848403 × 10+00 3.11168974 × 10−01 1.17490871 × 10+00 1.36068604 × 10−02 6.15960463 × 10−02 1.21922711 × 10+02
SF2 1.64769 1.65222 33.85 33.60 1.40301821 × 10+00 2.31767504 × 10−01 9.39056586 × 10−01 1.05795466 × 10−02 4.93226978 × 10−02 1.12405955 × 10+02
Glasses
SF66 1.92286 1.93325 20.88 20.73 2.07842233 × 10+00 4.07120032 × 10−01 1.76711292 × 10+00 1.80875134 × 10−02 6.79493572 × 10−02 2.15266127 × 10+02
SK51 1.62090 1.62335 60.31 60.02 1.44112715 × 10+00 1.43968387 × 10−01 8.81989862 × 10−01 7.58546975 × 10−03 2.87396017 × 10−02 9.46838154 × 10+01
K7 1.51112 1.51314 60.41 60.15 1.12735550 × 10+00 1.24412303 × 10−01 8.27100531 × 10−01 7.20341707 × 10−03 2.69835916 × 10−02 1.00384588 × 10+02
N-SF6 1.80518 1.81266 25.36 25.16 1.77931763 × 10+00 3.38149866 × 10−01 2.08734474 × 10+00 1.33714182 × 10−02 6.17533621 × 10−02 1.74017590 × 10+02
SF6 1.80518 1.81265 25.43 25.24 1.72448482 × 10+00 3.90104889 × 10−01 1.04572858 × 10+00 1.34871947 × 10−02 5.69318095 × 10−02 1.18557185 × 10+02
N-FK51 1.48656 1.48794 84.47 84.07 9.71247817 × 10−01 2.16901417 × 10−01 9.04651666 × 10−01 4.72301995 × 10−03 1.53575612 × 10−02 1.68681330 × 10+02
4.5 Optical Glasses
LithosilTM Q 1.45843 1.46004 67.87 67.67 6.69422575 × 10−01 4.34583937 × 10−01 8.71694723 × 10−01 4.48011239 × 10−03 1.32847049 × 10−02 9.53414824 × 10+01
551
Part 3 4.5
Table 3.4-16b Data for dn/dT

Glass type Data for dn/dT
106 D0 108 D1 1011 D2 107 E0 1010 E1 λTK (µm)
F2 1.51 1.56 − 2.78 9.34 10.4 0.250

K10 4.86 1.72 − 3.02 3.82 4.53 0.260
LASF35 0.143 0.871 − 2.71 10.2 15.0 0.263
LF5 − 2.27 0.971 − 2.83 8.36 9.95 0.228
LLF1 0.325 1.74 − 6.12 6.53 2.58 0.233
N-BAF10 3.79 1.28 − 1.42 5.84 7.60 0.220
N-BAF52 1.15 1.27 − 0.508 5.64 6.38 0.238
N-BAK4 3.06 1.44 − 2.23 5.46 6.05 0.189
N-BALF4 5.33 1.47 − 1.58 5.75 6.58 0.195
N-BASF64 1.60 1.02 − 2.68 7.87 9.65 0.229
N-BK7 1.86 1.31 − 1.37 4.34 6.27 0.170
N-FK56 − 20.4 − 1.03 0.243 3.41 4.37 0.138
N-KF9 − 1.66 0.844 − 1.01 6.10 6.96 0.217
Part 3 4.5
N-KZFS2 6.77 1.31 − 1.23 3.84 5.51 0.196

N-LAF2 − 3.64 0.920 − 0.600 6.43 6.11 0.220
N-LAK33 2.57 1.16 − 7.29 6.01 1.59 0.114
N-LASF31 2.29 0.893 − 1.59 6.52 8.09 0.236
N-PK51 − 19.8 − 0.606 1.60 4.16 5.01 0.134
N-PSK57 − 22.3 − 0.560 0.997 4.47 5.63 −
N-SF1 − 3.72 0.805 − 1.71 8.98 13.4 0.276
N-SF56 − 4.13 0.765 − 1.12 9.90 15.7 0.287
N-SK16 − 0.0237 1.32 − 1.29 4.09 5.17 0.170
N-SSK2 5.21 1.34 − 1.01 5.21 5.87 0.199
SF1 4.84 1.70 − 4.52 13.8 12.6 0.259
SF11 11.2 1.81 − 5.03 14.6 15.8 0.282
SF2 1.10 1.75 − 1.29 10.8 10.3 0.249
SF66 − − − − − −
SK51 − 5.63 0.738 − 6.20 3.91 2.64 0.230
K7 − 1.67 0.880 − 2.86 5.42 7.81 0.172
N-SF6 − 4.93 0.702 − 2.40 9.84 15.4 0.290
SF6 6.69 1.78 − 3.36 17.7 17.0 0.272
N-FK51 − 18.3 − 0.789 − 0.163 3.74 3.46 0.150
LithosilTM Q 20.6 2.51 − 2.47 3.12 4.22 0.160
Table 3.4-16c Chemical and physical data
Glass Stress- Chemical properties Density Viscosity (dPa s) Thermal properties Mechanical properties
type optical 1014.5 1013 107.6 Heat Heat Thermal expansion Young’s Poisson’s Knoop
coefficient K capacity conductivity modulus E ratio µ hardness
CR FR SR AR PR at temperature cp λ α(30/70) α(20/300)
(10−6 mm2 /N) (g/cm3 ) (◦ C) (◦ C) (◦ C) (J/g K) (W/m K) (10−6 /K) (10−6 /K) (103 N/mm2 ) HK
F2 2.81 1 0 1 2.3 1.3 3.61 432 421 593 0.557 0.780 8.20 9.20 57 0.220 420
K10 3.12 1 0 1 1 1.2 2.52 459 453 691 0.770 1.120 6.50 7.40 65 0.190 470
LASF35 0.73 1 0 1.3 1 1.3 5.41 774 − − 0.445 0.920 7.40 8.50 132 0.303 810
LF5 2.83 2 0 1 2.3 2 3.22 419 411 585 0.657 0.866 9.10 10.60 59 0.223 450
LLF1 3.05 1 0 1 2 1 2.94 448 426 628 0.650 − 8.10 9.20 60 0.208 450
N-BAF10 2.37 1 0 4.3 1.3 1 3.75 660 652 790 0.560 0.780 6.18 7.04 89 0.271 620
N-BAF52 2.42 1 0 1 1.3 1 3.05 594 596 723 0.680 0.960 6.86 7.83 86 0.237 600
N-BAK4 2.90 1 0 1.2 1 1 3.05 581 569 725 0.680 0.880 6.99 7.93 77 0.240 550
N-BALF4 3.01 1 0 1 1 1 3.11 578 584 661 0.690 0.850 6.52 7.41 77 0.245 540
N-BASF64 2.38 1 0 3.2 1.2 1 3.20 582 585 712 − − 7.30 8.70 105 0.264 650
N-BK7 2.77 2 0 1 2 2.3 2.51 557 557 719 0.858 1.114 7.10 8.30 82 0.206 610
N-FK56 0.68 1 0 52.3 4.3 4.3 3.54 422 416 − 0.750 0.840 − 16.16 70 0.293 350
N-KF9 2.74 1 0 1 1 1 2.50 476 476 640 0.860 1.040 9.61 10.95 66 0.225 480
N-KZFS2 4.02 1 4 52.3 4.3 4.2 2.55 491 488 600 0.830 0.810 4.43 5.43 66 0.266 490
N-LAF2 1.42 2 3 52.2 1 2.2 4.30 653 645 742 0.510 0.670 8.06 9.10 94 0.288 530
N-LAK33 1.49 1 1 51.3 1 2.3 4.26 652 648 − 0.554 0.900 6.00 7.00 124 0.291 780
N-LASF31 1.10 1 0 2 1 1 5.41 758 756 − − 0.910 6.80 7.70 124 0.299 770
N-PK51 0.54 2 0 51.2 3.3 4.3 3.96 496 486 − − − 12.70 14.40 74 0.295 400
N-PSK57 0.13 1 0 51.3 1.2 4.3 4.48 497 499 − 0.490 0.560 13.17 14.75 69 0.298 370
N-SF1 2.72 1 0 1 1 1 3.03 553 554 660 0.750 1.000 9.13 10.54 90 0.250 540
N-SF56 2.87 1 0 1 1.3 1 3.28 592 585 691 0.700 0.940 8.70 10.00 91 0.255 560
N-SK16 1.90 4 4 53.3 3.3 3.2 3.58 636 633 750 0.578 0.818 6.30 7.30 89 0.264 600
N-SSK2 2.51 1 0 1.2 1 1 3.53 653 655 801 0.580 0.810 5.81 6.65 82 0.261 570
SF1 1.80 2 1 3.2 2.3 3 4.46 417 415 566 − − 8.10 8.80 56 0.232 390
SF11 1.33 1 0 1 1.2 1 4.74 503 500 635 0.431 0.737 6.10 6.80 66 0.235 450
SF2 2.62 1 0 2 2.3 2 3.86 441 428 600 0.498 0.735 8.40 9.20 55 0.227 410
Glasses
SF66 − 1.20 2 5 53.4 2.3 4.2 6.03 384 385 482 0.340 0.530 9.01 11.48 51 0.258 310
SK51 1.47 2 3 52.3 1.3 4.3 3.52 597 579 684 − − 8.90 10.10 75 0.291 450
K7 2.95 3 0 2 1 2.3 2.53 513 − 712 − − 8.4 9.7 69 0.214 520
N-SF6 2.82 1 0 2 1 1 3.37 594 591 694 0.69 0.96 9.03 10.39 93 0.262 550
SF6 0.65 2 3 51.3 2.3 3.3 5.18 423 410 538 0.389 0.673 8.1 9 55 0.244 370
N-FK51 0.70 2 0 52.3 2.2 4.3 3.73 420 403 − 0.636 0.911 13.3 15.3 81 0.293 430
LithosilTM Q 3.40 1 1 1 2.20 980 1080 1600 0.790 1.310 0.50 72 0.170 580
4.5 Optical Glasses
− − −
Part 3 4.5
553
Table 3.4-16d Internal transmission and color code

