MCIC-78-37/March 1978

Corrosion of Metals in Marine Environments

W. K. Boyd, Manager
F. W. Fink, Staff Metallurgist

Corrosion and Electrochemical Technology

Research Section
Battelle's Columbus Laboratories
Columbus, Ohio

METALS AND CERAMICS INFORMATION CENTER

A Department of Defense Information Analysis Center

Approved for pUblic release; distribution unlimited.

 ACKNOWLEDGEMENT

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objective is to provide a comprehensive current resource of technical information on
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for the U.S. Defense Supply Agency; technical aspects of MCI C operations are monitored
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 Preface

This report is a companion volume to MCIC-74-23, "Corrosion of Metals in the Atmosphere", also written by
Boyd and Fink. It was originally printed in 1970 as DMIC Report 245 and was reprinted in 1975 as MCIC-75-245R.
In 1977, this report was updated by extending its coverage to information on the performance of metals in marine
environments which had become available since July of 1970. This search was greatly facilitated by the availability
to MCIC of a continuous series of reviews on the corrosion of metals which were published by MCIC in its respective
newsletters entitled "Reviews of Recent Developments - Corrosion and Compatibility", "Review of Metals Tech-
nology-Corrosion and Compatibility", and the "Current Awareness Bulletin" over the periods ending in December,
1972, December, 1976, and September, 1977, respectively. Many of these reviewed articles, which were all prepared
by W. E. Berry of the Battelle Columbus Corrosion and Electrochemical Technology Section, were incorporated
directly into this report. D. J. Maykuth of the Materials Development Section, who edited DMIC Report 245, also
performed this same service in the 1977 review.

I n preparing the revision, all of the new information was appended to the original body of the report in a
section entitled "Update 1977" which follows the same organization and format as the original report. I n addition,
several new sections were included to deal topically with the seawater corrosion of fasteners, coated structural
metals, and composites and miscellaneous materials in addition to a review of recent desalination experiences with
metals and alloys.

It should be noted that, in the recent data review, numerous references were noted to studies conducted using
3 to 3-1/2 percent sodium chloride solutions, particularly those involving stress corrosion crack ing and fatigue crack
growth. While such sodium chloride solutions are not equivalent, for most purposes, to seawater, these references
have been included in the updated section in the belief that these results will be useful to the reader.

ii
 TABLE OF CONTENTS

INTRODUCTION .

THE OCEAN ENVIRONMENT .

Factors Affecting the Corrosivity of Seawater 4

Forms of Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 6

CORROSION OF METALS IN THE MARINE ENVIRONMENT. . . . . . . . . . . . . . . . . . .. 9

Carbon Steel . .. . . . .. . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 9
Low-Alloy Steels 17
Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 23
Nickel and Nickel-Base Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
Cobalt 40
Copper and Copper-Base Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 40
Titanium and Titanium-Base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
Aluminum and Aluminum-Base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
Beryllium .. , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 70
Magnesium 71
Special-Purpose Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 72
Refractory Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 72
Noble Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 73
Lead, Zinc, Cadmium, and Tin 74
Cathodic Protection 76

Update 1977 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 81
The Ocean Environment 81
Factors Affecting the Corrosivity of Seawater 81
Forms of Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 81
Corrosion of Carbon and Low Alloy Steels 81
Splash, Tide, and Submerged 81
Stress Corrosion Cracking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 82
Corrosion of Stainless Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 82
Splash, Tide, and Submerged 82
Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 83
Stress Corrosion Cracking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 83
Corrosion of Nickel-Base Alloys 84
Corrosion of Copper and Copper-Base Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 84
Corrosion of Titanium and Titanium-Base Alloys .. . . . . . . . . . . . . . . . . . . . . . . .. 85
Corrosion of Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
Atmosphere, Splash, Tide, and Submerged 85
Galvanic Attack and Velocity Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 86
Stress Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 87
Corrosion of Fasteners. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 88
Corrosion of Composites and Miscellaneous Materials 88
Corrosion of Coated Structural Metals 88
Coatings for Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 88
Coatings for Aluminum Alloys 89
Desalination Experiences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 90
Galvanic Attack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 90
Carbon and Low Alloy Steels .,. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 90
Stainless Steel 90

iii
 TABLE OF CONTENTS (Continued)

Copper-Base Alloys " 91

Titanium and Titanium-Base Alloys " 91
Aluminum-Base Alloys 91
Cathodic Protection 92

References 94

Appendix: Designations and Compositions of Selected Copper and Aluminum Alloys .... " A-I

iv
 INTRODUCTION electrolyte. Most of our common metals and alloys of construc-
tion are attacked by seawater or mist-laden sea air. Since the
behavior of materials may vary widely, depending on the
The scientific exploration and exploitation of the ocean exposure conditions, their performance is commonly discussed
depths is now proceeding at a greatly accelerated pace. Hydro- according to the specific environmental zone involved, name ly.
space activities in general are receiving national attention. atmosphere. splash. tidal, shallow ocean, deep ocean, and mud.
Typical areas of current interest can be roughly classified as A classification of typical marine environments is presented in
off-shore mineral development (oil, gas, sulfur, salt, diamonds, Table I
and coal); food production (fish, shellfish, plants, etc.); sea-
water extraction (magnesium, bromine, salt, and fresh water);
and off-shore meteorology (control of storms). Atmosphere

There has been particularly rapid progress in the develop- In the atmosphere, the intensity of the attack is
ment of equipment for deep-ocean investigation and under- influenced greatly by the amount of salt particles or mist
water activities. A new deep-diving technology has been whIch collects on the metal surface. Salt deposition varies with
developed complete with special-purpose submersibles, some wind and wave conditions, height above the sea, exposure, etc.
with external work arms for salvage, recovery, and exploration. Since s("a salts, expecially the calcium and magnesium chlorides,
New types of surface vessels also are rapidly being developed - are hygroscopic. there is a tendency to form a liquid film on
examples being hovercraft, hydrofoil ships, nuclear-powered the meT al surface. This is particularly true where the dew point
and jet-engine-powered vessels, and a great variety of work is reached dunng daily or seasonal weather changes. Typically,
boats and research vessels. In addition, the oil and gas industry the value drops off rapidly, decreasing to a negligible amount
has built large numbers of off-shore platforms, pipelines, under- about I mile inland, except during violent wind storms. In
water storage, and shore facilities. There are now over 14,000 some aleas, however, measurable salt may be found well inland.
off-shore steel structures in the Gulf area alone and more are
being added. Another factor that affects corrosion behavior is solar
radiation. This may stimulate photosensitive corrosion reactions
All this increased activity has taxed the ingenuity of the on metals like copper or iron and biological activity such as
designers of equipment and facilities which must be specially fungi, which help trap corrosive moisture and dust. Coral dust.
tailored to meet the hostile ocean environments. Before combin~d with sea salt, is particularly corrosive at tropical
choosing the materials of construction for an off-shore sites.
structure, ship, submersible, ocean-floor installation, or instru-
ment package, many factors must be considered. Among these The amount of rain, and the distribution dunng a given
are the initial cost of the materials, their efficiency in the time period, affects the corrosion rate in marine atmospheres.
intended design, the predicted lifetime of the materials as Frequent rain may tend to reduce the attack by rinsing off any
influenced by corrosion processes, function, and interactions of salt reSidue. In some cases, corrosion on the sheltered side may
stress. In most systems for ocean service, a major expense is be worse than that on the exposed side. since dust and air-
the maintenance required to keep the facility or equipment in borne s,;a-salt contamination is not washed off.
operation.
Fungi and molds may deposit on the metal and increase
Many materials when fabricated into a system deteriorate corrosi\ity malllly by holding moisture to the surface.
in seawater service in unexpected manners, unlike their pre-
dicted behavior established in laboratory saline solutions. The In general, the tropical marine environments are con-
chemical reactions of seawater with materials are complex. The sidered more corrosive than arctic marine environments. with
organic and living matter also present tends to complicate temperate environments somewhere in between. Temperature
further the manner in which materials fail. alone, t)f course, is not the entire explanation for the observed
differences, since the other factors involved in corrosion also
This report is presented in response to the large number vary with geographical location.
of requests received by DMIC for assistance in the selection of
materials for equipment or facilities to be used in the ocean
environment. Before reviewing the corrosion behavior of the Splash Zone
individual materials, the factors which affect their behavior in
seawater and in the marine atmosphere are reviewed. Materials in the splash zone are almost continuously wet
with well-aerated seawater. Biofouling does not take place in
The report is based on a review of selected literature the splash zone. Where the wind and ocean combine to provide
items, discussions with marine technologists, and information violent seawater conditions, the impinging water may add to
derived from Battelle's own research programs in the marine the destruction at the splash zone.
corrosion field. Reports dealing primarily with corrosion results
and deterioration behavior in actual ocean environments rather For a number of materials, particularly steel, the splash
than in laboratory simulations have provided the most reliable zone is the most aggressive of all the marine zones. The
information. entrained air bubbles in the seawater also tend to make it more
destructive in removing protective films or dislodging coatings.
Paint films normally deteriorate more rapidly in the splash
THE OCEAN ENVIRONMENT zon~ than in other zones.

Metals lIke stainless steels and titanium tend to be

Seawater covers more than 70 percent of the earth's resistant in the splash zone. since the well-aerated condition
surface and is the most abundant naturally occurring promotes paSSIvity.
 2

TABLE I. CLASSIFICATION OF TYPICAL MARINE ENVIRONMENTS

Characteristic Corrosion
_M_an_·_n_e_Z_o_n_e D_e_scription of._E_n_v_ir_o_n_m_e_n_t _ Behavior of Steel

Atmosphere (above Minute particles of sea salt are carried by wind. Sheltered surfaces may deteriorate more
splash) Corrosivity varies with height above water, rapidly than those boldly exposed. Top
wind velocity and direction, dew cycle, rain- surfaces may be washed free of salt by rain.
fall, temperature, solar radiation, dust, Coral dust combined with salt seems to be
season, and pollution. Even bird droppings particularly corrosive to steel equipment.
are a factor. Corrosion usually decreases rapidly as one
goes inland.

Splash Wet, well-aerated surface, no fouling. Most aggressive zone for many metals. e.g.,
steel. Protective coatings are more difficult
to maintain than in other zones.

Tidal Marine fouling is apt to be present to high- Steel at tidal zone may act cathodically (well)
water mark. Oil coating from polluted aerated) and receive some protection from the
harbor water may be pr~sent. Usually, corrosion just below tidal zone. in case of a
ample oxygen is availabk. continuous steel pile. Isolated steel panels
show relatively high attack in tidal zone. Oil
coating on surface may reduce attack.

Shallow water Seawater usually is saturated with oxygen. Corrosion may be more rapid than in marine
( near surface and Pollution, sediment, fouling, velocity, etc., atmosphere. A calcareous scale forms at
near shore) all may play an active role. cathodic areas. Protective coatings and/or
cathodic protection may be used for corrosion
control. In most waters a layer of hard shell
and other biofouling restricts the available
oxygen at the surface and thus reduces corro-
sion. (Increased stress on structure from
weight of fouling must be provided for).

Continental- No plant fouling, very much less animal

shelf depths (shell) fouling with distance from shore.
Some decrease in oxygen, especially in the
Pacific, and lower temperature.

Deep ocean Oxygen varies, tending to be much lower Steel corrosion often less. Anode consumption
than at surface in Pacific but not too is greater to polarize same area of steel as at
different in Atlantic. Temperature near surface. Less tendency for protective mineral
o C. Velocity low; pH lower than at scale.
surface.

Mud Bacteria are often present, e.g., sulfate re- Mud is usually corrosive, occasionally inert.
ducing type. Bottom sediments vary in Mud-to-bottom water corrosion cells seem
origin, characteristics, and behavior. possible. Partly embedded panels tend to be
rapidly attacked in mud. Sulfides are a factor.
Less current than in seawater is consumed to
obtain cathodic polarization for buried part
____o"-f~structure.
.- ' = - ' - - ' - - - - - - - - . _ - - - - - _.. _ - - - - - - - _..- ' - - - - -
 3
Tide Zone cathodic sit~s. Cathodic sites may also develop a calcium
carbonate-type mineral scale which provides protection similar
As with the splash zone, surfaces at the tide zone are in to that provided by biofouling.
contact with well-aerated seawater, for at least a part of the
day. The temperature of the metal surface is influenced by When seawater is diluted, as in harbors, an unsaturated
both the temperature of the air and that of the seawater, but is condition ""ith respect to calcium carbonate may develop
most apt to be close or equal to the temperature of the ocean. which prevents the formation of protective mineral scale. Pollu-
Tidal flow varies with location, and for such materials as steel, tion may make the water more corrosive and may also kill
greater tidal movement is associated with an increase in rate of marine life, thus preventing biofouling. The sulfide content or
attack. Marine organisms will settle on the metal surface in the ammonia cc,ntent of polluted waters tends to increase the
tide zone. In some cases, this may result in partial protection corrosion act ion of seawater on copper-base metals and steel.
of a metal surface as for steel or the local attack may be
accelerated as with stainless steels. The factors that affect the rate of corrosion in shallow
waters also are of importance for waters above the continental
One also has to differentiate between the behavior of shelf. The d,.~pth of these waters varies, ranging up to approxi-
isolated experimental panels in the tide zone, and the typical mately 1000 feet.
case, occurring in practice, where a structure such as a pile
extends from the atmosphere through the splash and tide zones The oxygen supply may be somewhat less as the depth
into the submerged and mud zones. For a continuous steel pile, incrcases, and this, as explained elsewhere, affects the corrosion
rapid attack takes place on that part of the surface just below behavior. Tempcrat.He tends to drop with depth, especially the
the water line, with the portion at the water line being the first 100 feet or so. This tends to reduce the rate of attack, as
cathode and receiving protection at the expense of the metal compared WI th that in warmer, well-aerated, surface water.
below. Since this zone is shifting continuously and ample
oxygen is available, cathodic polarization is not likely to The velocity may drop to low values in many localities,
develop as it may on a portion of the surface continuously often at a depth of 60 to 100 feet. Corrosion rates of metals
immersed. like steel usually are lower under the less aggressive conditions.