Glass Color Internal transmission measured for 25 mm sample thickness at wavelength λ (nm)
type code 2500 2325 1970 1530 1060 700 660 620 580 546 500 460 436
F2 35/32 0.610 0.700 0.890 0.990 0.998 0.998 0.996 0.997 0.997 0.997 0.996 0.993 0.991
K10 33/30 0.520 0.630 0.850 0.983 0.996 0.997 0.994 0.993 0.993 0.992 0.991 0.990 0.988
LASF35 −/37 0.690 0.880 0.972 0.992 0.990 0.978 0.970 0.962 0.950 0.920 0.810 0.630 0.470
LF5 34/31 − 0.660 0.870 0.992 0.998 0.998 0.998 0.998 0.997 0.997 0.996 0.995 0.994
LLF1 33/31 0.500 0.610 0.840 0.990 0.996 0.997 0.996 0.996 0.997 0.997 0.996 0.996 0.996
N-BAF10 39/35 0.450 0.680 0.920 0.980 0.994 0.994 0.990 0.991 0.990 0.990 0.981 0.967 0.954
N-BAF52 39/35 0.390 0.630 0.890 0.975 0.994 0.993 0.990 0.989 0.990 0.989 0.980 0.967 0.954
N-BAK4 36/33 0.540 0.710 0.900 0.982 0.995 0.997 0.995 0.995 0.996 0.996 0.994 0.989 0.988
N-BALF4 37/33 0.580 0.740 0.920 0.984 0.993 0.997 0.995 0.995 0.996 0.995 0.993 0.986 0.983
N-BASF64 40/35 0.450 0.670 0.900 0.970 0.985 0.970 0.955 0.949 0.949 0.950 0.940 0.920 0.900
N-BK7 33/29 0.360 0.560 0.840 0.980 0.997 0.996 0.994 0.994 0.995 0.996 0.994 0.993 0.992
N-FK56 33/28 − − 0.979 0.991 0.996 0.996 0.996 0.996 0.996 0.996 0.996 0.996 0.995
Part 3 4.5
N-KF9 37/34 0.300 0.430 0.740 0.981 0.995 0.997 0.995 0.994 0.996 0.996 0.994 0.990 0.988
N-KZFS2 34/30 0.040 0.260 0.800 0.940 0.991 0.996 0.994 0.994 0.994 0.994 0.992 0.987 0.981
N-LAF2 40/34 0.400 0.690 0.930 0.990 0.997 0.996 0.993 0.992 0.993 0.994 0.983 0.962 0.940
N-LAK33 39/32 0.090 0.400 0.850 0.975 0.995 0.991 0.990 0.990 0.990 0.990 0.987 0.977 0.967
N-LASF31 45/32 0.540 0.810 0.960 0.992 0.993 0.994 0.994 0.993 0.993 0.990 0.973 0.940 0.910
N-PK51 35/29 0.890 0.920 0.965 0.985 0.992 0.991 0.991 0.992 0.994 0.995 0.993 0.989 0.987
N-PSK57 34/29 − − 0.950 0.970 0.982 0.996 0.996 0.996 0.996 0.996 0.992 0.991 0.991
N-SF1 41/36 0.460 0.580 0.850 0.973 0.995 0.990 0.986 0.987 0.990 0.986 0.968 0.940 0.910
N-SF56 44/37 0.590 0.680 0.900 0.981 0.996 0.986 0.981 0.981 0.983 0.976 0.950 0.910 0.860
N-SK16 36/30 0.260 0.540 0.880 0.973 0.995 0.996 0.994 0.993 0.994 0.994 0.991 0.984 0.981
N-SSK2 37/33 0.500 0.720 0.930 0.981 0.992 0.996 0.994 0.993 0.995 0.995 0.992 0.985 0.980
SF1 39/34 0.650 0.730 0.900 0.985 0.996 0.996 0.995 0.995 0.996 0.996 0.993 0.984 0.976
SF11 44/39 0.610 0.700 0.930 0.982 0.997 0.993 0.991 0.991 0.991 0.989 0.976 0.940 0.860
SF2 37/33 0.620 0.710 0.880 0.985 0.996 0.996 0.994 0.995 0.995 0.995 0.993 0.988 0.982
SF66 48/38 0.700 0.740 0.920 0.990 0.995 0.990 0.989 0.989 0.988 0.985 0.965 0.890 0.770
SK51 36/31 0.270 0.520 0.830 0.959 0.993 0.993 0.993 0.993 0.993 0.993 0.990 0.981 0.975
K7 33/30 0.340 0.500 0.790 0.980 0.994 0.996 0.995 0.995 0.994 0.994 0.993 0.990 0.990
N-SF6 45/37 0.850 0.880 0.962 0.994 0.994 0.987 0.980 0.979 0.980 0.970 0.940 0.899 0.850
SF6 42/36 0.730 0.780 0.930 0.990 0.996 0.996 0.995 0.995 0.995 0.994 0.989 0.972 0.940
N-FK51 34/28 0.750 0.840 0.940 0.980 0.994 0.995 0.995 0.996 0.997 0.997 0.996 0.993 0.992
LithosilTM Q 17/16 0.780 − − − − − − − − − − − −
Internal transmission measured for 25 mm sample thickness at wavelength λ (nm)

420 405 400 390 380 370 365 350 334 320 310 300 290 248 200 193
0.990 0.986 0.984 0.977 0.963 0.940 0.920 0.780 0.210 − − − − − − −

0.988 0.987 0.986 0.982 0.973 0.966 0.958 0.910 0.720 0.310 0.130 0.020 − − − −
0.320 0.170 0.120 0.050 0.010 − − − − − − − − − − −
0.993 0.992 0.992 0.984 0.973 0.961 0.954 0.880 0.570 0.040 − − − − − −
0.995 0.994 0.993 0.992 0.988 0.984 0.981 0.955 0.810 0.300 0.010 − − − − −
0.940 0.900 0.880 0.800 0.660 0.440 0.310 0.010 − − − − − − − −
0.938 0.900 0.880 0.800 0.650 0.370 0.210 − − − − − − − − −
0.987 0.983 0.980 0.967 0.940 0.890 0.840 0.550 0.070 − − − − − − −
0.981 0.970 0.964 0.940 0.900 0.820 0.750 0.380 − − − − − − − −
0.880 0.840 0.820 0.750 0.610 0.370 0.220 − − − − − − − − −
0.993 0.993 0.992 0.989 0.983 0.977 0.971 0.920 0.780 0.520 0.250 0.050 − − − −
0.994 0.996 0.996 0.995 0.992 0.985 0.975 0.920 0.760 0.460 0.210 0.060 0.010 − − −
− − − − − − − −
Part 3 4.5
0.985 0.975 0.965 0.940 0.880 0.770 0.680 0.210
0.975 0.967 0.963 0.950 0.930 0.910 0.890 0.800 0.590 0.240 0.030 − − − − −
0.915 0.865 0.840 0.760 0.630 0.430 0.310 0.025 − − − − − − − −
0.954 0.928 0.910 0.860 0.790 0.690 0.630 0.400 0.140 0.020 − − − − − −
0.880 0.840 0.820 0.750 0.650 0.530 0.460 0.210 0.040 0.020 − − − − − −
0.986 0.985 0.984 0.977 0.965 0.940 0.910 0.750 0.430 0.120 0.030 − − − − −
0.991 0.991 0.992 0.992 0.989 0.975 0.965 0.880 0.680 0.380 0.130 0.020 − − − −
0.870 0.760 0.700 0.520 0.250 0.030 − − − − − − − − − −
0.780 0.640 0.570 0.370 0.130 − − − − − − − − − − −
0.979 0.974 0.970 0.956 0.930 0.890 0.860 0.700 0.400 0.110 0.020 − − − − −
0.975 0.963 0.954 0.920 0.860 0.750 0.670 0.250 − − − − − − − −
0.961 0.930 0.920 0.870 0.790 0.640 0.500 0.030 − − − − − − − −
0.700 0.340 0.200 0.010 − − − − − − − − − − − −
0.975 0.962 0.954 0.920 0.870 0.790 0.720 0.370 − − − − − − − −
0.610 0.340 0.240 0.050 − − − − − − − − − − − −
0.971 0.963 0.958 0.940 0.910 0.850 0.800 0.600 0.300 0.100 0.030 − − − − −
0.990 0.990 0.990 0.988 0.983 0.976 0.971 0.940 0.780 0.420 0.100 − − − −
0.780 0.640 0.570 0.370 0.140 − − − − − − − − − − −
0.900 0.810 0.760 0.620 0.370 0.100 0.020 − − − − − − − − −
0.992 0.993 0.993 0.992 0.988 0.976 0.963 0.875 0.630 0.300 0.120 0.035 0.010 − − −
− − − − − − − − − − − − − 0.995 0.990 0.980
Viscosity tion range is distinguished by a distinct bending

As explained in the introduction, glasses pass through of the expansion curve, which results from the
three viscosity ranges between the melting temperature increasing structural rearrangement in the glass.
and room temperature: the melting range, the super- Above this range, the expansion again exhibits
cooled melt range, and the solidification range. The a nearly linear increase, but with a noticeably greater
viscosity increases during the cooling of the melt, slope.
starting from 100 –104 dPa s. A transition from a li- Two averaged coefficients of linear thermal expan-
quid to a plastic state is observed between 104 and sion α are usually given: α30/70 , averaged from −30 ◦ C
1013 dPa s. to +70 ◦ C, which is the relevant value for room tempera-
The softening point, i. e. the temperature where ture; and α20/300 , averaged from +20 ◦ C to +300 ◦ C,
the viscosity is 107.6 dPa s, identifies the plastic range which is the standard international value. These values
in which glass parts rapidly deform under their own are listed in Table 3.4-16.
weight. The glass structure can be described as solidi-
fied or “frozen” above 1013 dPa s. At this viscosity, the 3.4.5.4 Thermal Properties
internal stresses in glass anneal out equalize in approx-
imately 15 min. The temperature at which the viscosity Thermal Conductivity
is 1013 dPa s is called the upper annealing point, and is The range of values for the thermal conductivity of
important for the annealing of glasses. glasses at room temperature extends from 1.38 W/m K
In accordance with ISO 7884-8, the rate of change of (pure vitreous silica) to about 0.5 W/m K (high-lead-
the relative linear thermal expansion can be used to deter- content glasses). The most commonly used silicate
Part 3 4.6
mine the transformation temperature Tg , which is close glasses have values between 0.9 and 1.2 W/m K. All
to the temperature at which the viscosity is 1013 dPa s. data in Table 3.4-16c are given for a temperature of
Precision optical surfaces may deform and refractive 90 ◦ C, with an accuracy of ±5%.
indices may change if a temperature of Tg − 200 K is
exceeded during any thermal treatment. Specific Thermal Capacity
The mean isobaric specific heat capacities c p (20 ◦ C;
Coefficient of Linear Thermal Expansion 100 ◦ C) listed in Table 3.4-16c were measured from
The typical curve of the linear thermal expan- the heat transfer from a hot glass sample at 100 ◦ C
sion of a glass begins with an increase in slope into a liquid calorimeter at 20 ◦ C. The values of
from absolute zero to approximately room tempera- c p (20 ◦ C; 100 ◦ C) and also of the true thermal cap-
ture. Then a nearly linear increase to the beginning acity c p (20 ◦ C) for silicate glasses range from 0.42 to
of the plastic behavior follows. The transforma- 0.84 J/g K.
3.4.6 Vitreous Silica

Vitreous silica has a unique set of properties. It is pro- constant K as a function of wavelength are found in
duced either from natural quartz by fusion or, if extreme Fig. 3.4-29.
purity is required, by chemical vapor deposition or via The highest transmittance is required for applica-
a sol–gel routes. Depending on the manufacturing pro- tions in optical communication networks, in optics for
cess, variable quantities impurities are incorporated in lithography, and in high-power laser physics. For cer-
the ppm or ppb range, such as Fe, Mg, Al, Mn, Ti, tain applications, for example to increase the refractive
Ce, OH, Cl, and F. These impurities and radiation- index in the IR in fiber optics, the silica is “doped”
induced defects, as well as complexes of impurities and with GeO2 , P2 O5 , B2 O3 , etc. in the range of 5–10%.
defects, and also overtones, control the UV and IR trans- In such cases the scattering loss increases owing to
mittance. In the visible part of the spectrum, Rayleigh concentration fluctuations.
scattering from thermodynamically caused density fluc- There are also many technical applications which
tuations dominates. Defects are also responsible for make use of the chemical inertness, light weight, high
the damage threshold under radiation load, and for temperature stability, thermal-shock resistance, and low
fluorescence. The refractive index n and the absorption thermal expansion of vitreous silica. A very low thermal
Glasses 4.6 Vitreous Silica 557
Table 3.4-17 Electrical properties of vitreous silica

Refractive index n(λ ) Absorption constant k( λ )
(LithosilTM )
3.5 101
n
k Dielectric constant εr 3.8 ± 0.2
3.0
100 Dielectric loss angle ϕ 89.92◦ ± 0.03◦ at 25 ◦ C
2.5
and 1 MHz
10–1
2.0 tan δ (δ = 90◦ − ϕ) 14 ± 5 × 10−4
1.5 Electrical resistivity 1.15 × 1018 (Ω cm) at 20 ◦ C
10–2
1.0
10–3 3.4.6.2 Gas Solubility
0.5 and Molecular Diffusion
0 10–4
10–1 100 101 The relatively open structure of vitreous silica provides
Wavelength λ (µm)
space for the incorporation and diffusion of molecular
Fig. 3.4-29 Measured optical constants n(λ) and k(λ) of species. The data in the literature are not very consistent;
vitreous silica according to [4.16] Table 3.4-18 should serve as an orientation.
The pressure dependence of the solubility is small
expansion is obtained in ULE glass (Corning “ultralow up to about 100 atm.
expansion” glass) by doping with ≈ 9% TiO2 . The diffusion coefficient depends on temperature
Part 3 4.6
as
3.4.6.1 Properties of Synthetic Silica
D = D0 T exp (−Q/RT ) . (4.40)
The precise data for materials from various suppliers Water can react with the silica network:
differ slightly, depending on the thermal history and im-
H2 O + Si−O−Si = 2 Si−OH . (4.41)
purity concentration. The data listed in Table 3.4-16a–d
and in Table 3.4-17, are for LithosilTM Q0 (Schott The reaction has a strong influence on the concen-
Lithotec). The various quantities are defined in the same tration and apparent diffusion of dissolved molecular
way as for optical glasses, as described in Sect. 3.4.5. water.
Table 3.4-18 Solubility and diffusion of molecular gases in vitreous silica (LithosilTM )
Gas Molecular cglass /cgas Dissolved Diffusion Activation
diameter molecules S coefficient D0 energy Q
(nm) at (cm−3 atm−1 ) (cm2 /s) (kJ/mole)
200–1000 ◦ C at 200 ◦ C 25 ◦ C 1000 ◦ C
Helium 0.20 0.025 3.9 × 10−17 2.4 × 10−8 5.5 × 10−5 20

Neon 0.24 0.019 3.1 × 10−17 5.0 × 10−12 2.5 × 10−6 37
Hydrogen 0.25 0.03 4.7 × 10−17 2.2 × 10−11 7.3 × 10−6 36
Argon 0.32 0.01 1.5 × 10−17 − 1.4 × 10−9 111
Oxygen 0.32 0.01 1.5 × 10−17 − 6.6 × 10−9 105
Water 0.33 − − − ≈ 3.0 × 10−7 71
Nitrogen 0.34 − − − − 110
Krypton 0.42 − − − − ≈ 190
Xenon 0.49 − − − − ≈ 300
3.4.7 Glass-Ceramics
Glass-ceramics are distinguished from glasses and from 700 ◦ C. Wall thickness, wall thickness differences, and
ceramics by the characteristics of their manufacturing complicated shapes are of no significance.
processes (see introduction to this chapter 3.4) as well Another technical advantage is the exceptionally
as by their physico-chemical properties. high dimensional and shape stability of objects made
They are manufactured in two principal production from these materials, even when the objects are sub-
steps. In the first step, a batch of exactly defined com- jected to considerable temperature variations.
position is melted (as for a conventional glass). The The Zerodur® glass-ceramic, whose coefficient of
composition is determined by the desired properties of linear thermal expansion at room temperature can be
the endproduct and by the necessary working proper- kept at ≤ 0.05 × 10−6 /K (Table 3.4-19), was especially
ties of the glass. After melting, the product is shaped by developed for the production of large mirror blanks for
pressing, blowing, rolling, or casting, and then annealed. astronomical telescopes. Zerodur® has further appli-
In this second step, “glassy” articles are partly crystal- cations in optomechanical precision components such
lized by use of a specific temperature–time program as length standards, and mirror spacers in lasers. With
between 800 and 1200 ◦ C (this program must be defined
for each composition). Apart from the crystalline phase, ∆l/l/10–4
with crystals 0.05–5 µm in size, this material contains 20
a residual glass phase that amounts to 5–50% of the Soda–lime glass
volume. 15
Part 3 4.7
In the temperature range between 600 and 700 ◦ C,