For the isolated-panel situation, the corrosion rate in the Beyond depths of 60 to 100 feet, any biofouling is
tide zone tends to be higher than that under the conditions entirely animal, since plants cannot exist below the depths to
described above, since the isolated panel does not receive which solar radiation penetrates. Usually there is less fouling as
cathodic protection during a portion of each day. one proceeds away from shore, since the major source of
animal embryos is trom breeding activities near the shore. Also
there usually is apt to be considerably less fouling with increase
Immersed Condition in depth at any given distance from shore.

The corrosion behavior of metals in seawater may be

classified into two major types, according to whether the corro- Deep Ocean
sion rate is controlled (I) largely by the reaction at the
cathode or (2) by the presence of a tightly adherent, thin The oxygen supply at great depths is usually sufficient for
oxide, passive film. Steel is the best example of a metal whose some corrosion to take place. At several sites off the Pacific
rate of attack is under cathodic control in seawater. Zinc and coast, oceanographers have established that a minimum level
magnesium also are examples. Passive metals arc best illustrated (of about 02 ml of oxygen per liter of seawater) of oxygen
by the behavior of titanium or the high nickel-chromium- exists at ab,)Ut 2,000 feet down, which may be characteristic
molybdenum alloys such as Hastelloy C. In some seawater of the entire ocean near the West Coast( I) (sec Figure I). This
environments austenitic stainless steels are passive. is ascribed 10 the consumption of oxygen by decaying micro-
organisms descendll1g slowly from the surface. At greater
The noble metals platinum, gold, and silver, for example, depths in these Pacific areas, bottom currents originating in the
do not owe their corrosion behavior to a passive film. They are Arctic supply oxygenated water.
inherently resistant by virtue of their thermodynamic char-
acteristics, or nobility. Waters used in the Navy's Tongue of the Ocean (TOTO)
deep-sea test program in the Atlantic have a high oxygen level
Much of the discussion here concerns the behavior of all the way to the bottom. Oceanographers explain the fact
plain-carbon steel, since (I) it is the most widely used material that the biological oxygen demand is much less in the Atlantic
of construction in marine service and (2) the factors affecting waters because the total population of microorganisms is much
its behavior have been studied in great detail. The rate of smaller. In other words, decaying organisms in these Atlantic
attack of this steel is largely controlled by the availability of waters do not exhaust the available oxygen supply. The varia-
oxygen at the cathode. The oxygen supply and other factors tion in oxygen with depth at the TOTO site is given in Table
pertaining to steel corrosion are discussed below. 2.(2)

At shallow depths, the oxygen supply is normally at or Another factor that affects corrosion is the change in pH,
close to saturation. Biological activity likewise is at a maximum as shown in Figure I. The lower pH found in waters at great
and includes both plant and animal life. The temperature at the depth may be partly explained on thermodynamic grounds,
surface is considerably warmer than at moderate or great since the pH is reduced by extreme pressure alone. However, it
depths and varies with geographical location. is also known that the carbon dioxide-calcium bicarbonate-
calcium carbonate equilibrium tends to be shifted; that is, the
Biofouling, particularly of the hard-shell variety, reduces dissolved calcium carbonate in the deep ocean tends to be
attack on steel by (I) reducing the velocity of oxygen-carrying slightly below saturation, while, conversely, at the surface it is
seawater and (2) acting as a diffusion barrier to oxygen at frequently supersaturated,(3) One would, therefore, expect that
 4
in deep waters, there would be less tendency to form a pro-
Oxygen, mill tective mineral scale, as compared with surface waters. It has
been observed, for example, that the consumption of sacrificial
o 2 3 4 5 6
anodes, for providing cathodic protection, is significantly
Surface 1--""-'~:~~':::~~~~f~F~ greater at extreme depths, e.g., 5,000 feet, than in surface
waters.

1,000
Mud Zone
~I
~/~~ The environmental behavior of the mud zone is complex,

'I ~
and studies have only been made in a few instances. The
~~ ~
physical, chemical, and biological properties of sediments can
be expected to influence corrosivity.
~ Ii
-
Q;
Q)

..r:::
a.
3/XX)
~I
~I
~

~
Bottom sediments, both shallow and deep, usually contain
bacteria. The sediments are anaerobic, and gases developed by
bacterial action include NH3, H2S, and CH4. The pressure may
Q)
increase the bacterial activity. The sulfate-reducing bacteria,
0
I ~
which also are found in soils, produce sulfides which are
~ t- PH corrosive to metals such as steel and copper.
4,000
I ~ ~
Practical experience with the mud zone comes from
~
I observations of off-shore structures, and with experimental
I piles driven in shallow waters. Steel often is attacked more

.
~
~
~
~
5/XX) slowly in the mud zone than in the seawater above. Polariza-
~~ tion by cathodic current is more readily achieved, largely
~
...~I ~
because of the restricted oxygen supply.

6,000
0 2 4 6 8 10 12 14 16 18 Factors Affecting the Corrosivity of Seawater
Temperature, C
33.0 33.2 33.4 33.6 33.8 34.0 342 34.4 34.6 34.8
Salinity, ppt Since seawater is a complex, delicately balanced solution
6.4 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 8.2 of many salts containing living matter, suspended silt, dissolved
pH gases, and decaying organic material, the individual effect of
each of the factors affecting the corrosion behavior is not
FIGURE 1. OCEANOGRAPHIC DATA TAKEN IN readily separated, as is the case for a simple salt solution.
THE PACIFIC OCEAN AT A SITE WEST OF PORT Because of the interrelation between many of the variables in
HUENEME, CALIFORNIA(l) the seawater environment, an alteration in one may affect the
Used with perm ission of U. S. Naval Civil Engineering Laboratory relative magnitude of others.

TABLE 2. HYDROGRAPHIC ASPECTS OF TONGUE- The factors which affect the amount and rate of corrosion
OF-THE-QCEAN WATER (ATLANTIC may be divided into chemical, physical, and biological. An
OCEAN)(2) overall summary of these environmental factors and their rela-
tion to iron corrosion is presented in Table 3.

Depth, Temperature, Salinity, Oxygen, The roles of oxygen, biological activity, temperature,
feet C 0/00 mill velocity, salinity, and pH are discussed in more detail in the
following paragraphs.
Surface 24.08 36.79 4.59
33 36.73 4.58
66 24.09 36.72 4.61 Oxygen
164 24.14 36.73 4.26
249 24.13 36.78 4.42 The dissolved oxygen content is a major factor affecting
331 24.14 36.79 4.42 the corrosivity of seawater. For many common metals, a higher
495 23.92 36.74 4.15 oxygen content is accompanied by an increase in the rate of
663 22.35 36.70 4.15 attack. This results from the fact that corrosion rate of local
820 19.27 36.56 4.13 anodes is dependent on the cathode reaction. Depolarization is
1158 17.31 36.36 3.92 more rapid with the increase in arrival of oxygen at the
1654 13.78 35.82 3.46 cathode, and this in turn is a function of the amount dissolved
1985 11.73 35.55 3.19 in the seawater and the velocity of flow at the surface. Water
2316 10.03 35.33 3.11 low in oxygen flowing at a high velocity could provide as much
2648 8.09 3.59 oxygen to the cathodic surface as water high in oxygen moving
3310 35.04 4.96 slowly past the surface.
4967 4.18 35.00 5.73
5100 4.12 35.00 5.26 The oxygen level in seawater may range up to 12 ppm( 4).
19567 4.0 5.73 Photosynthesis of green plants, wave action, etc., tend to
 5
increase the oxygen level, whereas the biological oxygen A variety of other biofouling organisms also are found
demand of decomposing dead organisms will reduce it. For a associated with the above types, some of which have a degree
given location, seasonal variation in oxygen level resulting from or more of mobility.
the above actions will, in turn, influence corrosion behavior.
Fouling is a major factor in the performance of marine
For metals like copper and iron, complete elimination of facilities. Structures in the water can be overloaded by the
oxygen will reduce the corrosion to negligible amounts. This extra weight of fouling; buoys can lose buoyancy, and fuel
method is under active study for control of corrosion in consumption becomes excessive on the badly fouled hulls of
desalination equipment. ocean-going vessels.

Metals depending on a passive film for corrosion protec-

tion, e.g., aluminum or stainless steel, often corrode rapidly Temperature
where the oxygen supply to the metal surface is restricted.
An increase in temperature normally is expected to speed
TABLE 3. FACTORS IN SEAWATER ENVIRONMENT(a) up a chemical reaction according to thermodynamic considera-
tions. This also would be the case for the corrosion reaction in
seawater wer~ it possible to hold all other variables fixed. Since
Chemical Physical BiologIcal
it is not normally possible to do this, the effect of temperature
has to be established indirectly. Oxygen solubility decreases
Dissolved Gases( I) VelocityC3) Biofouling(6) with increase in temperature; biological activity increases as one
Oxygen Air bubbles Hard-shell types goes from, e.g., cold arctic to warm tropic water; and the
Carbon dioxide Suspended sil t Types without hard shells chemical equilibrium involved in the precipitation of calcium
Mobile and semi mobile types
carbonate and magnesium hydroxide is altered so that
Chemical EquiJibrium(2) Temperature( 4 ) Plant Life calcareous scale is more likely to deposit on the metal as the
Salinity Oxygen generation temperature :s raised.
pH Carbon dioxide consumption
Carbonate solubility For temperature variations of a seasonal nature, iron,
copper, and many of their alloys show a higher rate of attack
Pressure(5) Animal Life during the warm months. On the other hand, when seawater is
Oxygen consumption heated at atmospheric pressure, it loses dissolved gases,
_ _ _ _ Carbon dioxide gener:atio_n_
especially oxygen, and it has a tendency to precipitate a pro-
(a) Using Iron as reference, the following trends are typical: tective scale. Both these actions tend to reduce the attack.
(I) Oxygen is a major factor in promoting corrosion.
(2) The tendency to form protective scale (carbonate-type) increases
with higher pH.
(3) Increasing velocity tends to promote corrosion, especially if
Velocity
entrained matter also is present.
(4) Temperature increase tends to accelerate attack. Many metals are sensitive to velocity effects in seawater.
(5) Pressure may affect corrosion, see text. For metals like iron or copper, there is a critical velocity,
(6) Biofouling can reduce attack, or promote local corrosion cells. beyond which corrosion becomes excessive. Passive metals, e.g.,
titanium, certain nickel-chrome-molybdenum alloys, and stain-
less steels tend to be more resistant in high-velocity seawater.
Biological Activity
Special forms of corrosion are associated with seawater
When a metal or other surface is first immersed in sea- velocity, e.g.. (I) erosion-corrosion caused by high-velocity silt-
water, a biological slime tends to develop in a matter of hours. bearing seawater; (2) impingement attack, where air bubbles are
Some authorities consider this film of living bacteria and other present, and (3) cavitation, where collapsing vapor bubbles
microorganisms to be attractive to embryonic fouling organisms cause mechanical damage and often corrosion damage as well.
looking for a place to settle. During an active season, a great
variety of organisms are found on an immersed surface. Usually
of most concern, from a corrosion point of view, are the sessile Salinity
organisms. They arrive at the slime-covered surfaces in minute
embryonic form and become firmly attached. Once attached, The major oceans of the world are completely connected
they rapidly transform to the mature form and become in the Southern hemisphere and mixing is continuous. The
immobile. Clapp, on page 433 of Reference 4, lists the follow- composition of seawater for a salinity of 35 %d*) is given in
ing most common forms of sessile fouling organisms: Table 4. It is important to note that, in most cases, the relative
proportion of salts does not vary appreciably in interconnected
(I) Organisms which build hard shells: seas. Variations in salinity in open-ocean surface water typically
(a) Annelids range from 32 to 37.5 0/00. In this range, the corrosion of
(b) Barnacles common metals is not appreciably affected.
(c) Encrusting bryzoa
(d) Mollusks *Salinity is defined as the total weight in grams of solid matter
(e) Corals. dissolved in 1000 grams of water. Thus, a salinity of 35 0/00
indicates a solid matter content of 35 grams per 1000 grams
(2) Organisms without hard shells of seawater or a solid content of 35,000 ppm. Salinity is
(a) Marine algae usually determined by measurement of chlorinity (i.e.,
(b) Filamentous bryzoa chloride-ion content in grams per 1000 grams of water) of the
(c) Coelenterates or hydroids seawater, and then derivation from the relationship S 0/00 =
1.805 Cl 0/00 + 0.030,(5)
(d) Tunicates
(e) Calcareous and silaceous sponges.
 6
TABLE 4. COMPOSITION OF SEAWATER AND IONIC Forms of Corrosion
CONSTITUENTS( 6)

G/Kg of Water of The factors which affect the corrosion of exposed metal
Constituent Salinity, 35 0/00 Cations, percent Anions, percent. surfaces in the different environmental zones have been
discussed in the preceding sections. When actual metal struc-
Chloride 19.353 Na+ 1.056 Cl- 1.898 tures are exposed to these ocean environments certain types of
Sodium 10.76 Mg++ 0.127 S04- 0.265 attack are most commonly experienced.(8) Often these are
Sulphate 2.712 Ca++ 0.040 HC03- 0.014 related to features in the design or metallurgy.
Magnesium 1.294 K+ 0.038 Br- 0.0065
Calcium 0.413 Sr++ 0.001 F- 0.0001 The most common forms of corrosion for environments
Potassium 0.387 are galvanic corrosion, pitting, and crevice attack. Sand or dust
Bicarbonate 0.142 Total 1.262 Total 2.184
erosion by wind action can augment corrosion in a marine
Bromide 0.067
Strontium 0.008 atmosphere, whereas seawater velocity effects such as impinge-
Boron 0.004 ment or cavitation may be important in an application involv-
Fluoride 0.001 ing underwater service.