small amounts of nucleating agents (e.g. TiO2 , ZrO2 , 10
or F) induce precipitation of crystal nuclei. When the Duran®
borosilicate glass
temperature is increased, crystals grow on these nuclei. 5
Their type and properties, as well as their number and
size, are predetermined by the glass composition and 0
the annealing program. By selection of an appropriate Glass-ceramics
program, either transparent, slightly opaque, or highly –5
–200 0 200 400 600 800
opaque, nontransparent glass-ceramics can be produced. Temperature (°C)
Unlike conventional ceramics, these glass ceramics are
fully dense and pore-free. Fig. 3.4-30 Thermal expansion of glass-ceramics com-
Like the composition of glasses, the compo- pared with borosilicate glass 3.3 and soda–lime glass
sition of glass-ceramics is highly variable. Some Table 3.4-19 Coefficient of linear thermal expansion α,
well-known compositions lie within the following sys- density, and elastic properties of Zerodur® and Ceran®
tems: Li2 O−Al2 O3 −SiO2 , MgO−Al2 O3 −SiO2 , and glass-ceramics
CaO−P2 O5 −Al2 O3 −SiO2 .
Glass-ceramics of the Li2 O−Al2 O3 −SiO2 system, Zerodur® Ceran® Units Product
which contain small amounts of alkali and alkaline- class
earth oxides, as well as TiO2 and ZrO2 as nucleating α0/50 0 ± 0.05 − 10−6 /K 1
agents, have achieved the greatest commercial impor- 0 ± 0.1 − 10−6 /K 2
tance. On the basis of this system, glass-ceramics with 0 ± 0.15 − 10−6 /K 3
coefficients of linear thermal expansion near to zero α20/300 + 0.1 − 0.2 10−6 /K
can be produced (Fig. 3.4-30 and Table 3.4-19). This α20/500 − − 0.01 10−6 /K
exceptional property results from the bonding of crys- α20/600 + 0.2 − 10−6 /K
talline constituents (such as solid solutions of h-quartz, α20/700 − + 0.15 10−6 /K
h-eucryptite, or h-spodumene) which have negative co-
Density 2.53 2.56 g/cm3
efficients of thermal expansion with the residual glass
Young’s
phase of the system, which has a positive coefficient of
modulus E 91 × 103 92 × 103 N/mm2
thermal expansion.
Such “α = 0 glass-ceramics” can be subjected to vir- Poisson’s
tually any thermal shock or temperature variation below ratio µ 0.24 0.24
Glasses 4.8 Glasses for Miscellaneous Applications 559
a length aging coefficient A (where L = L 0 (1 + A∆t), high elastic modulus and thus stiffness: Neoceram
∆t = time span) below 1 × 10−7 /y, Zerodur® has excel- (NEG), and products from Corning and Ohara;
lent longitudinal stability. • glass-ceramics with extremely good weathering
The Ceran® glass-ceramic is colored and is designed properties for architectural applications: Neoparies
for applications in cooker surface panels. (NEG) and Cryston (Asahi Glass);
As in glasses, the variability of the composition can • biocompatible, bioactive glass-ceramics based on
be used to design very different sets of properties of apatite and orthophosphate crystals for dental
glass-ceramics. Some examples are: restoration or bone replacement in medicine: Cera-
bone (NEG), Bioverit (Vitron), Ceravital, IPS
• photosensitive, etchable glass-ceramics based on Ag
Empress, etc.;
doping: Foturan (Schott), and Fotoform and Fotoce-
ram (Corning);
• highly transparent glass-ceramics and glass-
ceramics with specific dopings for temperature-
• machinable glass-ceramics based on mica crystals,
resistant fiber optic components, high-temperature
for example for electronic packaging: Macor and
loaded color filters, and luminescent solar collectors.
Dicor (Corning), and Vitronit (Vitron and Jena);
• glass-ceramics used as substrates for magnetic disks, An excellent overview and many details can be found
based on spinel or gahnite crystals, resulting in a very in [4.4].
3.4.8 Glasses for Miscellaneous Applications
Part 3 4.8
3.4.8.1 Sealing Glasses influence on the degree and distribution of seal stresses.
The material combinations for sealing between metals
Glasses are very well suited for the production of and ceramics recommended for Schott glasses are shown
mechanically reliable, vacuum-tight fusion seals with in Fig. 3.4-32.
metals, ceramics, and mica. Some particularly favor-
able properties are the viscosity behavior of glass and Types of Sealing Glasses
the direct wettability of many crystalline materials by Sealing glasses may be classified by reference to the
glasses. As a result, the production technology for expansion coefficients of metals (e.g. tungsten and
such seals is characterized by uncomplicated procedures molybdenum) and alloys (Ni–Fe–Co, Ni–Fe–Cr, and
with few, easily manageable, well-controllable process other alloys) with which they are used. Hence sealing
steps.
A necessary condition for the stability and mech-
Optical path difference =^ Sealing stress (cm)
anical strength of glass seals is the limitation of the 1000
Tension
mechanical stress in the glass component at tem-
peratures encountered during production and use. To 800
ensure “sealability” (which means that the thermal con- 600
tractions of the two sealing components match each
other below the transformation temperature of the 400
glass), glasses of special compositions, called sealing
200
glasses, have been developed. Apart from sealability,
such glasses must very often fulfill other require- 0
ments such as high electrical insulation or special
optical properties. The sealability can be tested and –200
evaluated with sufficient accuracy and certainty by Compression
–400
stress-optical measurements in the glass portion of a test 100 200 300 400 500
Temperature (°C)
seal (ISO 4790).
Apart from characteristic material values such as Fig. 3.4-31 Influence of the cooling rate on the sealing
the coefficient of linear thermal expansion, transforma- stress in an 8516–Ni/Fe combination. The lower curve cor-
tion temperature, and elastic properties, the cooling rate responds to a low cooling rate; the upper curve corresponds
(Fig. 3.4-31) and the shape can also have a considerable to a high cooling rate
Ceramics Glasses Metals Solder glasses

Application range
α (20 °C/300 °C) Devitri- Vitreous

(10–6 K) fying and
composites
Fused silica
8228
2 8229 2
8230
3 3
8330
8448
G 017–002
4 8409 8487 8337 B 4
Part 3 4.8
8486
Tungsten
Hard porcelain 8449
KER 110/111
8447
8412 8250
5 Vacon 10, Kovar 5
8245
G 017–339
Molybdenum
8450
6 6
2954
8454
G 017–383
Vacon 20
8455 8436 G 017–508
G 017–393
7 Vacon 70 7
Steatite
KER 220/221
8593
Al2O3 ceramic 8456

Sapphire
G 017–340
8 8
8596
N 16 B
8465
8350 8512 8516

G 017–695
9 Platinum Vacovit 501 9

8531
Cu-sheathed wire
Forsterite 8405
8467
KER 225 8095 Vacovit 465–485

8490
8587
10 51–53 Ni–Fe 10
8468
51 Ni–1Cr–Fe
8470
Technical glasses Intermediate sealing glasses

Tried-out, unrestricted seals with stresses ≤ 8 N/mm2 at room temperature 11
Producible seals, limited with regard to size and geometry, with stresses
between 8 N/mm2 and 20 N/mm2 at room temperature
Fig. 3.4-32 Recommended material combinations for “graded seals”

Table 3.4-20 Special properties and principal applications of technically important sealing glasses, arranged according to their
respective sealing partners
Metal Glass Glass Principal applications

α20/300 number characteristics as sealing glass
(10−6 /K)
Tungsten 8486 Alkaline-earth borosilicate, high Lamp bulbs
(4.4) chemical resistance, high working
temperature. Suprax®
8487 High boron content, low melting tempera- Discharge lamps, surge diverters
ture
Molybdenum 8412 Alkaline-earth borosilicate, high chemical Lamp bulbs
(5.2) resistance. Fiolax® clear
8253 Alkaline-earth aluminosilicate glass Lamp interior structures, lamp bulbs
Molybdenum and 8250 High boron content, low melting tem- Transmitter tubes, image converters, TV
28Ni/18Co/Fe perature, high electrical insulation, low receiver tubes
(5.1) dielectric losses
8245 High boron content, low melting tempera- X-ray tubes
Part 3 4.8
ture, low X-ray absorption
28Ni/23Co/Fe 8454 Alkali–alkaline-earth silicate, sealable Intermediate sealing glass
(7.7) with steatite and Al2 O3 ceramics
8436 Alkali–alkaline-earth silicate, sealable Special applications
with sapphire, resistant to Na vapor and
alkalis
51Ni/1Cr/Fe 8350 Soda–lime silicate glass. AR glass Tubes
(10.2)
Cu-sheathed wire 8095 Alkali–lead silicate, high electrical insula- Lead glass, stem glass for electric lamps
(α20/400 radial 99, tion and tubes
α20/400 axial 72) ⎫
8531 Dense lead silicate, Na- and Li-free, ⎪
⎬ Low-temperature encapsulation of
low melting temperature
⎪
⎭ diodes
8532 High electrical insulation
52–53Ni/Fe 8512 Contains FeO for hot forming by IR, lead- Reed switches
(10.2–10.5) free
8516 Contains FeO for hot forming by IR, low Reed switches
volatilization, lead-free
glasses may be referred to as “tungsten sealing glasses”, 8245) characteristically contain relatively high amounts
“Kovar glasses”, etc. (see Table 3.4-20). of B2 O3 . These glasses have additional special proper-
Alkaline-earth borosilicate glasses (8486 and 8412) ties, such as high electrical insulation, low dielectric
and aluminosilicate glasses (8252 and 8253) have the loss, and low X-ray absorption, and meet the most
necessary sealability and thermal resistance to be par- stringent requirements for vacuum-tube technology and
ticularly suitable for the tungsten and molybdenum seals electronic applications.
frequently used in heavy-duty lamps. For Ni–Fe–(Cr) alloys, which are frequently used
Ni–Fe–Co alloys, which often substitute for molyb- in technological applications, as well as for copper-
denum, require that the transformation temperature be sheathed wire, glass groups belonging to the soft-glass
limited to 500 ◦ C maximum. Suitable glasses (8250 and category are recommended. Such glasses usually meet
certain special requirements, such as high electrical insu- Glasses for Sealing to Ceramics
lation (e.g. alkali–lead silicate, 8095) or an exceptionally Dielectrically superior, highly insulating ceramics such
low working temperature (e.g. the dense-lead glasses as hard porcelain, steatite, Al2 O3 ceramics, and forsterite
8531 and 8532). exhaust almost the complete expansion range offered
FeO-containing glasses (8512 and 8516) are fre- by technical glasses. Hard porcelain can generally be
quently used for hermetic encapsulation of electrical sealed with alkaline-earth borosilicate glasses (for ex-
switches and electronic components in an inert gas. ample 8486), which are also compatible with tungsten.
Hot forming and sealing are easily achieved by the ab- Glass seals to Al2 O3 ceramics and steatite are possi-
sorption of IR radiation with an intensity maximum at ble with special glasses such as 8454 and 8436, which
1.1 µm wavelength (Fig. 3.4-33). The presence of a pro- will also seal to a 28Ni/18Co/Fe alloy. Soft glasses with
portion of Fe2 O3 makes these glasses appear green. At thermal expansions around 9 × 10−6 /K are suitable for
appropriately high IR intensities, they require consider- sealing to forsterite.
ably shorter processing times than do flame-heated clear
glasses. Intermediate Sealing Glasses
Glasses whose thermal expansion differs so widely from
Compression Seals that of the partner component that direct sealing is
A common feature of all compression seals is that the impossible for reasons of stress must be sealed with
coefficient of thermal expansion of the external metal intermediate sealing glasses. These glasses are designed
part is considerably higher than the thermal expansion in such a way that for the recommended combinations
coefficients of the sealing glass and the metallic in- of glasses, the sealing stress does not exceed 20 N/mm2
Part 3 4.8
ner partner (conductor). As a result, the glass body is at room temperature (Table 3.4-21).
under overall radial pressure after sealing. This pre-
stressing protects the glass body against dangerous 3.4.8.2 Solder and Passivation Glasses
mechanical loads. Because the compressive stress of the
glass is compensated by a tensile stress in the jacket, the Solder glasses are special glasses with a particularly
jacket wall must be sufficiently thick (at least 0.5 mm, low softening point. They are used to join glasses to
even for small seals) to be able to permanently with- other glasses, ceramics, or metals without thermally
stand such tension. If the thermal expansion of the damaging the materials to be joined. Soldering is car-
metallic inner partner is lower than that of the seal- ried out in the viscosity range 104 –106 dPa s of the
ing glass, an additional prestressing of the glass body solder glass; this corresponds to a temperature range
results. Tsolder = 350–700 ◦ C.
One must distinguish between vitreous solder
glasses and devitrifying solder glasses, according to their
Transmission (%)
100 behavior during the soldering process.
Emission spectrum of a Vitreous solder glasses behave like traditional
90 tungsten–halogen lamp
80 glasses. Their properties do not change during soldering;
70
upon reheating of the solder joint, the temperature de-
pendence of the softening is the same as in the preceding
60
Thickness soldering process.
50 Unlike vitreous solder glasses, devitrifying sol-
0.5 mm
40 der glasses have an increased tendency to crystallize.
30 They change into a ceramic-like polycrystalline state
20 Thickness during soldering. Their viscosity increases by sev-
1 mm
10 eral orders of magnitude during crystallization so that
0 further flow is suppressed. An example of this time-
200 500 1000 2000 5000 10 000 dependent viscosity behavior is shown in Fig. 3.4-34
Wavelength (nm)
for a devitrifying solder glass processed by a spe-
Fig. 3.4-33 IR absorption of Fe-doped glasses compared cific temperature–time program. Crystallization allows
with the emission of a tungsten–halogen lamp at 3000 K a stronger thermal reloading of the solder joint, up to
(in relative units). The transmission of reed glass 8516 with the temperature range of the soldering process itself
thicknesses 0.5 mm and 1 mm is shown (e.g. glass 8596 has a soldering temperature of approx-
Table 3.4-21 Intermediate sealing glasses and the combinations of sealing partners in which they are used
Glass Sealing α20/300 Transform- Temperature at Density Tk100

no. partners a ation viscosity
temperature Tg 1013 dPa s 107.6 dPa s 104 dPa s
(10−6 /K) (◦ C) (◦ C) (◦ C) (◦ C) (g/cm3 ) (◦ C)
⎧ ⎫
KER 250 ⎪ ⎪
⎨ N16B
⎬
N16B Vacovit 501 − 8456 8.8 540 540 720 1045 2.48 128
⎪ ⎪
Platinum ⎫ ⎭ ⎩ (Red Line® )
KER 220 ⎪⎬
2954 KER 221 − 2954 6.3 600 604 790 1130 2.42 145
⎪
Vacon 20 ⎭
4210 Iron–4210 12.7 450 455 615 880 2.66 −
8228 Fused silica–8228–8229 1.3 ∼ 700 726 1200 1705 2.15 355
8229 8228–8229–8230 2.0 630 637 930 1480 2.17 350
8230 8229–8230–8330 2.7 570 592 915 1520 2.19 257
8447 8412–8447–Vacon 10 4.8 480 505 720 1035 2.27 271
8448 8330–8448–8449, 8486, 8487 3.7 510 560 800 1205 2.25 263

Part 3 4.8
8449 8486 − 8449 − 8447 4.5 535 550 785 1150 2.29 348
8487 8412
8450 8412–8450 − KER 220 5.4 570 575 778 1130 2.44 200
2954, 8436
8454 KER 221 −8454 − Vacon 70 6.4 565 575 750 1070 2.49 210
Al2 O3⎫
2954 ⎪⎬
8455 8436 ⎪ –8455–8456 6.7 565 − 740 1030 2.44 −
8454 ⎭
8456 8455–8456 − N16B 7.4 445 − 685 1145 2.49 −
8350
a Type designation of ceramics according to DIN 40685; manufacturer of Vacon alloys Vacuumschmelze Hanau (VAC).
imately 450 ◦ C and a maximum reload temperature of

log η (dPa s) Temperature (°C)
approximately 435 ◦ C). 14 500
The development of solder glasses (Table 3.4-22)
with very low soldering temperatures is limited by 12
Temperature
the fact that reducing the temperature generally means 450
increasing the coefficient of thermal expansion. This ef-
10
fect is less pronounced in devitrifying solder glasses.
It can be avoided even more effectively by adding 400
log η
inert (nonreacting) fillers with low or negative coef- 8
ficients of thermal expansion (for example ZrSiO4 or
350
β-eucryptite). The resulting glasses are called compos- 6
ite solder glasses. As a rule, the coefficient of thermal
expansion of a solder glass should be smaller than 4 300
the expansion coefficients of the sealing partners by 0 10 20 30 40 50 60
Time (min)
∆α = 0.5–1.0 × 10−6 /K.
Up to their maximum service temperature, solder Fig. 3.4-34 Variation of the viscosity of a crystallizing
glasses are moisture- and gas-proof. Their good elec- solder glass during processing
Table 3.4-22 Schott solder glasses

Glass α(20/300) Tg T at viscosity Firing conditions Density Tk100 εr tan δ
number 107.6 dPa s T thold
(10−6 /K) (◦ C) (◦ C) (◦ C) (min) (g/cm3 ) (◦ C) (10−4 )
Vitreous and composite solder glasses

G017-002a 3.6 540 650 700 15 3.4 − 6.8 37
G017-339a 4.7b 325 370 450 30 4.0 320 11.5 19
G017-383a 5.7b 325 370 430 15 4.7 325 13.0 15
G017-393a 6.5b 320 370 425 15 4.8 305 11.6 15
G017-340a 7.0b 315 360 420 15 4.8 320 13.4 14
8465 8.2 385 460 520 60 5.4 375 14.9 27
8467 9.1 355 420 490 60 5.7 360 15.4 29
8468 9.6 340 405 450 60 6.0 335 16.3 31
8470 10.0 440 570 680 60 2.8 295 7.7 15.5
8471 10.6b 330 395 440 30 6.2 − 17.1 52
8472 12.0b 310 360 410 30 6.7 − 18.2 47
8474 19.0b 325 410 480 30 2.6 170 7.2 5
Part 3 4.8
Devitrifying solder glasses

G017-508 6.5 365 − 530c 60 5.7 340 15.6 206
8593 7.7 300 − 520c 30 5.8 230 21.3 260
8596 8.7 320 − 450c 60 6.4 280 17.4 58
G017-695 8.9 310 − 425c 45 5.7 275 15.4 54
8587 10.0 315 − 435c 40 6.6 265 22.1 33
a Composite. b α20/250 . c Heating rate 7–10 ◦ C/min.
trical insulating properties are superior to those of many • A thinner passivation glass layer. Schott recom-
standard technical glasses. They are therefore also suit- mends a maximum thickness for this layer.
able as temperature-resistant insulators. The chemical • Slow cooling in the transformation range. As
resistance of solder glasses is generally lower than that a rough rule, a cooling rate of 5 K/min is suit-
of standard technical glasses. Therefore, solder glass able for passivation layers in the temperature range
seals can be exposed to chemically aggressive environ- Tg ± 50 K.
ments (e.g. acids or alkaline solutions) only for a limited • Use of composite glasses. Composites can be made
time. with an inert filler such as a powdered ceramic with
Passivation glasses are used for chemical and a very low or negative thermal expansion.
mechanical protection of semiconductor surfaces. They
are generally zinc–borosilicate or lead–alumina–silicate Properties of Passivation Glasses
glasses. The electrical insulation, including the dielectric break-
To avoid distortion and crack formation, the differ- down resistance, generally depends on the alkali content,
ent coefficients of thermal expansion of the passivation particularly the Na+ content. Typical contents are be-
glass and the semiconductor component must be taken low 100 ppm for Na2 O and K2 O, and below 20 ppm for
into account. If the mismatch is too large, a network of Li2 O. Heavy metals which are incompatible with semi-
cracks will originate in the glass layer during cooling or conductors are controlled as well. The CuO content, for
subsequent processing and destroy the hermetic protec- example, is below 10 ppm.
tion of the semiconductor surface. There are three ways Because the mobility of charge carriers increases
to overcome this problem: drastically with increasing temperature, a temperature
limit, called the junction temperature Tj , is defined up portional to the concentration, and we obtain Beer’s
to which glass-passivated components can be used in law,