In some of the more isolated seas, a great variation in

salinity is observed (see Table 5). Since the salinity variations
Galvanic Attack
are accompanied by other changes, the total effect on the
corrosion behavior has to be established in each case. Oxygen
Because seawater is an excellent electrolyte, severe corro-
solubility will be appreciably lower in the Caspean Sea than in
sion often occurs when two different metals are coupled
seawater of 35 0(00 salinity. Diluted seawater, as found in
together and exposed to a marine environment. One metal in
mouths of rivers, may be more corrosive even though the
the couple will be anodic to the other. The degree of attack
electrolyte itself may be less aggressive. Ordinary seawater is
depends partly on the relative position of the two metals in the
usually more saturated with respect to carbonate solubility; in
galvanic series for seawater. A galvanic series for flowing
diluted seawater, however, an unsaturated condition exists and
seawater is presented in Table 6. Usually the farther apart in
there is less tendency to form protective carbonate-type scale
the series, i.e., the greater the difference in potential, the
which, in effect, increases corrosivity. Marine-organism activity
greater will be the acceleration of the attack on the anodic
is reduced or eliminated in diluted seawater, and there may be
member of the couple. However, polarization effects tend to
less tendency to form a protective layer of biofouling.
alter the behavior. In seawater, coupling of titanium or stainless
steel to carbon steel tends to cause less acceleration of attack
than coupling of copper to steel, because the former two
TABLE 5. TOTAL SOLIDS IN OCEAN metals are more readily polarized than the latter. It can be
WATERS(7) shown for a metal like carbon steel, whose corrosion rate is
usually controlled by the total cathodic area available, that the
Total Dissolved ratio between the area of the cathode and the anode is
Body of Water Solids, ppm important. A small anode (e.g., steel) coupled to a large
cathode (e.g., copper) and immersed in seawater will result in a
greatly increased rate of attack. The reverse situation of a small
Baltic Sea 8,000
cathode coupled to a large anode will have only a minor
Black Sea 22,000 influence on the rate of attack.
Atlantic Ocean 37,000
Mediterranean Sea 41,000 To control or prevent the accelerated attack involved in a
Caspian Sea 13,000 galvanic couple, certain principles should be observed. First, the
32,500 possibility of breaking the electrical circuit by providing an
Irish Sea
insulating barrier at the junction of the two metals should be
considered. Second, if dependable isolation is not feasible, the
cathodic member of the couple should be covered with a
nonconducting protective coating. By reducing this area, or
pH eliminating the cathode entirely, corrosion is correspondingly
controlled in a safe manner. Under no circumstances should
The pH of seawater may vary slightly depending on the only the anode be painted. Any defect or holiday in the
photosynthetic activity. Plant matter consumes carbon dioxide coating then will ~esult in the entire cathodic area being
and affects the pH during daylight hours. The carbon dioxide coupled to a small 'area of-anode material, and extremely high
content in seawater is influenced, close to the surface, by the rates of penetration can be expected.
exchange with carbon dioxide in the atmosphere. The slight
daily shift in pH from, say, 8.0 to 8.2 has little direct effect on In the atmosphere, galvanic-couple corrosion is confined
the corrosion behavior; however, it can be a factor in to a short distance, usually a fraction of an inch, from the
calcareous-scale deposition, which affects the corrosivity. joint between the two metals. Under immersed conditions,
galvanic-couple corrosion may be significant for metals in
As pressure is increased, pH is reduced according to electrical contact as much as, say, 100 feet or more apart, such
thermodynamic considerations. Thus, at great depths, there is as between the bronze propeller and an exposed area on the
some evidence of less tendency for protective carbonate-type steel hull of an oceangoing vessel. Some examples of galvanic
scale formation. couples and their corrosion behavior are given in Table 7.
 7
TABLE 6. GALVANIC SERIES IN SEAWATER FLOWING TABLE 7. EXAMPLES OF GALVANIC
AT 13 FPS (TEMPERATURE ABOUT COUPLES IN SEAWATER
25 C)(9)
Metal A Metal B Comments

Steady-State Electrode
Potential, volts Cou~ That Usually Give Rise to Undesirable Results
(Saturated Calomel on One or Both Metals
Material Half-Cell)
Magnesium Low-alloy steel Accelerated attack on ~,
Zinc -1.03 danger of hydrogen
Aluminum 3003-(H) -0.79 damage on 13-
Aluminum 606l-(T) -D.76
Cast iron -D.6l Aluminum Copper Accelerated pitting on ..:h
Carbon steel -D.61 ions from -B attack -.
A.
Stainless steel, Type 430, active -D.57 Reduced corrosion on B
Stainless steel, Type 304, active -D.53 may result in biofouling
Stainless steel, Type 410, active -0.52 on B.
Naval rolled brass -DAO
Copper -D.36 Bronze Stainless steel Increased pitting on A.
Red brass -D.33
Bronze, Composition G -D.31 Borderline, May Work, But Uncertain
Admiralty brass -0.29
90Cu-IONi,0.82Fe -D.28 Copper Solder Soldered joint may be at-
70Cu-30Ni,OA7Fe -D.25 tacked but may have
Stainless steel, Type 430, passive -D.22 useful life.
Bronze, Composition M -D.23
Nickel -D.20 Graphite Titanium or
Stainless steel, Type 410, passive -D.15 Hastelloy C
Titanium(a) -D.15
Silver -D.13 Monel-400 Type 316 SS Both metals may pit.
Titanium(b) -0.10
Hastelloy C -0.08 Generally Compatible
Monel-400 -0.08
Stainless steel, Type 304, passive -0.08 Titanium Inconel 625
Stainless steel, Type 3 I 6, passive -D.05
Zirconium(c) -0.04 Lead Cupronickel
Platinum(C) +0.15

(a) Prepared by powder-metallurgy techniques. Sheath-

compacted powder, hot rolled, sheath removed, cold
rolled in air.
(b) Prepared by iodide process. Flow Condifion
'Stognonf Quiescent Moderate High
(c) From other sources. Alloy
. (crevicel
....:..::..:..:..:..c::..:..:....- Speed
---=..:'-'-
Aluminum
Crevice Attack
2024, 2219, 7178
7079, 7075, 3003 ~
This form of corrosion usually is most serious under
immersed conditions or in the splash zone. Metals that require
2014,6061, X7002,
5052, 5154, 1100 ~&
plenty of oxygen to continuously repair the breaks in the 5456, 5086, 5052 [':::':;.':' :.!,::~<:':.~. ;:;1
oxide film and thus maintain passivity tend to be susceptible to 5083

crevice attack in seawater. The relative susceptibility to crevice 90/10 CuNi

attack as depicted in Figure 2, shows stainless steels and some
of the aluminum alloys to be the most sensitive. 70/30 CuNi

If the oxygen in the stagnant seawater in the crevice is Monel, Ni fW0/#@·?:~:-\::~~·,·:.;;·:i~:;·:i~~

consumed in repairing new breaks in the passive film at a
Stainless steels ~@ffi:'..:.~·:.',~: . !::~
higher rate than fresh oxygen can diffuse in from the outside,
rapid corrosion tends to take place under the crevice, as Hastelloy C, Ti
illustrated in Figure 3. The driving force comes from a
differential aearation cell, with the surface outside the crevice Key C ~
in contact with oxygen-bearing seawater acting as the cathode. No Little or Moderate Considerable
attock nil attock attock attock
In accordance with electrochemical principles, the cathodic and
anodic currents must be equal. In the typical case, because of
the small area of the anode under the crevice, the current FIGURE 2. COMPARATIVE LOCALIZED ATTACK
density or rate of local attack can be extremely high. Once (CREVICE CORROSION AND PITTING) OF SOME
such a cell has been initiated it is difficult to arrest. IMPORT ANT MARINE ALLOYS AS A FUNCTION
OF SEAWATER FLOW CONDITIONS(10)
Used with permissio1 of Penton Publishing Company
 8

.!!!
E
35

0
/0
.c
a.
CIl
a
25
c::
E
::J
E
Oxide film breaks down because )(

of low oxygen; underlying metal c

:::!;
corrodes 15
CIl
C>
~
CIl
FIGURE 3. CREVICE CORROSION OF STAINLESS STEEL >
<I:
AT AN O-RING SEAL IN SEAWATER(lO)
Used with permission of Penton Publishing Company
Ellis and LaQue(l I) have demonstrated, using Type 430
stainless steel, the effect of enlarging the area external to the
crevice on attack. Figure 4 shows a straight-line relation
between weight loss and external area as might be expected
from Faraday's law. A plot of pit depth against area in Figure FIGURE 5. RELATION BETWEEN AVERAGE MAXIMUM
5 shows more scatter. This experiment was conducted in sea- PIT DEPTH WITHIN THE CREVICE VERSUS AREA OF
water flowing at I to 2 feet per second for 87 days. Crevice SPECIMEN OUTSIDE THE CREVICE( II)
attack can be controlled, as demonstrated here, by reducing the
area of metal external to the crevice. Cathodic protection will For copper and its alloys, crevice attack usually is not too
largely eliminate the attack by polarizing the cathodic area to significant in the atmosphere. However, under immersed condi-
that of the anode under the crevice. tions, a different form of attack from that with ferrous- or
aluminum-base materials is observed. Both in the crevice and
external surface, copper ions enter solution. The flowing sea-
water tends to remove copper ions from the external surface,
resulting in a differential metal-ion cell. The higher concentra-
10 tion of copper ions in the crevice becomes cathodic, and the
external area just outside the crevice becomes the anode.

Crevices are developed because of design features such as

'"c e
E
gaskets, washers, rivets, etc., and also may be formed by
marine fouling organisms, such as barnacles or mollusks,
C. settling on the surface.
<Ii
'"
0
....J
6
Pitting
.<:
.~ 0 Corrosion that develops in highly localized areas on a
CIl
~

/
4 metal surface, where the remaining metal surface often is not
CIl
C>
attacked to any great extent, is referred to as pitting. Pitting
~ on metals exposed to the atmosphere may be initiated by
CIl
> discrete salt particles or atmospheric contaminants. Surface
<I: 2
0 features or metallurgical factors, such as inclusions, breaks in
/ the protective film, segregation, and surface defects, also may
be involved in the initiation of pitting.
0L-...I._.l.-_ _....._ _...._ _.....I._ _--l_...I-...J
o 1.5 3 6 9 12 15 16.5 Under immersed conditions the envIronmental factors that
2
Area Outside Crevice, in. favor pitting usually are (1) relatively stagnant conditions, (2)
the presence of heavy metal ions such as copper (in the case of
FIGURE 4. AVERAGE WEIGHT LOSS OF SPECIMENS AS aluminum), and (3) local deposits of foreign matter. In respect
RELATED TO AREA OF SPECIMEN OUTSIDE THE to the third factor, pitting resembles crevice attack. Usually a
CREVICE(1I) metal susceptible to pitting also will be found susceptible to
crevice attack.
Crevice attack also is observed in the atmosphere. A con-
ductive film will form when both salt deposit and high Impingement
humidity or moisture are present. This continuous film of salt
water at the crevice is needed to permit the operation of the Many metals are sensitive to seawater velocity. Copper and
corrosion cell. steel are good examples. As the velocity is increased beyond
some critical point, rapid attack may ensue. Often. under Atmosphen,
turbulent conditions, air bubbles are entrapped in the water.
When the rapidly flowing seawater with bubbles impinges
against a metal surface, protective films may be destroyed and Steel. Mild steel corrodes in a marine atmosphere at rates
the metal may be locally attacked. Deposits on the metal ranging froll I to 30 mpy.(12) Some of this wide variation can
surface may promote local turbulence. A horseshoe-shaped be ascribed to fac~ors in the environment, some to variations in
groove often develops when the stream is diverted around an certain resi,lual elements in the steel, and some to the surface
object. The pattern of horseshoe "prints" is that of a horse condition C'f the s,eel as originally exposed.
moving upstream.
The first and most important factor influencing steel's
When there is suspended matter in the seawater, the com- performance in a marine atmosphere is the type of exposure.
bined erosion-corrosion can be much more severe than the sum Whenever the prevailing wind and surf combine to cause large
of the individual erosion and corrosion effects when each is amounts of spray to be entrained and transported to the metal
determined separately. surface. high corrosion rates are normally observed. The rate of
attack also may be affected by rainfall, humidity, temperature,
Impingement corrosion and cavitation damage arc some- solar radiation, dust, fungi, bird droppings, etc. Tropical marine
times mistaken for each other. In some cases both types of environmen ts usually are more severe than those in the tem-
damage may be involved. perate wne.( 13)