blocking operations.
τi (λ) = exp − εn (λ)cn d , (4.43)
Various types of passivation glasses are listed in
Table 3.4-23. where ε now depends only on the wavelength and the
specific species or process n. In glasses, the extinc-
3.4.8.3 Colored Glasses tion is caused by electronic and phononic processes in
the UV and IR regions, respectively, and by absorption
In physics, color is a phenomenon of addition or sub- and scattering by ions, lattice defects, and colloids and
traction of parts of the visible spectrum, due to selective microcrystals in the visible region. Different oxidation
absorption or scattering in a material. The light transmis- states of one atom, for example Fe2+ and Fe3+ , must be
sion through a sample of thickness d at a wavelength λ treated as different species. Charge transfer and ligand
is described by Lambert’s law, fields are examples of multiatom mechanisms that mod-
ify the absorption characteristics. The position of the
τi (λ) = exp − εn (λ, cn , cm )d , (4.42) maximum-extinction peak depends on the refractive in-
dex of the base glass; for example, for Ag metal colloids
where ε is the extinction coefficient, which depends the position of the peak shifts from λmax = 403 nm in
on the wavelength and the concentration of the active Duran® , with n d = 1.47, to λmax = 475 nm in SF 56,
agents. For low concentrations, ε is additive and pro- with n d = 1.79.
Part 3 4.8
Table 3.4-23 Schott passivation glasses
Glass Type Typical α(20/300) Tg Pb Sealing Sealing Tj Layer
number applications content temp. time thickness
(10−6 /K) (◦ C) (wt%) (◦ C) (min) (◦ C) (µm)
G017-057 Zn−B−Si Sintered glass diodes 4.5 546 1–5 690 10 180 −
G017-388 Zn−B−Si Thyristors, high-blocking 3.6 550 1–5 700 5 180 ≤ 30
composite rectifiers
G017-953 Zn−B−Si 2.81 a 1–5 770 30 180 −
composite
composite
G017-984 Zn−B−Si Stack diodes 4.6 538 5–10 720 10 180 −
G017-096R Pb−B−Si Sintered glass diodes, pla- 4.8 456 10–50 680 5 160 −
nar and mesa diodes
G017-004 Pb−B−Si Mesa diodes 4.1 440 10–50 740 5 160 ≤ 30
G017-230 Pb−B−Si Power transistors 4.2 440 10–50 700 5 160 ≤ 25
composite
G017-725 Pb−B−Si Sintered glass diodes 4.9 468 10–50 670 10 180 −
G017-997 Pb−B−Si Wafers 4.4 485 10–50 760 20 180 −
composite
G017-209 Pb−Zn−B ICs, transistors 6.6 416 10–50 510 10 180 ≤ 5
G017-980 Pb−Zn−B Varistors 10–50 − −
Vitreous 6.5 393 520 30 − −
Devitrified 5.8 a 620 30 − −
G018-088 Pb−Zn−B Varistors 4.88 425 10–50 560 30 − −
composite
a Cannot be determined.
Colored glasses are thus technical or optical col- Table 3.4-25 DIN nomenclature for optical filter glasses
orless glasses with the addition of coloring agents.
A collection of data can be found in [4.17]. They are Band-pass filters BP λmax /∆λHW , where
widely used as optical filters for various purposes, such λmax = wavelength of maximum
as short-pass or long-pass edge filters, or in combina- internal transmission, and
tions of two or more elements as band-pass or blocking ∆λHW = bandwidth at 50%
filters. internal transmission.
Owing to the absorbed energy, inhomogeneous Short-pass filters KP λ50% , where
heating occurs (between the front and rear sides, and, es- λ50% = cutoff wavelength at
pecially, in the radial direction), which results in internal 50% internal transmission.
stress via the thermal expansion under intense illumina-
Long-pass filters LP λ50% , where
tion. Precautions have to be taken in the mechanical
λ50% = cutoff wavelength at
mounting to avoid breakage. The application tempera-
50% internal transmission.
ture T should satisfy the conditions T ≤ Tg − 300 ◦ C in
the long term and T ≤ Tg − 250 ◦ C for short periods. Neutral-density N τ, where τ = internal transmission
Prestressing may be necessary to improve the breaking filters at 546 nm.
strength in heavy-load applications.
The Schott filter glasses are classified into groups
listed in Table 3.4-24:
Internal transmission (%)
Part 3 4.8
Table 3.4-24 Groups of Schott Filter glasses 100

90
80
UG Black and blue glasses, ultraviolet-transmitting 70
60
BG Blue, blue–green, and multiband glasses 50
VG Green glasses 40 V2O5
30 Cr2O5
OG Orange glasses, IR transmitting 20 Co2O3
10
RG Red and black glasses, IR-transmitting 0
300 400 500 600 700 800 900
NG Neutral glasses with uniform attenuation in the Wavelength (nm)
visible Internal transmission (%)
100
WG Colorless glasses with different cutoffs in the UV, 90
80
which transmit in the visible and IR 70
60
KG Virtually colorless glasses with high transmis- 50
sion in the visible and absorption in the IR (heat 40
30 MnO2
protection filters) 20 NiO2
FG Bluish and brownish color temperature conver- 10
0
sion glasses 300 400 500 600 700 800 900
Wavelength (nm)
Internal transmission (%)
DIN has defined a nomenclature to allow one to see the 100
main optical properties for a reference thickness d from 90
80
the identification symbol (see Table 3.4-25): 70
Multiband filters and color conversion filters are not 60
50
specified by DIN. 40
30 CuO
20 Fe2O3
Ionically Colored Glasses 10
Ions of heavy metals or rare earths influence the color 0
300 400 500 600 700 800 900
when in true solution. The nature, oxidation state, and Wavelength (nm)
quantity of the coloration substance, as well as the type
of the base glass, determine the color (Figs. 3.4-35 – Fig. 3.4-35 Spectral internal transmission of BK7, colored
3.4-38, and Table 3.4-26). with various oxides; sample thickness 100 mm
Transmission (%) Transmission (%)

100 100
WG280 (3 mm)
80 80
Cr3+ NG4 (1 mm)
Cr(IV)
60 60
2+
Fe3+ Co Co2+
Cr(IV) GG19 (1 mm) Fe3+
40 40
GG457 (3 mm)
Fe3+ Fe2+
20 20
0 0
200 300 400 500 600 700 800 200 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
Fig. 3.4-36 Transmission spectra of yellow glasses Fig. 3.4-38 Transmission spectra of gray and white glasses
Transmission (%) Colloidally Colored Glasses

100 The colorants of these glasses are, in most cases, ren-
BG39 (1 mm) dered effective by a secondary heat treatment (striking)
80 of the initially nearly colorless glass. Particularly impor-
Part 3 4.8
VG14 (1 mm)
tant glasses of this type are the yellow, orange, red, and
60 black filter glasses, with their steep absorption edges. As
Cr3+ with ionic coloration, the color depends on the type and
40 concentration of the additives, on the type of the base
Cr(VI) Cu2+ glass, and on the thermal history, which determines the
20 number and diameter of the precipitates (Fig. 3.4-39 and
Table 3.4-27).
0
200 300 400 500 600 700 800
Wavelength (nm) Table 3.4-27 Colors of some metal colloids
Fig. 3.4-37 Transmission spectra of blue and green glasses Element Peak position nd Color
(nm)
Table 3.4-26 Colors of some ions in glasses
Ag 410 1.5 Yellow
Element Valency Color Cu 530–560 ? Red
Fe 2+ Green, sometimes blue Au 550 1.55 Red
Fe 3+ Yellowish brown Se 500 ? Pink
Cu 2+ Light blue, turquoise
Cr 3+ Green
Cr 6+ Yellow Transmission (%)
Ni 2+ Violet (tetrahedral coordination) 100
Ni 2+ Yellow (octahedral coord.) RG6 (2 mm)
80 RG610 (3 mm)
Co 2+ Intense blue
Co 3+ Green
Mn 2+ Pale yellow 60
Mn 3+ Violet
V 3+ Green (silicate), brown (borate) 40
Au0
Ti 3+ Violet (reducing melt)
Pr 3+ Light green 20
Nd 3+ Reddish violet
Er 3+ Pale red 0
200 300 400 500 600 700 800
Fig. 3.4-39 Transmission spectra of red glasses Wavelength (nm)
Doping with semiconductors results in micro-

Transmission (%)
crystalline precipitates which have band gap energies 100 e
in the range 1.5–3.7 eV, corresponding to wavelengths 90
e a KzSF N2
in the range 827–335 nm. The preferred materials are f b BK1
80 h h c BaSF2
ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe, which also g
70 d LLF1
form solid solutions. By mixing these dopants, any cutoff f e Ultran 20
wavelength between 350 nm and 850 nm can be achieved 60 d f IRG7
(Table 3.4-30). 50 g IRGN6
c h IRG2
40
b e
3.4.8.4 Infrared-Transmitting Glasses 30
a
20
The transmission in the infrared spectral region is lim- 10
ited by phonons and by local molecular vibrations and 0
their overtones. The vibration frequencies decrease with 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
increasing atomic mass. This intrinsic absorption has Wavelength (µm)
extrinsic absorption caused by impurities and lattice Fig. 3.4-41 Infrared transmission spectra of some Schott
defects, such as hydroxyl ions, dissolved water, and optical and special IR glasses; thickness 2.5 mm. The OH
microcrystals, superimposed on it. An overview can be absorption of the glasses may vary owing to differences in
found in [4.12]. the raw materials and the melting process
Part 3 4.8
Oxide Glasses Halide Glasses

The transmission is determined by the vibrations of the These glasses use F, Cl, Br, and I (halogens) as anions
common network formers [4.19] (Fig. 3.4-40). The vi- instead of oxygen. The transmission range is extended
brations of the network modifiers are found at longer up to approximately 15 µm [4.20]. The oldest halide
wavelengths. glasses are BeF2 , ZnCl2 , and AlF3 , which, however,
The heavy-metal oxide (HMO) glasses are transpar- have limited application owing to their toxicity, tendency
ent up to approximately 7 µm for a 1 mm thickness. But toward crystallization, and hygroscopic behavior.
often they show a strong tendency toward devitrification, Some new glasses use ZrF4 , HfF4 , and ThF4 as glass
which very much limits the glass-forming compositions. formers, and BaF2 , LaF3 (heavy-metal flourides, HMFs)
The transmission of some commercial glasses is shown as modifiers. They are often named after their cation
in Fig. 3.4-41. composition; for example, a glass with a cation compo-
sition Zr55 Ba18 La6 Al4 Na17 would be called a ZBLAN
glass.
Absorbance
1.0
0.9 Chalcogenide Glasses
0.8
These glasses use S, Se, and Te (chalcogens) as anions
instead of oxygen. The transmission range is extended
0.7
up to approximately 30 µm. Stable glass-forming re-
0.6 gions are found in the Ge−As−S, Ge−As−Se, and
0.5 B Si Ge Te Bi Ge−Sb−Se systems; an example of a commercial glass
0.4 is Ge30 As15 Se55 .
0.3 A combination of chalcogenides with halides is
0.2 found in the TeX glasses, for example Te3 Cl2 S and
0.1 Te2 BrSe.
The main properties of infrared-transmitting glasses
0
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 are compiled in Tables 3.4-29 and 3.4-30.
Wavelength (µm)
Fig. 3.4-40 Infrared absorbance of analogous oxide
glasses with different network-forming cations [4.18]; sam-
ple thickness 1.85 mm, except for Bi, where the thickness
was 2.0 mm
Table 3.4-28 Properties of Schott filter glasses
Glass DIN Reference Density Refractive Chemical resistance Transformation Thermal expansion Temp.
type identifi- thickness dr index nd Stain Acid Alkali temperature Tg α−30/+70 ◦ C α20/300 ◦ C coeff. TK
cation (mm) (g/cm3 ) FR SR AR (◦ C) (10−6 /K) (10−6 /K) (nm/K)
UG1 BP 351/78 1 2.77 1.54 0 1.0 1.0 603 7.9 8.9 −
UG5 BP 318/173 1 2.85 1.54 0 3.0 2.0 462 8.1 9.4 −
UG11 BP 324/112
+ BP 720/57 1 2.92 1.56 0 3.0 2.0 545 7.8 9 −
BG3 BP 378/185 1 2.56 1.51 0 1.0 1.0 478 8.8 10.2 −
BG4 BP 378/165 1 2.66 1.53 0 1.0 1.0 536 7.7 9 −
BG7 BP 466/182 1 2.61 1.52 0 1.0 1.0 468 8.5 19.9 −
BG12 BP 409/140 1 2.58 1.52 0 1.0 1.0 480 8.6 10.1 −
BG18 BP 480/250
+ KP 605 1 2.68 1.54 0 2.0 2.0 459 7.4 8.8 −
BG20 Multiband − 2.86 1.55 0 1.0 1.0 561 8.3 9.3 −
BG23 BP 459/232
+ KP 575 1 2.37 1.52 0 1.0 1.0 483 8.9 10.2 −
BG24A BP 342/253 1 2.72 1.53 0 3.0 1.0 460 8.5 9.7 −
BG25 BP 401/156 1 2.56 1.51 0 1.0 1.0 487 8.7 10.1 −
BG26 − 1 2.56 1.51 0 1.0 1.0 494 8.8 10.3 −
BG28 BP 436/156
+ KP 514 1 2.60 1.52 0 1.0 1.0 474 8.7 10 −
BG34 Color conversion 2 3.23 1.59 0 1.0 1.0 441 9.9 10.7 −
BG36 Multiband − 3.62 1.69 1 52.2 1.2 660 6.1 7.2 −
BG38 BP 487/334
Glasses
+ KP 654 1 2.62 1.53 0 2.0 2.0 466 7.5 8.9 −

BG39 BP 475/269
+ KP 609 1 2.73 1.54 0 5.1 3.0 321 11.6 13.1 −
BG40 BP 482/318
+ KP 641 1 2.67 1.53 0 5.1 3.0 305 11.9 13.7 −
BG42 BP 478/253
+ KP 604 1 2.69 1.54 0 2.0 2.0 477 7.3 8.7 −
VG6 BP 523/160 1 2.90 1.55 0 1.0 1.0 470 9.1 10.6 −
VG9 BP 530/114 1 2.87 1.55 0 1.0 1.0 470 9.2 10.6 −
VG14 BP 52487 1 2.89 1.56 0 1.0 1.0 470 9.2 10.6 −
GG385 LP 385 3 3.22 1.58 0 2 2.3 459 7.7 8.8 0.07
GG395 LP 395 3 3.61 1.62 0 1 2.3 438 7.7 8.6 0.08
GG400 LP 400 3 2.75 1.54 3 4.4 1.0 595 9.6 10.5 0.07
GG420 LP 420 3 2.76 1.54 3 4.4 1.0 586 9.6 10.5 0.07
4.8 Glasses for Miscellaneous Applications
Part 3 4.8
569
Part 3 4.8
Table 3.4-28 Properties of Schott filter glasses, cont. 570

Part 3
GG435 LP 435 3 2.75 1.54 3 4.4 1.0 605 9.5 10.5 0.07
GG455 LP 455 3 2.75 1.54 3 4.4 1.0 600 9.7 10.5 0.08
GG475 LP 475 3 2.75 1.54 3 4.4 1.0 594 9.8 10.6 0.09
GG495 LP 495 3 2.75 1.54 3 4.4 1.0 600 9.6 10.6 0.10
OG515 LP 515 3 2.76 1.54 3 4.4 1.0 597 9.7 10.6 0.11
OG530 LP 530 3 2.75 1.54 3 4.4 1.0 595 9.7 10.6 0.12
OG550 LP 550 3 2.75 1.54 3 4.4 1.0 597 9.6 10.7 0.13
OG570 LP 570 3 2.75 1.54 3 4.4 1.0 596 9.7 10.7 0.14
Classes of Materials
OG590 LP 590 3 2.75 1.54 3 4.4 1.0 599 9.8 10.6 0.15
RG9 BP 885307
+ LP 731 3 2.76 1.54 3 4.4 1.0 581 9.8 10.7 0.07
RG610 LP 610 3 2.75 1.54 3 4.4 1.0 595 9.8 10.7 0.16
RG630 LP 630 3 2.76 1.54 3 4.4 1.0 597 9.6 10.7 0.17
RG645 LP 645 3 2.76 1.54 3 4.4 1.0 597 9.6 10.7 0.17
RG665 LP 665 3 2.75 1.54 3 4.4 1.0 592 9.8 10.8 0.17
RG695 LP 695 3 2.76 1.54 3 3 1.0 599 9.6 10.6 0.18
RG715 LP 715 3 2.75 1.54 3 3 1.0 589 9.8 10.7 0.18
RG780 LP 780 3 2.9 1.56 5 52.4 1.0 571 9.7 10.7 0.22
RG830 LP 830 3 2.94 1.56 5 53.4 1.0 569 9.5 10.5 0.23
RG850 LP 850 3 2.93 1.56 5 53.4 1.0 571 9.5 10.5 0.24
RG1000 LP 1000 3 2.75 1.55 0 1 1.2 478 9.2 9.9 0.38
NG1 N 10-4 1 2.49 1.52 1 2.2 1.0 466 6.6 7.2 −
NG3 N 0.09 1 2.44 1.51 1 2.2 1.0 462 6.5 7.3 −
NG4 N 0.27 1 2.43 1.51 1 3.2 2.0 483 6.7 7.2 −
NG5 N 0.54 1 2.43 1.5 1 3.2 2.0 474 6.6 7.3 −
NG9 N 0.04 1 2.44 1.51 1 3.2 2.0 487 6.4 7.3 −
NG10 N 0.004 1 2.47 1.52 1 3.2 2.0 468 6.4 7.2 −
NG11 N 0.72 1 2.42 1.5 1 3.4 2.0 473 6.9 7.5 −
NG12 N 0.89 1 2.34 1.49 4 51.4 2.0 460 5.9 6.4 −
WG225 LP 225 2 2.17 1.47 3 51.3 3.3 437 3.8 4.1 0.02
WG280 LP 280 2 2.51 1.52 0 1 2.0 563 7.0 8.3 0.04
WG295 LP 295 2 2.51 1.52 0 1 2.0 557 7.1 8.3 0.06
WG305 LP 305 2 2.59 1.52 0 1 1.0 546 8.2 9.6 0.06
WG320 LP 320 2 3.22 1.58 0 1 2.3 413 9.1 10.6 0.06
KG1 KP 751 2 2.53 1.52 0 2.0 3.0 599 5.3 6.1 −
KG2 KP 814 2 2.52 1.51 0 2.0 3.0 605 5.4 6.3 −
KG3 KP 708 2 2.52 1.51 0 2.0 4.0 581 5.3 6.1 −
KG4 KP 868 2 2.53 1.51 0 2.0 3.0 613 5.4 6.2 −
KG5 KP 689 2 2.53 1.51 0 3.0 4.0 565 5.4 6.2 −
FG3 Color conversion 2 2.37 1.5 0 1.0 1.0 564 5.4 6 −
FG13 Color conversion 2 2.78 1.56 1 3.4 1.0 556 9.6 10.5 −
Table 3.4-29 Property ranges of various infrared-transmitting glass types
Glass type Transparency Refractive Abbe Thermal Microhardness Transformation Density