The amount of sea salt deposited on a surface decreases

Cavitation rapidly with increasing distance inland. Detectable amounts
have been observed from I to 10 miles inland. For example,
If the ambient pressure is reduced to the vapor pressure of Ambler anJ Bain( 4 ) made a study of the amount of salt
seawater at the seawater temperature, boiling occurs. Under particl"s ectlected on wet cloth in relation to distance from the
high-velocity conditions, local boiling is often observed in prac- coast of Nigeria. The salt collected was compared with the
tice. For example, seawater passing at high speeds over the CDITOSlOn nte of mild steel at each site. These data, presented
surface of an impeller or propeller will develop extremely low in Figure 1>, suggest that considerable salt is carried up to 10
pressures at sudden changes in section, such as at the blade miles inland. TIle surf at the Nigerian coast is very violent and
tips. Vapor bubbles are formed which may collapse again at a mist cloud some 30 feet high is plainly visible at all times
some other point downstream. The repeated pounding caused except Jurillg violent wind storms.
by the collapse of these vapor bubbles tends to promote, in
time, local compressive failures on the metal surface. Flakes of
metal are removed, leaving fresh active metal exposed to the
corrosive seawater. Thus, cavitation in seawater usually involves 10
both loss of metal by mechanical damage and by corrosion. Logos 50 yd
Cavitation often can be controlled by (I) reducing the
speed or velocity as in a ship's propeller or a pump impeller or
{:'
c:
o
Dungeness
Lagos 400 yd 75 ft uP>
~Llan~ystyd
(2) increasing the seawater pressure. E
......... ~ Lagos 200 yd
E
(,)
Lagos 400 yd
o Oshodi
Q
......
0> •
CORROSION OF METALS IN THE c:
o Bori.
"0;
MARINE ENVIRONMENT
~
8 01 •
Nk7aku Obanokoro
• Benin
Carbon Steel
• Makurdi

Plain-carbon steel is the most important metal in marine

service, and has been widely used for many years in marine 0.01 .....----~-----.....
10 100
------"_--..l
1000
construction. More recently, low-alloy steels of higher strength
have been finding increasing application. Related ferrous mate- Salinity, mg/m 2/day
rials such as cast irons, wrought iron, and ingot iron are FIGURE 6. RELATION BETWEEN CORROSION OF
sometimes used in special applications. Steels are selected for MILD STEEL AND SALINITY AT EXPOSURE SITES
marine service because of such factors as availability, cost, ease IN NIGERIA( 14)
of fabrication, design experience, and physical and mechanical Airborne salt was measured as salinity of water on a wet
properties. cylindrical cloth (wet-candle method).

The behavior of steel and other ferrous materials tends to Th~ same effect on the corrosion behavior IS also
show striking differences in the various exposure zones. Thus, illustrated by results from two corrosion test lots at Kure
one cannot apply the results from an atmospheric exposure to Beach, North Carolina. At the SO-foot lot (distance from mean
an application involving fully immersed conditions. The sec- tide line), one set of open-hearth iron panels showed an average
tions which follow give selected details of the corrosion of steel rate of attack of 31.5 mpy compared with 2.6 mpy for the
in each type of marine environment. 80D-foot lot.
 lG
At Cristobal, Panama Canal Zone, the NRL rack is 300
feet from shore and 55 feet above sea level. Panels at this 5
location show an attack rate of 2.3 mpy compared with 1.5
mpy for a similar steel at the 80(}-foot rack at Kure Beach. 4
From other experience at Kure Beach, N. c., it is known that
if the panels were raised from the normal rack height of a few
3
feet above sea level to the 55-foot elevation, the rate of attack
would increase and would be more nearly that observed at
Cristobal. Thus, location of the test site and the local climate 2 Total
immersion
both influence the corrosion rate. E
I
I /
E I / I
y---+---
Hadfield and Main(l5) reported the results of the British /
/ I
I /
/

Sea Action Committee. Four different heats of carbon steels // 1//

and three irons were exposed for 5 years to the marine atmo-
sphere at Aukland, New Zealand, Plymouth, England,
-en
0)
c-
O)
0
Colombo Auckland

Colombo, Ceylon, and Halifax, Nova Scotia. The average pene- 0) a. Ordinary Steels
0
tration for these seven materials is shown graphically in Figure ....0 6
7 (along with half tide and total immersion results), and pitting
behavior is presented in Figure 8. From a marine-corrosion .c::.
0- 5
standpoint, Halifax appears to have the mildest climate, and 0)
0
Colombo the most severe. For steels, the maximum depth of
pitting was at Colombo. The comparison also demonstrates the 4
wide differences in corrosivity among the three environmental
zones, namely, atmospheric, half tide, and total immersion. 3

2 Total
immersion
Toto I
immersion

E O"'-~-~~~-~~'--~-~"":-"""''''''''-­
E Colombo Auek land
or o.~-:-_~~L~_~"::::::===~~~2L_
g' Colombo Plymouth b. Rolled Irons
Ui
~ a. Ordinary Steels FIGURE 8. INFLUENCE OF CLIMATE AND CONDITIONS
OF 5 YEARS' EXPOSURE ON THE PITTING OF THE
ORDINARY STEELS AND ROLLED IRONS( 15)
2 Total
immersion TABLE 8. MARINE ATMOSPHERIC CORROSION
BEHAVOIR OF FERROUS MATERIALS AT
DIFFERENT MARINE SITES(l2,15)
Corrosion Rate, mpy
~1L.o~m":"b-o-~p~l-ym.lLou:"t~h-~A~u-c:rk2Ia:n:d==::::l~~.9l_­ Exposure L[a1ct!lateQ. From_~~lght Loss) . _

------------
Site __ __. ~~; __ ope~r;ea:~~S~~~n ~;~~~r)~_
b. Rolled Irons
Kurc Beach. N. C I 31.5
(80-foot lot) 1.5 to 3.5 47
FIGURE 7. INFLUENCE OF CLIMATE AND CONDITIONS Daytona Beach. Fla. 9.1
OF 5 YEARS' EXPOSURE ON THE GENERAL WASTAGE 1300-foot lot)
OF THE ORDINARY STEELS AND ROLLED IRONS(l5)
Sandy Hook. N. J. 3.3

Marine-exposure data from atmospheric test stations with Kure Beach, N. C. I 2.6
widely different climates are presented in Table 8. From a (800-foot lot) 1.5 nib) 1.6
study of the data, one is tempted to draw conclusions as to the 35 1.5
7.5 1.3
relative corrosivity of the marine environments in each local
region. In view of the above discussion on the location of test Block Island. R. I. 1.1 8.6(b) 2.7
racks, it is apparent that these results should not be interpreted 3.3 2.6
too literally. Halifax. Nova Sootia 1.2 0.62 1.2

The second factor that affects the performance of steel in Auckland. New Zealand 3.3 1.37 2.2
the marine atmosphere is the presence of residual elements, 2.03 4.7
Plymouth. England 82
such as copper, in the composition. Steels of the highest purity
tend to corrode at the maximum rate. Residual amounts of Colombo. Ceylon 17.9 17.3 IJ.O
copper, nickel, chromium, silicon, and phosphorus are found to
Cnstobal. Panama Canal 0 to 4 28 3.5
reduce the rate of attack. (9,12,16) These elements are inten- Zone (300-foot 10tl <l_tc>Jl _ 2.3 2.1
tionally added to develop strength, as will be discussed later in
the section on Low-Alloy Steels. Their presence affects the (a) Exposed for same perioo as carbon steel panels.
(b) High-purity iron with 0.02 percent copper.
 IJ
tightness of the rust coat and therefore its relative protective-
ness. Marine climates, where there is frequent wetting and
drying of the rust film, show this effect more markedly. Eillht- Year Corrosion Behavior, mils
Me'ol W.l. Low-C S'eel Cu Sleet Law-Alloy St..,
A third factor affecting the steel's performance in the AvO red in thlckne.. 22.1 20.4 17.6 9.0 to 10.1
marine atmosphere is the condition of the surface as exposed. AvO of deepu' 20 pits 29 34 32 12 to /8
For example, when hot-rolled steel is used for construction, the Deepes' pit 61 (P) 67- 66IP} 17 to 63IP}
mill scale is sometimes left on. The rate of penetration, based
on weight loss, and the depth of pitting are greater for a
P = perforated * probably perforated

mill-scaled surface than for, say, a pickled surface. This point is

illustrated by the results of 8 years' exposure of steel panels at
20 X Carbon steel at Cristobal and
Cristobal, Panama Canal Zone (see Figure 9).(17) When the 'f;l Kure Beach, N.C. (800 - ft lot)

•
surface is wet with salt spray, the mill scale will serve as a
relatively large cathode to the small anodes formed at breaks in Low -alloy steels
the scale, and this will result in intense local attack. 0
Wrought iron
0
.!!! 6 Copper steel
'E
etl 15
VI
Q)

~ -;; 25 Reduction in Thickness

e
.><
.~
~VI .J:::
VI 0 I--
~..J20 r-
e e
.>< -
.~~ e
.J::: . -
I--
e
~ 15
E
-
g
U
:J
'0
10

9 tt
Q)

10 r-"'" Il::
U'O Q)

-6~ 0>
~
& ~:J
Q)~
0>0
5 .!!
0

~ :;c
..
'0
.!!
0
~ ..
'0

:;c
Q)
>
<t
0 0
OU
~~ i 11: i a:: 5
~ 0 I...-~U-..L._=--U-..L....J
<t Exposed Exposed Exposed Exposed
4 yeors B yeors 4 yeors B years

FIGURE 9. COMPARISON OF EFFECTS OF MILLSCALE

AND PICKLED SUBSURFACES ON THE CORROSION
°oL.-...J..--I....----I....----.l.--------!e
RESISTANCE OF UNALLOYED LOW-CARBON STEEL 2 4 6
EXPOSED TO THE TROPICAL MARINE ATMOSPHERE Exposure Time, years
AT CRISTOBAL, CANAL ZONE( 17)
FIGURE 10. CORROSION RESULTS FOR WROUGHT IRON
AND 5TH LS AFTER EIGHT YEARS' ATMOSPHERIC
Wrought Iron. As made in this country in recent years,
EXPOSURE AT CRISTOBAL, CANAL ZONE(l2,13,17)
wrought iron is essentially a dead mild steel to which an
oxide-silicate slag has been added, while still molten. As is the
case with carbon steel, unprotected wrought iron is rapidly Splash and Tide
attacked by exposure to marine atmospheres. A comparison of
the behavior of wrought iron and steel is shown in Figure 10 Carbon steel corrodes particularly rapidly in the splash
for the first 8 years of the 16-year Navy exposure program at zone. The corrosion rates in the splash zone may be of the
Cristobal, Panama Canal Zone. (13,17) Carbon-steel behavior at order of ten times higher than those for the same steel in the
the 80(}.foot lot, Kure Beach, N. c., is also shown for compari- submerged condition. The ready access of oxygen and the fact
son. It is to be noted that the rate of penetration for steel and that the surface is continuously wet with seawater tends to
wrought iron after 8 years' exposure is quite similar. Both make the splash zone the most aggressive of marine environ-
materials showed considerable pitting. ments. Figure II gives the results of a short-term experiment in
which continuous 12-foot steel strips as well as individual steel
The excellent marine resistance of the older type of panels were exposed to the splash and tide zones. Note that
puddled wrought iron is frequently mentioned. Some wrought- one individual panel in the splash zone had a weight-loss
iron Coast Guard lighthouses at the Gulf and Florida coasts penetration of 24.1 mils or about 50 mpy.(l6) This was about
have lasted for over 100 years. It is reported that a frequent jive to six times that for the completely submerged panels.
maintenance application of a protective zinc and wool fat Note also that the continuous-strip panel evinced a rate of
mixture played a role in the good performance. (Both above attack in the splash zone about half that for an individual
and below the water line, good corrosion behavior was panel at the same location. Humble( 18), see Figure 12, shows
exhibited by these puddled-wrought-iron structures, although the typical corrosion profile of a steel pile after a 5-year
damage in the splash zone has had to be repaired several times exposure at Kure Beach, N. C. The splash zone shows more
durin~ the 100 years.)
than four times the rate of the immersed zone.
 12
Penetration, the submerged zone as will be discussed. Isolated panels, as
12 ~ ~_m~ils,-- __
shown in Figure 11, corrode almost as rapidly in the tide zone
c
o
~ G as in the splash zone. Longer exposure periods would have

~---------"P ~;~I EJ
·iii II 38
Q; demonstrated the protective effect of biofouling in the tide
E lone .

~
.5 -- ------{iVg-hTghtide ~~ -1.;;~r
, --- A graphical comparison of corrosion behavior in the tide
.c: I ft wide strip b 1.9 20.5 zone with that in the atmosphere and immersed c)ndition is

:*
1 1

fr I / --- ':hown in Figures 7 and 8. Note the maximum depth of pitting

: ......dl ft sq panel 2.1 I [14iJ 'or both carbon stcels and rolled irons at the tide zone at each

~ l~ mA~I;w-",.mt~:-rT:~l
site. Pitting shows a different order of severity from the gcneral
attack. For ordinary steels, panels exposed at Colombo show
the greatest weight loss but those at Halifax show the deepest
pitting.

~4 15JE] The results of exposing carbon steel at the mean tide level

~: 4! 1:~:l ~
in the Pacific Ocean off the Panama Canal Zone are shown in
Figure 13( 19). The average rate of penetration, calculated from
Q)

1 n
4.61
---~
B weight loss, was 2.7 mpy. The maximum pit depth, however,
was 98 mils for the 16-year period. Wrought iron tested for 8
z ~ 4.1 i 50 years showed a lower rate of attack, i.e., 1.4 mpy.
o0~-51-""10-""15--2.l.0-"'2'-5----"'S-'-ri-pI-'-P-an-•..I.I~
Penetration, mils (Calculated From Weight Loss)

FIGURE II. CORROSION OF STEEL EXPOSED ABOVE,

60r---------------------,
IN, AND BELOW TIDAL RANGE FOR lSI DAYS AT x Average pitting penetration
KURE BEACH, N.C.i 18 )
~
'--v--' Maximum pit depth, mils x
Used with perm ission of NatiorlJI Association of Corrosiun
o Average penetration calculated
t ngineers 50 l1 from weight loss
Zone I.
Atmospheric
Corrosion 40
Zone 2.
Splash Zone
Above High c
Tide .2 30-
Zone 3. ~
Q)
c
Tidal Q)
CL
20
Zone 4.
Continuously
Submerged 10

Mud line

o0~......-2~--4~---~8~---------16
Zone 5. Exposure Time, years
Subsoi I

FIGURE 13. CORROSION OF CARBON STEEL AND

Relative Loss in Metal Thickness WROUGHT IRON AT MEAN TIDE IN PACIFIC OCEAN
OFF PANAMA CANAL( 19)
FIGURE 12. CORROSION PROFILE OF STEEL PILING
AFTER 5 YEARS' EXPOSURE IN SEAWATER AT *R c is the final rate based on the tangent to the curve.
KURE BEACH, N.C. (INTERNATIONAL NICKEL CO.)( 18)
Used with permission of National Association ot Corrosion
Engineers
Biofouling may develop in the tide zone and confer some It should be emphasized that the splash zone and also, in
protection. (Barnacles for example can live alternately in and some cases, the tide zone are the sites where corrosion
out of the water, doing their feeding during the period when protection is most needed. Figures 14 and 15 illustrate the
they are submerged.) This helps explain the lower corrosion severely localized deterioration in the splash zone when no
rates in the tide zone. which often arc less than those in the provision is made for corrosion control. Either extra wall
splash zone, as can be seen in Figure 11 and in Figure 12. The thickness or a suitable protective coating should have been
tide 7.One receives some cathodic protection from the attack in provided.
 13
TABLE 9. CORROSION FACTORS FOR CARBON
STEEL IMMERSED IN SEAWATER

Factor in
.~_§~awale_.r __ .~~_~ffect on Iron and Steel

Chloride ion Highly corrosive to ferrous metals. Carbon

steel and common ferrous metals cannot be
passivated. (Sea salt is about 55 percent
chloride.)

Electrical High conductivity makes it possible for anodes

conductivity and cathodes to operate over long distances,
thus corrosion possibilities are increased and
the total attack may be much greater than
that for the same structure in fresh water.

Oxygen Steel corrosion is cathodically controlled for

the most part. Oxygen, by depolarizing
the cathode, facilitates the attack; thus a
FIGURE 14. LOCALIZED CORROSION IN SPLASH ZONE high oxygen content increases corrosivity.
OF BULKHEAD AND SHEET STEEL PILING ON
PACIFIC ISLAND(20) Velocity Corrosion rate is increased, especially in tur-
Used with permis::,ion of R. W. Roe and Parlr1f'r:; bulent flow. Moving seawater may
(I) destroy rust barrier and (2) provide
more oxygen. Impingement attack tends to
promote rapid penetration. Cavitation
damage exposes fresh steel surface to
further corrosion.

Temperature Increasing ambient temperature tends to ac-

celerate attack. Heated seawater may de-
posit protective scale, or lose its oxygen;
either or both actions tend to reduce
attack.

Biofouling Hard-shell animal fouling tends to reduce

attack by restricting access of oxygen.
Bacteria can take part in corrosion reaction
in some cases.

Stress Cyclic stress sometimes accelerates failure of

a corroding steel member. Tensile stresses
FIGURE 15. RESULTS OF NINE YEARS' EXPOSURE OF near yield also promote failure in special
IO-INCH BARE-STEEL H PILING AT BRIDGE PIER situations.
EXPOSED TO SEAWATER(20)
Used with permission of R. W. Roe and Partners
Pollution Sulfides, which normally are present in pol-
Submerged luted seawater greatly accelerate attack on
steel. However, the low oxygen content of
polluted waters could favor reduced
General Behavior. A summary of the factors which affect corrosion.
the rate of attack of carbon steel immersed in seawater is given
in Table 9. Since the corrosion behavior of steel is under Erosion of the steel surface by suspended
Silt and sus-
cathodic control, any action which affects the rate of deliyery matter in the flowing seawater greatly in-
pended
of the oxygen needed to depolarize cathodic regions can have a creases the tendency to corrode.
sediment
marked effect on the rate of attack. Normally a rust coating, a
calcareous scale, or a layer of biofouling will develop within a
few months on the surfa<:'? and provide an interfering barrier. Film formation A coating of rust, or rust and mineral scale
The decrease in corrosion rate with time for steel and wrought (calcium and magnesium salts) will interfere
iron is illustrated in Figure 16.(21) Biofouling and calcareous with the diffusion of oxygen to the
scale, no doubt, played a major role in the rapid decrease cathode surface, thus slowing the attack.
observed during the first year of ex posure for these
experiments.
 14
Specific Results. In panel tests in seawater at widely
8 different marine locations, average rates of penetration for steel
x Low C steel, Atlantic and other related ferrous materials were found to range from 2
o Wrought iron, Pacific - Canal zone to 5 mpy. For example, carbon-steel panels immersed for
7 • Low C steel, Pacific - Canal zone
>. periods up to 16 years in the Pacific Ocean near the Panama
0-
E Canal Zone showed an average corrosion rate between the 2nd
and 16th year of 2.7 mpy (Figure 18), while wrought iron
Q) 6
C showed 2.4 mpy between the 2nd and 8th year. Reinhart's
cr data showing the relation between corrosion rate and exposure
c time for ferrous metals is presented in Figure 16. A rapid
0 5
·in decline in rate after the first few years is evident.
t
0
<.)
4

90
3 0!--~2+00~--40.i-0--6.l.0-0--810:0::==I::!OOO::=O-- ~
X
Exposure Time, days
X Average pitting penetration
80
'-v-' Maximum pit depth, mils
FIGURE 16. CORROSION RATES OF STEEL AND
WROUGHT IRON IN SEAWATER AT SHALLOW 0 Average penetration calculated
from weight loss
DEPTHS(21)
70

For exposures where the velocity is high or turbulent,

protective deposits may be removed (or may not form) and the

~
more rapid oxygen delivery to cathodic areas allows the attack 60
to proceed at the anode sites at a greatly increased rate.
.!!!
Other factors which can be expected to increase the rate ·E

/
50
of attack are pollution, increase in temperature, and erosion by
C
suspended solids. Sulfides in polluted water promote local 0

attack, although their presence often is accompanied by less

oxygen. The temperature effect has been observed at
~
Q)
c 40
X
Wrightsville Beach, N. c., where the corrosion rate of steel in Q)
a..
seawater during the summer when the water temperature is 80 /'
to 85 F is 50 percent higher than that during the winter when /,/weight loss
30 /'
the water temperature is only 45 F, even though the total
oxygen content is lower. Oxygen-solubility data are plotted in ./
Figure 17. Tidal currents carrying silt or a slurry of sand have /
been observed to increase the attack on steel piling. 20

10
Temperature, C
o 4 8 12 16 20 24 28
0 ......1-......_ ...... ...... ......

012 4 8 16
Exposure Time, years

FIGURE 18. CORROSION OF CARBON STEEL AND

WROUGHT IRON CONTINUOUSLY IMMERSED IN
SEAWATER(19)

c Larrabee(23) has examined heavy sections of I D-inch H

:g, 4 piling taken from the sea after 23.6 years at the Santa Barbara,
>.
>< California, waterfront. For those sections between low tide and
o
2
5 feet above the ocean bottom, the attack rate was 1.5 ± 0.25
mpy. On the basis of this experience, the rate for steel exposed
under similar conditions would be expected to be no more
0 .....- ......- - -.....- -......- -......- - -......- -.... than 2 mpy. A summary of the average rate of penetration for
32 40 50 60 70 80
mild steel at various sites is given in Table 10.
Temperature, F

Hadfield and Main's results from their 5-year program,

FIGURE 17. SOLUBILITY OF OXYGEN IN SEAWATER show little difference from site to site for the average corrosion
OF 35 0/00 SALINITy(22) penetration, namely 3.4 to 4 mpy (see FIgure 7).(15)
 15
TABLE 10. CORROSION BEHAVIOR OF MILD CARBON Pitting attack tends to vary with the type of seawater
STEEL IMMERSED IN SEAWATER AT involved. In polluted San Diego Harbor( 25 ), corrosion pitting
VARIOUS SITES(19,23-25) for mild steel was found to be as high as 60 mpy in I year, see
Table 12. For steel piping in ships systems handling aerated
Exposure seawater pitting rate may range up to 50 mpy.(26)
Time, Penetration Rate,
Site years m.I2i'.-___ TABLE 12. PITTING CORROSION OF MILD STEEL
SUBMERGED IN SAN DIEGO HARBOR
Harbor Island, N. C. 3.3 2.1 (POLLUTED SEAWATER)(a)(25)
Kure Beach, N. C. 7.5 4.0
8 2.2 Exposure Penetration, mils
Time, No. of Avg. ot 5 Deepest Deepest Pit
Santa Barbara, California 23.6 1.25 to 1.75
days Panels Pits per Panel per Panel
Panama Canal (Pacific Ocean) 16 2.7
San Diego (polluted 1.5 2.2 155 6 13 to 24 18 to 30
seawater)
361 12 20 to 53 29 to 60