rangea index nd value expansion α temperature
(µm) νd (10−6 /K) HV Tg (◦ C) (g/cm3 )
Fused silica 0.17–3.7 1.46 67 0.51 800 1075 2.2
Oxide glasses 0.25–6.0 1.45–2.4 20–100 3–15 330–700 300–700 2–8
Fluorophosphate 0.2–4.1 1.44–1.54 75–90 13–17 − 400–500 3–4
glasses
Fluoride glasses 0.3–8.0 1.44–1.60 30–105 7–21 225–360 200–490 2.5–6.5
Chalcogenide 0.7–25 2.3–3.1b 105–185c 8–30 100–270 115–370 3.0–5.5
glasses
a 50% internal transmission for 5 mm path length.
b Infrared refractive index at 10 µm.
c Infrared Abbe value ν8−12 = (n 10 − 1)/(n 8 − n 12 ).
Table 3.4-30 Commercial infrared-transmitting glasses
Part 3 4.8
Glass type Glass Transparency Refractive Density Thermal Transformation Manufacturer
name rangea index n (g/cm3 ) expansion temperature
(µm) α (10−6 /K) Tg (◦ C)
Fused silica SiO2 0.17–3.7 1.4585b 2.20 0.51 1075 Corning, Heraeus,
General Electric,
Quartz et Silice,
Schott Lithotec
Silicates IRG7 0.32–3.8 1.5644b 3.06 9.6 413 Schott
IRG15 0.28–4.0 1.5343b 2.80 9.3 522 Schott
IRG3 0.40–4.3 1.8449b 4.47 8.1 787 Schott
Fluorophosphate IRG9 0.36–4.2 1.4861b 3.63 16.1 421 Schott
Ca aluminate 9753c 0.40–4.3 1.597d 2.80 6.0 830 Corning
IRG N6c 0.35–4.4 1.5892b 2.81 6.3 713 Schott
WB37Ac 0.38–4.7 1.669b 2.9 8.3 800 Sasson
VIR6 0.35–5.0 1.601b 3.18 8.5 736 Corning France
IRG11 0.38–5.1 1.6809b 3.12 8.2 800 Schott
BS39B 0.40–5.1 1.676b 3.1 8.4 − Sasson
Germanate 9754 0.36–5.0 1.664b 3.58 6.2 735 Corning
VIR3 0.49–5.0 1.869b 5.5 7.7 490 Corning France
IRG2 0.38–5.2 1.8918b 5.00 8.8 700 Schott
Heavy-metal oxide EO 0.5–5.8 2.31d 8.2 11.1 320 Corning
Heavy-metal ZBLA 0.30–7.0 1.5195b 4.54 16.8 320 Verre Fluoré
fluoride Zirtrex 0.25–7.1 1.50b 4.3 17.2 260 Galileo
HTF-1 0.22–8.1 1.517d 3.88 16.1 385 Ohara
Table 3.4-30 Commercial infrared-transmitting glasses, cont.

Glass type Glass Transparency Refractive Density Thermal Transformation Manufacturer
name rangea index n (g/cm3 ) expansion temperature
(µm) α (10−6 /K) Tg (◦ C)
Chalcogenide AMTIR1 0.8–12 2.5109e 4.4 12 362 Amorph. Materials
IG1.1 0.8–12 2.4086e 3.32 24.6 150 Vitron
AMTIR3 1.0–13 2.6173e 4.7 13.1 278 Amorph. Materials
IG6 0.9–14 2.7907e 4.63 20.7 185 Vitron
IG2 0.9–15 2.5098e 4.41 12.1 368 Vitron
IG3 1.4–16 2.7993e 4.84 13.4 275 Vitron
As2 S3 1.0–16 2.653e 4.53 30 98 Corning France
IG5 1.0–16 2.6187e 4.66 14.0 285 Vitron
IG4 0.9–16 2.6183e 4.47 20.4 225 Vitron
1173 0.9–16 2.616e 4.67 15 300 Texas Instruments
a 50% internal transmission for 5 mm path length.
b Refractive index at 0.587 µm.
c This glass contains SiO2 .
d Refractive index at 0.75 µm.
e Refractive index at 5 µm.
Part 3 4
References
4.1 S. R. Elliott: Physics of Amorphous Materials (Long- 4.11 A. Paul: Chemistry of Glasses (Chapman and Hall,
man, Harlow 1990) New York 1982)
4.2 H. Bach, D. Krause (Eds.): Analysis of the Composition 4.12 H. Bach, N. Neuroth (Eds.): The Properties of Optical
and Structure of Glass and Glass Ceramics (Springer, Glass, Schott Series on Glass and Glass Ceramics, 2nd
Berlin, Heidelberg 1999) 2nd printing printing (Springer, Berlin, Heidelberg 1998)
4.3 H. Bach (Ed.): Low Thermal Expansion Glass Ceramics 4.13 A. Winckelmann, F. O. Schott: Über thermische
(Springer, Berlin, Heidelberg 1995) Widerstandskoeffizienten verschiedener Gläser in
4.4 W. Höland, G. Beall: Glass Ceramic Technology ihrer Abhängigkeit von der chemischen Zusam-
(American Ceramic Society, Westerville 2002) mensetzung, Ann. Phys. (Leipzig) 51, 730–
4.5 N. P. Bansal, R. H. Doremus: Handbook of Glass 746 (1894)
Properties (Academic Press, Orlando 1986) 4.14 H. Scholze: Glass (Vieweg, Braunschweig 1965)
4.6 O. V. Mazurin, M. V. Streltsina, T. P. Shvaiko- 4.15 Schott: Schott Technical Glasses (Schott Glas, Mainz
Shvaikovskaya: Handbook of Glass Data, Part A, 2000)
Silica Glass and Binary Silicate Glasses; Part B, Single 4.16 H. R. Philipp: Silicon dioxide (SiO2 ) (glass). In: Hand-
Component and Binary Non-silicate Oxide Glasses; book of Optical Constants of Solids, ed. by E. D. Palik
Part C, Ternary Silicate Glasses, Physical Sciences Data (Academic Press, New York 1985) pp. 749–763
Series, Vol. 15, (Elsevier, Amsterdam 1983–1987) 4.17 C. R. Bamford: Colour Generation and Control in
4.7 R. Blachnik (Ed.): Taschenbuch für Chemiker und Glass (Elsevier, Amsterdam 1977)
Physiker, D’Ans-Lax, Vol. 3, 4th edn. (Springer, 4.18 W. H. Dumbaugh: Infrared-transmitting oxide
Berlin, Heidelberg 1998) glasses, Proc. SPIE 618, 160–164 (1986)
4.8 MDL SciGlass, Version 4.0 (Elsevier, Amsterdam) 4.19 N. Neuroth: Zusammenstellung der Infrarotspektren
4.9 INTERGLAD (International Glass Database), Version 5, von Glasbildnern und Gläsern, Glastechn. Ber. 41,
New Glass Forum 243–253 (1968)
4.10 S. English, W. E. S. Turner: Relationship between 4.20 J. Lucas, J.-J. Adam: Halide glasses and their opti-
chemical composition and the thermal expansion cal properties, Glastechn. Ber. 62, 422–440 (1989)
of glasses, J. Am. Ceram. Soc. 10, 551 (1927); J. Am. W. Vogel: Glass Chemistry (Springer, Berlin, Heidel-
Ceram. Soc. 12 (1929) 760 berg 1994)

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Glasses

3.4.1 Properties of Glasses –

The SiO2 tetrahedra are interconnected by the bridging

0 200 400 600 800 1000

3.4.1 Properties of Glasses – General Comments

worldwide. amization) coefficient of thermal expansion, often

3.4.2 Composition and Properties of Glasses

Table 3.4-2 Composition of selected technical glasses

Glass type Code a Main components (wt%) Minor components

Lead glass S 8095 57 28 Al2 O3 , Na2 O, K2 O

3.4.3 Flat Glass and Hollowware

Soda–lime glass Container glass Borofloat® 33

3.4.4 Technical Specialty Glasses

Non-alkaline-earth borosilicate glass: with SiO2

of aluminium. On the other hand, complex-forming

in [4.2, 15] and summarized in Tables 3.4-4–3.4-6. The

Table 3.4-4 Hydrolytic classes according to DIN 12111 (ISO 719)

Hydrolytic Acid consumption of Base equivalent Possible designation

Acid Designation Half loss in weight Alkali Designation Loss in weight

for many purposes, and its brittleness (susceptibility to

the rate of increase of the stress by a factor of 10 results

(Table 3.4-9) and various other values below Tg can be

Dielectric constant ε r Dissipation factor tan δ

–100 0 100 200

Dielectric Strength of up to 4 × 10−6 mm2 /N. High-lead-content glasses can

8405 Highly UV-transmitting soft glass

Table 3.4-11 Characteristic data of technical specialty glasses

8095 TP 9.2 435 435 635 985 3.01 60 0.22 0.9

Table 3.4-11 Characteristic data of technical specialty glasses, cont.

Tk100 Logarithm of Dielectric properties Refractive Stress- Classes of chemical

330 9.6 7.6 6.6 11 1.556 3.1 3 2 3

315 9.2 7.5 4.7 22 1.476 4.1 3 4 3

3.4.5 Optical Glasses

1.90 N-type and conventional type 46 1.90

Fig. 3.4-25 Abbe diagram of glass families

Table 3.4-13 Examples of glass codes

651562 LaCL2 651562 S-LAL54 720460 LAM61

847238 SF57 847238 FDS9 847238 TIH53 ∆Pi,g = (n i − n g )/(n F − n C )

can be derived from classical dispersion theory with

Table 3.4-16b Data for dn/dT

F2 1.51 1.56 − 2.78 9.34 10.4 0.250

N-KZFS2 6.77 1.31 − 1.23 3.84 5.51 0.196

Table 3.4-16d Internal transmission and color code

Internal transmission measured for 25 mm sample thickness at wavelength λ (nm)

0.990 0.986 0.984 0.977 0.963 0.940 0.920 0.780 0.210 − − − − − − −

Viscosity tion range is distinguished by a distinct bending

3.4.6 Vitreous Silica

Table 3.4-17 Electrical properties of vitreous silica

200–1000 ◦ C at 200 ◦ C 25 ◦ C 1000 ◦ C

Helium 0.20 0.025 3.9 × 10−17 2.4 × 10−8 5.5 × 10−5 20

In the temperature range between 600 and 700 ◦ C,

3.4.8 Glasses for Miscellaneous Applications

Ceramics Glasses Metals Solder glasses

α (20 °C/300 °C) Devitri- Vitreous

Al2O3 ceramic 8456

8350 8512 8516

9 Platinum Vacovit 501 9

KER 225 8095 Vacovit 465–485

Technical glasses Intermediate sealing glasses