552 6 32 to 41 26 to 50
It may seem a bit surprising to find wide variations in the
rate of attack for steel in the atmosphere, and only minor (a) Weight-loss penetration averaged 2.2 mpy for this
differences in the behavior of steel under immersed conditions exposure.
at widely different geographical locations. In tropical waters,
the fouling is massive and tends to restrict the attack. In cold
waters, there is much less fouling and more oxygen. Such Pitting may be more intense if the mill scale is left on.
factors as these apparently are self-compensating, and help Mill scale, as in the atmosphere, is protective except at breaks
explain the observed similarity. in the scalf which become anodic. Because of the relatively
large cathodic area, the rate of attack at the local anodes is
intense.
Pitting Behavior. From the discussion so far one would
expect that all the designer has to do is to adopt about a The rate of attack is difficult to establish for cast iron
3-mpy corrosion allowance and not worry about the since it tends to graphitize (form of parting) in seawater. On
protection of a fully submerged steel structure. The pitting first inspection, specimens may appear in excellent condition.
behavior, however, must be considered, especially for a pipe, However, specimens which have been exposed for a period of
tank, or vessel where perforation results in failure. years usually show an outer soft layer of graphite and
corrosion pcoducts. Graphitized cast iron acts as a cathode
Pitting was noted in the 16-year experiments at the Canal when couplfd to, say, a fresh piece of steel or iron. Cast iron
Zone area of the Pacific, see Figure 18. For the first 2 years, has long life largely because of the heavy wall required to
the mean of 60 deepest pits (10 per panel) was about 53 mils produce a cast structure. Its actual rate of attack in seawater
or 10 times the average rate per year. After 2 years, the curve often is double that for steel.
for pit depth plotted against time is roughly parallel to the
weight-loss curve, with an indicated increase of about 2.2 mpy.
A pit with a depth of ISS mils, however, was observed on one Deep Ocean. Corrosion rates for carbon steels tend to be
of the replicate panels after 16 years. lower in the deep ocean than in surface waters. This is shown
in a recent summary of the behavior of iron and steel given by
Hadfield and Main show pitting behavior at four sites in Reinhart( I) (see Figures 19 and 20). In general, the rate of
Figure 8. A summary of this information is given in Table II. attack tend, to decrease with time. The average penetration,
The maximum pitting for the immersed condition is up to calculated from the weight loss for this series of experiments,
eight times the penetration rate calculated from the weight ranges from about 0.6 to 8 mpy. The low temperature and the
loss. very low rate of movement of bottom waters at both the
Atlantic and Pacific sites may help explain the lower rates
observed.
TABLE II. AVERAGE DEPTH OF MAXIMUM
PITTING FOR CARBON STEELS In the Pacific, the oxygen content of the seawater at
AND IRONS AFTER 5 YEARS' around 2,000 feet reaches a minimum; this is ascribed to the
EXPOSURE TO SEAWATER AT biological oxygen demand of decaying organisms and waste
DIFFERENT SITES( 15) products. In the Atlantic, oxygen levels are fairly high at all
depths. These differences are illustrated in the tabulation
below.
Average Pitting Depth, mils
Site Half Tide Total Immersion Depth, Oxygen Content, mils!1
f('et Atlantic Pacific
Auckland 13.4 87.5
Halifax 51.6 40.9 o 4.59 5.8
Plymouth 111.8 67.6 2000 3.11 0.25
Colombo 132.2 147.5 5000 5.73 1.0
 16
For steel structures standing in the mud, not only may
B the anodic and cathodic sites be a considerable distance apart,
but their location may shift somewhat with time.
7
4,500 ft
Low-Alloy Steels
6
>-
Q. Pacific, surface
E
5 Low-alloy high-strength steels contain small amounts of
.; such elements as copper, chromium, nickel, molybdenum,
C silicon, and manganese to provide added strength to the
0::: 4
carbon-steel base. Low-alloy steels are not sold on the basis of
c
0 ,::~ analysis but on the basis of their strength. The total of the
'iii :3
g added elements is usually around 2 to 3 percent. Most of the
u
0 low-alloy steels are outstandingly resistant, as compared with
2
5,600 ft plain, low-carbon steel, when exposed to the atmosphere. This
is especially true for industrial sites but there also is
5,500 ft considerable advantage in their use at marine locations.

0 The low-alloy steels show greatly improved resistance to

0
marine atmospheres, as a result of the development of a
fine-grained tightly adherent rust coat. The life of a low-alloy
steel structural part may be approximately five times as long as
FIGURE 19. CORROSION RATES OF CARBON STEELS that of a similar carbon steel part. Many low-alloy high-strength
IN THE ATLANTIC AND PACIFIC OCEANS AT steels also show superior performance in the splash zone. A
VARIOUS DEPTHS( I) good marine coating will last longer when applied to a properly
prepared low-alloy-steel surface than when applied to a carbon
steel substrate.

Under mean tide or fully immersed conditions, low-alloy

B r--.r--::::-7:,...,....----------------..., steels are no more resistant than carbon steel. For submerged
conditions, high strength is becoming an important
consideration. Under this design criterion, as will be seen, the
7 corrosion allowance for low-alloy high-strength steel must be
equal to or greater than that provided for carbon steel in
submerged service. This extra corrosion allowance tends to
6 offset the normal weight-saving advantage of high-strength
steels when they are employed in seawater.
>-
Q.
E 5 x
The characteristic behavior of low-alloy steels in the dif-
C
.;
~
Atlantic
ferent marine environmental zones is discussed separately in the
0::: sections which follow.
4 4,250 ft
c
.Q 0..........
V>
~ o .......... ....... _ Atmosphere
:3 ~----x
8 ...........
.... _<Atlantic, 5,600 ft
The first indication that composition affected corrosion
behavior was the observation some 55 years ago that
2
........... copper-bearing steels showed improved endurance in industrial
......"0
atmospheres. Later it was found that the copper-bearing steels
Pacific, 5,500 ft also performed better than plain-carbon steel at ocean sites.

Among others, the Navy and the ASTM have provided

information on the excellent behavior of copper-bearing and
low-alloy steels at marine sites. In the Navy program, after an
8-year exposure at Cristobal, Panama Canal Zone(l3,17), the
penetration rate calculated from weight loss, for low-alloy
steels ranged from 0.7 to 0.9 mpy, as illustrated in Figure 10.
FIGURE 20. CORROSION RATES OF LOW-CARBON At the 800-foot lot at Kure Beach, N. c., the 15.5 year results
STEELS AT VARIOUS LOCATIONS(I) indicated a rate of 0.3 mpy or less for low-alloy steels. Table
13 identifies the compositions of the steels used in the ASTM
tests and gives the weight losses determined. Selected results
Mud from Table 13 are plotted in Figure 21, which shows total
alloy content versus weight loss due to corrosion for the
Bottom conditions vary, but local attack is sometimes 15.5-year exposure. A wide range of compositions gave
observed just above the mud zone or in the bottom mud itself. improved resistance. In general, a total alloy content of 2.0
As in the soil, bottom mud is often aggressive to steel because percent for these types of steels seems to provide the
of the presence of sulfate-reducing bacteria. maximum return in performance.
 17

TABLE 13. CORROSION OF LOW-ALLOY STEELS IN A MARINE ATMOSPHERE - 15.5 YEARS AT 80D-FooT LOT,
KURE BEACH, N.C'< 12)

Approx.
Composition, percent Total Alloy Wei~ht
Manga- Phos- Molyb- Content, Loss a)
Group Description Carbon nese Silicon Sulfur phorus Nickel Copper Chromium denum percent mg/dm 2

High-purity iron 0.020 0.020 0.003 0.03 0.006 0.05 0.020

plus copper 0.020 0.023 0.002 0.03 0.005 0.05 0.053 0.1 43
0.02 0.07 0.01 0.03 0.003 0.18 0.10 0.4 29.8

II Low-phosphorus 0.040 0.39 0.005 0.02 0.007 0.004 1.03 0.06 1.5 17.3
steel, plus copper

III High-phosphorus 0.09 0.43 0.005 0.03 0.058 0.24 0.36 0.06 1.2 16.9
steel, plus copper 0.095 0.41 0.007 0.05 0.104 0.002 0.51 0.02 1.0 16.5

IV High-manganese 0.17 0.67 0.23 0.03 0.012 0.05 0.29 0.14 1.4 16.6
and -silicon
steels, plus
copper

V Copper steel, plus 0.072 0.27 0.83 0.02 0.140 0.03 0.46 1.19 2.9 6.3
chromium and
silicon

VI Copper steel, plus 0.17 0.89 0.05 0.03 oms 0.16 0.47 0.28 1.9 11.8
molybdenum

VII Nickel steel 0.16 0.57 0.020 0.02 0.015 2.20 0.24 3.0 9.4
0.19 0.53 0.009 0.02 0.016 3.23 0.07 3.9 9.2
0.17 0.58 0.26 0.01 0.007 4.98 0.09 5.9 6.1
0.13 0.23 0.07 0.01 0.007 4.99 0.03 0.05 5.4 7.5

VIII Nickel steel, plus 0.13 0.45 0.23 0.03 0.017 1.18 0.04 0.65 0.01 2.6 10.5
chromium

IX Nickel steel, plus 0.16 0.53 0.25 0.01 0.013 1.84 0.03 0.09 0.24 3.0 9.8
molybdenum

X Nickel steel, plus 0.10 0.59 0.49 0.01 0.013 1.02 0.09 1.01 0.21 3.4 6.5
chromium and 0.08 0.57 0.33 0.01 0.015 1.34 0.19 0.74 0.25 3.4 7.6
molybdenum

XI Nickel-copper 0.12 0.57 0.17 0.02 0.01 1.00 1.05 2.8 10.6
steel 0.09 0.48 1.00 0.03 0.055 1.14 1.06 3.8 5.6
0.11 0.43 0.18 0.02 0.012 1.52 1.09 3.2 10.0

XII Nickel-copper 0.11 0.65 0.13 0.02 0.086 0.29 0.57 0.66 2.4 10.5
steel, plus 0.11 0.75 0.23 0.04 0.020 0.65 0.53 0.74 2.9 9.3
chromium 0.08 0.37 0.29 0.03 0.089 0.47 0.39 0.75 2.4 9.1

XIII Nickel-copper 0.03 0.16 0.01 0.03 0.009 0.29 0.53 0.08 l.l 18.2
steel, plus 0.13 0.45 0.066 0.02 0.073 0.73 0.573 0.087 2.0 11.2
molybdenum

(a) A weight loss of 10 mg/dm 2 jI 5.5 years = 0.32 mpy.

 18
Effect of Copper. The addition of 0.3 percent copper to
mild steel would provide the maximum performance, as

N 20
I
3 29.8 • iJlustrated by Figure 23. Assuming that the attack is equal on
each side of the panel (which usually is not the case), the
E Group I X
Cl average rate of penetration for a 0.2 percent copper-bearing

XX~X
"- 16 steels
0>
E
steel would be about 1.4 mpy, or about half the rate for
open-hearth iron at this same site. As shown in Figure 24, an
",-
12
'"0 even lower rate of 1.1 mpy is obtained for 0.2 percent copper
........ X X X X X

-
-.J X--X X steel when the higher phosphorus content of Bessemer steel is
8 X-X
..r::::
X
used as the base.
0> X
'iii X
~ 4

01..- ...l.. 1.- ...l.. .....J

o 1 2 3 4
Approximate Total of Added Elements, weight percent
'"e
Q)
'"E E
FIGURE 21. CORROSION OF SELECTED LOW-ALLOY ~ .~
STEEL PANELS EXPOSED IN MARINE ATMOSPHERE 0>0.
(f)
•
AT THE 80o-FOOT LOT, KURE BEACH, N.C., FOR en
",..r::::
15.5 YEARS(l2) 0 u 30
-.J'::;
,
.£:(D 20
A general picture of the relative resistance of low-alloy 0>
.- >,
steels, copper-bearing steels, and pure iron in a marine atmo- Q).o

~v 10
sphere is shown in Figure 22. Endurance is shown as the time
required for a 4 x 6-inch panel to lose 12 grams. For a pure
0
iron panel, the time required was only 5 months, but for a 0 02 0.4 06 0.8 1.0
typical low-alloy steel panel, 32 months was required, or over 6 Copper Content, percent
times as long.
FIGURE 23. EFFECT OF COPPER CONTENT ON
CORROSION OF OPEN-HEARTH STEEL IN
MARINE ATMOSPHERE AT KURE BEACH, N.C.
"'eQ)
E
35 ~
(90 MONTHS' EXPOSURE)(9)
'u
Q)
~
0. r--
0.
(f) n; 0
U
301- 0.
0.
..r::::
u 0 ~
0
u
..s, v
0~ N 50
(D
25 l- ci '"e
>,
.0
V
L()
0
ci -Q) - Q)
'"
E E
o ·0 40
~ Q)
Q)

2
Q)
~

-Q) - '"
2
'"
0>0.
(f)

'"'"
0
-.J
20 0.
0.
0
2Vl n;
0.
>,
0
~.J::
o u
30
U 0. -.J'::;
e 0 0
1: 20
0> ~ 0 U I -'
.J::(D
'iii
~
15
0
~
0 r-- .:?
~ 0>
.- ,., 0.01 % copper destroyed
39 months - 185 grams
in
0 U ~.o 10
ci
E
~
- .J::
0.
e
v
C 0
(9
, 10 e ~Vl 0 02 04 0.6 0.8 1.0
N
, Copper Content, percent
~ ~ .J::
.E :J .~
Cl. I
.; 5- FIGURE 24. EFFECT OF COPPER CONTENT ON
~ r--
e CORROSION OF BESSEMER STEEL IN MARINE
0
E ATMOSPHERE AT KURE BEACH, N.C.
ar a (90 MONTHS' EXPOSURE)(9)
E
f=
Other information indicates that the major improvement,
over pure iron, is imparted by the first 0.03 percent of
FIGURE 22. RELATIVE DURABILITIES OF STEELS
copper.( 9 ) While there is no question of the increased benefit
IN A MARINE ATMOSPHERE(27)
Used with permission of American Society for Testing and from the addition of, say, 0.15 to 0.3 percent copper, some
Materials authorities recommend 0.4 to 0.5 percent for maximum
LaQue(9) published a series of curves showing the
performance.
individual benefit of copper, nickel, and chromium additions to
steel in his Edgar Marburg lecture. These data are for 7.5 years
of exposure at the 80o-foot lot, Kure Beach, N. c., and are
Effect of Nickel. Nickel additions to iron in the range of
summarized in the paragraphs which follow.
0.1 to 0.5 percent are less effective than copper additions in
promoting increased resistance to the marine atmosphere.
 19
However, higher additions of nickel, e.g., I to 5 percent, are TABLE 14. FIVE-YEAR WEIGHT LOSS AS DETERMINED
effective in promoting corrosion resistance, as call be seen in GRAPHICALLY FOR STEEL WITH COPPER,
Figure 25. In the experiment depicted in the figure, corrosion NICKEL, OR CHROMIUM ADDITIONS
was reduced 50 percent, as compared with that for iron, by the
addition of 2 percent nickel. Nickt'1 Chromium
Amount AddL'd, I) 0.2 o 0.2 o 0.2
wt

W<ight 1.0" ra > 50 34 28 48 42 3\ 25 32 30 " 17

5Oc---------------------, Panel, gram~

Alloy Combinations. In light of the above comparisons, it

is interesting to compare the effects on the marine resistance
when different alloy combinations of these and other elements
afC tried. Data for a series of low-alloy steels with total alloy
additions of up to 3.5 percent are presented in Figure 27.
Note, for example, that the corrosion resistance of Alloy M
with phosphorus, silicon, copper, nickel, and chromium addi-
tions is equivalent to that of Alloy F with negligible chromium
or silicon and higher levels of copper and nickel.

0 " - - - -....- - -..2 - - -....3 1 - . - - -.1.------'5 13 r - - - - - - - - - - - - - - - - - - - ,

0 4
Nickel Content, percent L

FIGURE 25. EFFECT OF NICKEL CONTENT ON ",. II

CORROSION OF STEEL IN MARINE ATMOSPHERE '"

(l)

~ 10
AT KURE BEACH, N.C. (90 MONTHS' EXPOSURE)(9)
."
.£;
1- ~l
,~

o 8
Effect of Chromium. The results for a series of alloys c J
containing chromium exposed to the marine atmosphere are o
t>::I 7
shown in Figure 26. Of importance to this discussion is the '0
effect of chromium additions of 2 percent or less as compared (~ 6 p
with the effect of similar additions of copper or nickel. Some
estimate can be obtained by reading off the values correspond-
(l)
01
o
Cl
N
ing to 0.2, 1.0, and 2.0 percent additions in Figures 24 through ~
~
4
26. With I to 2 percent addition of either copper, nickel. or
F
chromium, the corrosion rate is half that for an unalloyed al 3 M
carbon-steel panel (see Table 14). o.::1 2
A
U
Cl
U

0L-....._J.-....I._..l..........L_...........L_...l-_L..-...J
30 o 2 3 4 5 6 7 8 9 /0
Exposure Time, yeors

~ 25
'"E .,E FIGURE 27. EFFECT OF EXPOSURE TIME ON
o .- CORROSION OF STEELS IN MARINE ATMO-
~~20 SPHERE AT KURE BEACH, N.C.(28)
.Cfl
'"~ "5 15
...J..=; Composition, percent
- I Steel C Mn P S Si Cu Ni Cr
-g, ID 10
-_.

~~ ACa) 0.09 0.24 0.15 0.024 0.80 0.43 0.05 1.1

M(a) 0.06 0.48 0.11 0.030 0.54 0.41 0.5 I 1.0
r<l 5
F(a) 0.05 0.36 0.05 0.016 0.008 1.1 2.0 0.01
N(a) 0.11 0.55 0.08 0.026 0.06 0.55 0.28 0.31
......
0L-~_..J....--I_....1.._~~=:::l.-~ o(a) 0.16 1.4 0.013 0.021 0.18 0.30 0.50 0.03
o 12 14 16 18
percent rCa) 0.23 1.5 0.018 0.021 0.19 0.29 0.04 0.08
J(b) 0.19 0.52 0.008 0.039 0.01 0.29 0.05 0.05
L(b) 0.16 0.42 0.013 0.021 0.01 0.02 0.02 0.01
FIGURE 26. EFFECT OF CHROMIUM CONTENT ON
CORROSION OF STEEL IN MARINE ATMOSPHERE (a) High-strength low-alloy steels.
AT KURE BEACH, N.C. (90 MONTHS' EXPOSURE)(9) (b) Structural carbon and structural copper steels.
 20
The following groups of alloys, selected from Table 13, TABLE 15. COMPOSITION RANGES AND TYPICAL
show excellent resistance to the marine environment. COMPOSITION FOR HIGH-STRENGTH
LOW-ALLOY STEEL(a)

Alloy Content, weight percent

--- Weight Loss,
Composition, percent
Group Mn Si Ni Cu Cr Mo Total mg, dm 2
Element Range Typical
v 0.27 0.83 0.03 0.46 1.19 2.9 6.3
C 0.12 max 0.09
VII 0.58 0.26 4.98 0.09 5.9 6.1
Mn 0.20-0.50 0.38
x 0.59 0.49 1.0 0.09 1.01 0.21 3.4 6.5 P 0.07-0.15 0.09
S 0.05 max 0.033
XI 0.48 1.00 1.14 1.06 3.8 5.6 Si 0.25-0.75 0.48
eu 0.25-0.55 0.41
Cr 0.30-1.25 0.84
Ni 0.65 max 0.28
The example alloys from Groups V, X, and XI all are
about equal in total alloy content and performance. The Group (a) COR-TEN, U.S. Steel Corp.
VII example alloy, which features a high nickel content,
requires a higher total alloy content for the same resistance.

Tight Rust Formation. The benefit derived from the addi- c- - 80 - foot lot
tion of copper to steel exposed to an industrial atmosphere has
o
0.;:
- - 800 - foot lot
U
::J
been ascribed to the relatively insoluble basic sulfates, from the
S02 in the polluted air, which slowly develop in the rust film. "& 10
Carbon ",_
Additions of nickel, chromium, and - to a lesser degree - vo \.isteel..,.....
vo
silicon and phosphorus also were found to promote relatively Q)
c /.... High -strength
insoluble corrosion products.< 12) -'"
,/h/ low-alloy
'r'r
u steel
:c
.-A----- --~--~
f-- 5
The film of electrolyte on a panel at a marine atmospheric
"'C .. ....,. ...
site is high in chlorides, as one would expect, and lower in
sulfate. Since basic chlorides are not so insoluble as the basic ~
4) ,

~;. .
"
"..-

sulfates predominating in the hydrated iron oxide film ~ Y I I I

developed at industrial sites, one would not expect the film

8 °O~---"'-:5~--"""":I~O:-"--~1~5----2~O::---~25

developed at a marine site to be as protective. This is found to Exposure Time, years

be the case. The manner in which protective rust coats do form
under marine conditions is less understood than that in the FIGURE 28. COMPARISON OF CORROSION RESULTS
case of the industrial atmosphere. FOR VARIOUS STEELS IN MARINE ATMOSPHERE,
KURE BEACH, N. C,(29)
The formation of the rust coat is influenced by the
amount of salt mist carried in by the prevailing wind, rainfall,
sunshine, fungi, humidity cycle, dust, and, at some marine Pitting Attack. Some idea of the pitting performance of
sites, pollution. (Occasionally, a trace of S02 is present in the low-alloy steels in a severe marine climate is provided by the
atmosphere at the Kure Beach, N. C., lots, some IS miles from results from the Canal Zone site. A few of the exposure panels
Wilmington, the nearest city). As with carbon steel, the amount were perforated after 8 years, i.e., they showed greater than 63
of sea salt reaching the exposed surface and retained on the mils penetration. More typically, the deepest pits ranged from
surface greatly affects the rate of attack. 17 to 28 mils. Thus, a pitting allowance of 4 mils per year
would be conservative for a low-alloy-steel structure where
A well-known widely used alloy, Cor-Ten, has the com- perforation would cause failure,( 13, 17) Pitting data are
position range shown in Table IS. The ASTM specification tabulated above Figure 10.
covering this type of alloy does not provide for a specific
composition range. For marine service, a heat containing, say,
about 0.3 percent or more copper plus other additions such as Splash and Tide
nickel, chromium, and silicon, totaling at least 1. 5 percent, is
recommended. Ordinary steels, it will be recalled, corrode at extremely
high rates in the splash zone. When the exposure is such that
The 8(}'foot lot at Kure Beach, N. c., is one of the most the steel is almost continually wetted by surf and spray, the
corrosive test sites in use for marine-atmosphere testing. Even corrosion rate, based on weight loss, may average as high as 50
under these severe conditions, the low-alloy steel corrodes at a mpy at least initially.
lower rate than mild steel, see Figure 28. However, the indi-
cated rate for the low-alloy steel at this location is sufficiently In recent years it has been demonstrated that some low-
high to require protection in comparable environments for alloy steels undergo decidedly less corrosion at the splash zone
many applications. than does carbon steel.
 21
Some experimental results developed by Larrabee(30) are 0.----------,
presented in Table 16. At the 1.5- and 2.5-foot level, the loss T
in thickness for the carbon steel (BO 1468) was several times I
2 l
higher than that for the low-alloy steels. The alloy with 0.5 I
I
percent copper and 0.5 percent nickel (BO 1458) performed ,J> Approx High-Tide Line
particularly well. Although the plot of corrosion rate versus ;"---- ---
4
alloy content plot reveals some scatter in the data, as a general
rule the alloys with higher alloy content are proportionally
I
I"
•I
more resistant. I
.... .... ......
,
6

TABLE 16. AVERAGE DECREASE IN THICKNESS OF

c
Q)
E
....'P
-1-:--- --
..""
\
-..,---
20-FooT SPECIMENS AFTER 5 YEARS' ·u
Q)
a.
,,
~ Approx Low-Tide Line

EXPOSURE TO SPLASH, SEAWATER, AND MUD (j)

ZONES AT HARBOR ISLAND, N. c.C a )(30)

tI +
I
l
\ ~
\,,
,t,,
Decrease in Thickness, mils

801468 801458 801389 801457 1101459 801467 801456 E I

Average
Feet Sheet Ni-0.54% Ni-0.55% Ni-0.54% Ni-0.55% Ni-Q.28% Ni-0.28%
o
~
12
\,
From Steel Cu-0.52% Cu-O.22% Cu-0.20% Cu-0.20% Cu-0.20% Cu-O.22% ~
Top Piling P-0.12% P-0.17% P-O.II% P-0.14% P-0.14% P-0.17%
Q)
u
c
o 14 - -~+-ApprO:;: Grou,;d Line --2- /'
0.5(b)
1.5
2.5
9
87
98
II
13
17
12
16
9
30
24
18 21
10
21
-:;;
o ",/ I ,"
26 54 30 45 73
16 \\ _.- Measured max thickness
Approximate High-Tide Line
---- Measured min thickness

3.5
•
I - - Calculated avg thickness
(loss of weight)
~I
48 4 9 9
18
4.5 I I 2 I
5.5 o I 2
\
2 7
6.5 14 37 34 41 29 28 24
20 ~
Approximate Low-Tide Line
200 100 0 200 100 o
7.5 56 52 52 64 53 42 46 Residual Thickness After 5 Years, mils
85 45 41 44 49 42 38 34
9.5 52 38 41 49
801458 Steel 801468 Steel
49 43 32
105 53 48 40 49 42 41 32
11.5 45 39 35 49 42 37 32 FIGURE 29. COMPARISON OF CORROSION RESULTS
125 46 37 38 46 32 35 33 FOR TWO STEELS IN MARINE ENVIRONMENTS(30)
Used with permission of National Association of Corrosion
Approximate Ground Line Engineers

13.5 45 13 24 37 II 12 18
14.5 29 6 24 24 6 7 17
15.5 21 5 5 14 5 6 18
16.5 22 10 13 II 7 15 28
17.5 30 18
Submerged
10 12 28 31
18.5 30 12 15 10 22 25 34
19.5 27 15 24 17 39 38 31 Low-alloy steels show weight-loss penetrations in the range
==== of about 2.5 to 5 mpy when fully immersed in seawater. Thus,
Note- Approximate mean high tide 2 to 3 feet from tops of specimens; approximate
mean low tide about 6 feet from tops of specimens. a low-alloy steel offers no particular corrosion advantage over
(a) Specimens were exposed in 1951; figures quoted were calculated from losses in
carbon steel in applications involving submergence in the ocean.
weight.
(b) Unrealistic values because of partial protection from top supporting member.

Examples of corrosion rates for plain-carbon steel and

low-alloy steels after 8 and 16 years in the Pacific Ocean near
the Panama Canal are given in Table 17 and Figures 30, 31,
If carbon steel were used as sheet steel piling at this site, a and 32. The corrosion rate based on the weight loss of 2 and 5
corrosion allowance of 20 mpy would be required, and the percent nickel steels is similar to that of carbon steel, see
highest loss would be just above the high tide line. With Alloy Figure 30. However, in some instances, the low-alloy steels
Steel B01458, a 10 mpy corrosion allowance would be ample, evince rates of attack higher than that of carbon steel. Thus,
and this would provide for the attack in the submerged condi- the pitting penetration after 8 years on the nickel-bearing steels
tion. A graphical comparison of the 5-year results for these two (Figure 30) was much deeper than that for plain-carbon steel.
steels is shown in Figure 29. It is of particular interest to Also, over 16 years' exposure, the rate of attack for Alloys J
compare the shape of the minimum thickness curve for each and L was almost double that for mild steel (see Figure 31).
steel, which shows that the maximum attack for each zone is
less, on the whole, for the low-alloy steel. Other experiences
with low-alloy steels, especially in exposures where the wave Corrosion rates in the same range are found at Kure
action is vigorous, also indicate that they have considerable Beach, N. c., on the basis of 4.5 years of exposure (see Table
merit for splash-zone service. 18).
 22
TABLE 17. COMPOSITION OF STRUCTURAL STEELS AND
THEIR CORROSION RATES IMMERSED 14 FEET 90r-------------------,
DEEP IN THE PACIFIC OCEAN NEAR THE
Pitting Penetration (8 yrs), mils
PANAMA CANAL ZONE(l9)
Average A 1... J.. K. ...10..
Composition. perccp.t
_.. _ .. _ - - - - - - - - - - - - - -
CorrOSlCiIl
80 20 Deepest 66 82 80 56 97
- - -- -- - - - ------ RJ~~_,_mn
Type C >.In S, Cr ;\i eu Mo g Yr 16 Yr Deepest 86 152 175 139 P
--- ----

P= Perforotion of 1/4-in plote

Unalloyed 0.24 048 0040 0.027 0008 0.03 0051 0080 2.9 ;7 70
low carbun I A)

Copper 0,22 0.44 0.019 0.033 0009 Tracl' 0.14 0.35 3.0
bearing (0)

Sickel (2(ir,) (El 0.20 0.54 0.012 0023 o 18 015 1.94 0.63 38 27
• ..c
l"ickel (5%) (F/ 0.13 0.49 0.010 0.014 o 16 010 551 0.062 3.6 2 7 c "a;
o '"
:;:: ~ 50
Chromium 0.08 0.44 0.010 0.017 0.13 316 016 0.11 0.02 5.8 3.8 2
(3'k) (C) Q; E
c 0
Chromium G.GH 041 0.020 0.019 0.20 5.06 011 0.062 0,52 43 3.5
'" ~
o..l.L
(S'k) (H) 40
",-0
",,,,
Low alloy 0.08 0.47 0.007 0.026 0.060 None 1.54 0.87 3,0:; 7 0-
~~
(Cu-Ni)([J
'"
> :::J
<I:~ 30
Low alloy 0.15 0450113 0.026 0.47 0.68 0.49 0.42 53 48 0
(Cu-Cr-Si) (J)
u

Low alloy (K) 0.078 075 0.058 0.022 0.04 TrJct' on 0.61 o 13 .. , I 2.:-
(Cu-Ni-Mn-Mo) 20 (A) Mi Id - carbon steel
Low alloy 013 0.60 0.089 0.021 o 15 055 0.30 061 0059 5,) 50 Proprietary low - alloy steels
(Cr-Ni-Mn) (ll
--_ .. - - - ------------
(I) Cu - Ni
--------- - ---
10 (J) Cu-Cr-Si
(K) Cu-Ni-Mn-Mo
TABLE 18. CORROSION RATES OF STEELS IN SEAWATER (L) Cr-Ni-Mn
AT KURE BEACH, N.cJ28)
2 4 8 16

__~~er!1~ P~_~~!~_~~~~~_12~);~~h .S~rf~~~_~J2Z __ Exposure Time, years

~ - - _ .
Sleel
__ . ~ ~ -
1.5 Yr 25 Yr
-----------
4.5- -
Yr

Cor-Ten 4.2 4.3 3.8 FIGURE 31. SEA-lMMERSlON CORROSION OF

Tri~Ten 4.4 38 3.0 PROPRlETARY LOW-ALLOY STEELS( 19)
Ni-Cu 5.3 4.5 3.5 Used with p':~rrnissi()n of Natioil31 Association of Corrosion
Cr-Mo 1.4 1.6 1.6 F nqineers
Structural carbon 4.8 4.1 3.3

Pitting Penetration (8 yrs), mils

Mo 70 A
o(G)
Average J2.. J:i
20 Deepest 66 65 63
Deepest 86 78 90

052 60

Vl
(/!
(/! 0
=...J
E 50
:;:: ..... (A)
6Or---------------------, -",
c .- ~ ",
Pitting Penetration (8 yrs) , mils o '"
:;:~ "\ ~~/C steel
Average .A. l .£.. 2 'l,.;"
20 Deepest 66 94 117 Q; E 40 " ;"
c 0 ~~;"
Deepest 86 179 214 ~Lt ;"
;"
-0 ",
'"0"'-'"0 30 ;"
~ - ;"
'"
> u:::J ",
<I: '0
U /'/'
20
",
;"

10

o L..J1..-1..-_1..- .l...- ...L-...1

o 2 4 8 16
Exposure Time, years 2 4 8 16
Exposure Time, years
FlGURE 30. SEA-IMMERSION CORROSlON OF 2 PERCENT
AND 5 PERCENT NlCKEL STEELS( 19) FIGURE 32. SEA-lMMERSION CORROSION OF 3 PERCENT
Used with permission of Natior"al Association of Corrosion AND 5 PERCENT CHROMIUM STEEL( 19)
Engineers
 23
The early work reported by Hudson in England, and some Pitting Attack. The low-alloy steels. as a group, develop
results at Kure Beach, N. c., reported by LaQue, suggested deeper pits than does carbon steel. This is demonstrated by the
chromium additions were beneficial in seawater. In the many 8"year resulls from the Panama-Pacific exposures given in Table
experiments with the alloying elements usually considered for 21. The total penetration calculated from the weight loss
low-alloy steels, significant improvement was obtained only for (Column I) is compared with the average of the 20 deepest
chromium. There appeared to be a benefit with an addition of pits (Column 2) and with the deepest pit (Column 3). Assum-
about 3 percent chromium, particularly in retarding the rate of ing that the average of the 20 deepest pits is a more significant
attack over the first few years. More recent results, however, criterion than the deepest pit, one can compare this average
have demonstrated that for longer term exposures, the pitting value with the weight-loss penetration. The ratio of
chromium-bearing steels tend to corrode at rates considerably these two values for low-carbon steel at the 14-foot depth is
higher than that of carbon steel. See, for example, the 16-year 2.6. The range for the alloy steels, some of wh ich have higher
exposure data from the immersed condition in the Pacific weight-loss penetrations to start with, is 1.6 to 3.7. At the
Ocean off the Panama Canal plotted in Figure 32. After the mean tide level, the factor is lower, as is the pit depth for
third year, the corrosion rates for the 3 and 5 percent many of the steels involved in the comparison.
chromium steels are higher than that for the unalloyed carbon
steel. (I 9) For a given strength, the designer would be tempted to
specify a thinner wall for a low-alloy steel in a seawater
Since the resistance of low-alloy steels to the marine application. Since the corrosion rate is higher if anything,
atmosphere is often, say, two to ten times more than that of corrosion failure would be more rapid. Thus, from a design
ordinary carbon steel, it is of interest to inquire why this is not standpoint, the corrosion allowance for a low-alloy steel should
also true in seawater. The special conditions in the atmosphere be greater than that for a low-carbon steel. However, low-alloy
which lead to the formation of basic salts and subsequent tight steels have good strength characteristics and if protective coat-
rust coats on low-alloy steels are found not to operate in the ings were applied, these steels could be employed to advantage.
submerged condition. For low-alloy steels and carbon steel, the Cathodic protection must be applied wi th care for high-strength
rust coat formed in contact with seawater is closely similar in low-alloy steels since some tend to be more susceptible to
its effect of gradually slowing down the rate of attack with hydrogen damage than does carbon steel.
time, i.e., retarding the arrival of oxygen at cathodic surfaces.

In deep-ocean experiments conducted west of Port Stainless Steels

Hueneme, California, carbon steel and low-alloy steels (for
composition, see Table 19) show corrosion rates ranging from
0.5 to 2.0 mpy (see Table 20). These rates are lower than Stainless steels, as a class, find only limited application in
those that would be obtained in surface waters for the same marine environments. Their successful use is predicated on
period of time. A comparison of the Pacific Ocean results with control of the environment to maintain passivity or the use of
data from other sites is shown in Figure 33. The curve for protective measures to control local attack. Stainless steels
carbon steel in surface water at Harbor Island, N. C. is believed usually do well in marine atmospheres where the passivity can
to be typical of steels in such environments. be maintained by bold exposure of the surface. High-velocity
conditions in seawater also are favorable. In quiet seawater,
local attack ',uch as pitting is apt to cause failure.

TABLE 19. CHEMICAL COMPOSITION OF IRON AND STEELS, WEIGHT PERCENT( I)

..
.. _ - - - - -
--------------
-------. , ---, -------
----_._._---
-------------.-__ - ---
._---

Alloy C Mn P S Si Ni Cr Mo ClI V B- TI Other

--------

Wrought iron 0.02 0.06 0.13 0.01 0.13 2.5 slag

A1SI CIOIO 0.12 0.50 0.004 0.023 0.060
A1SI CIOIO 0.11 0.52 0.016 0.024 0.048
ASTM A36 0.24 0.70 0.011 0.027 0.055
ASTM A36 0.20 0.55 0.010 0.020 0.064
ASTM A387, 0.06 0.49 0.013 0.021 0.24 2.20 I.O:~
Grade D
HSLA No. I(a) 0.18 0.86 0.014 0.023 0.28 0.05 0.64 0.1i-: 0.047 0.0028 0.020
HSLA No. 2(a) 0.12 0.30 0.015 0.025 0.27 2.34 l.25 0.20 0.17
HSLA No. 3(a) 0.17 0.28 0.020 0.018 0.20 2.96 1.76 0.40
HSLA No. 3(a) 0.10 0.28 0.014 0.010 0.25 2.91 1.59 0.52
HSLA No. 4(a) 0.07 0.38 0.11 0.025 0.54 0.31 O.i-:i-: 0.2i-:
HSLA No. 5(a) 0.14 0.78 0.020 0.025 0.23 0.74 0.56 0.4:' 0.22 0.36 0.0041
A1SI4340 0.43 0.73 0.013 0.014 0.27 1.77 0.82 0.24
A1SI Type 502 0.06 0.48 0.020 0.010 0.33 4.75 0.5:
- - --- ------ --_ _ - - - - - - - , - -
..
- - - - . - - - - - - --- ------~
,----,--
(a) High-strength, low-alloy steel.
 24
TABLE 20. CORROSION OF WROUGHT IRON AND STEELS
IN DEEP-OCEAN WATER WEST OF PORT
8 HUENEME, CALIFORNIA( I)
x
j>e,ni.!~_'!!L~I1J1!!£L_~_ _ _ _ _ _ _ _ _
Atlantic Ocean - surface, Wrought Carbon ASTM flighcSl~l1Jltl1.-~~Alloy Ste~_~
Harbor Island I N.C. ~:_XP?S~T~_ Iron Steel A36 No. I No.2 ----_._.-----_._.
No.3 No.4 - -
No.5
-
7
:.9 yr at O.I)(a) 0.8 Oli 0.6(a) 0.5 07(3) I.I(a) 0.7(a)
5.300 f! 10.6' (0.7) (0.8)

(1.54 yr at 2.0 l.5(a) 1.7(a) 1.4(;iI 14(a) 14(a)

6 Carbon steel 2.340 ft ( 1.5) (1.7) (1.3, ( 1.5) (14)
CIOIO steel
HSLA No.2 (a) Sample showed crevice attack and, where measured, the amount of this attack is given in
C1010 steel parcnthese,s.
» A36 steel
Co 5
E HSLA No 4 TABLE 21. CORROSION PENETRATION OF ALLOY STEELS
HSLA No. 2 IMMERSED IN THE PACIFIC OCEAN NEAR THE
~ HSLA No 5 PANAMA CANAL ZONE AFTER 8 YEARS( 19)
0
a:: 4 HSLA No. I [Sec Table 17 for the Composition( 19)1

c
0 ________________ ~<:.!.!!!:tion mils
'Vi ___ M~_<!!)Ji~ 14 Ft Below Surface
, ~_~~~! __-_I_~_~!_ Ratio~
~ S~eeJ Type I
(; 3 23,2 25.5 H6 2.6
U Low carbon 40 65 1.7 66
D Copper bt=aring 24.2 45 63 19 27.7 63 108 1.3
Ni (2',7,) 22.9 39 50 1.7 31.7 94 179 3.0
2
NI (5":) 10.0 39 75 2.0 32,0 117 214 3.7
C; Cr(YI) 25.7 X::' 93 3.2 40.5 65 78 1.6
Pacific Ocean I
H Cr (5(}) 145 X8 99 3.6 32.0 63 90 2.0
5,500 ft
Low:Jlloy JY.7 70 134 18 26.4 81 152 3.2
(eu-Nil

Low:llloy ~1.1 47 54 " 43.2 RO 175 18

oL-_--J_ _--L._ _--l.._ _-l.._ _..J..._---J (Cu-Cr-Si)

o 200 400 600 1000 1200 K Low alloy

(Cu·Ni-Mn-Mol
24.8 40 94 1.6 15.5 56 139 2.2

Exposure Time,
Low alloy 10.5 )9 50 19 439 97 159 (p)(C) 2.1
(Cr-Ni·Mn)

(a) Ratio of <Ive-rage of 20 deept~t pits to weight-loss penetration. The higher the number, the
FIGURE 33. CORROSION RATES OF LOW grtater is the pining tendency in relation to the corrosion rate.
ALLOY STEELSO) Cb) 1 "'- .::alcul<lted from weight loss
::' ;;; JH:HgC of 20 deepest pits

See Table 19 for compositions. 3;;; deepcst pit.

(l'I P ;;; completdy perforated.

Stress-corrosion-cracking failures also have occurred. How-

ever, high-strength stainless steels, when correctly chosen,
strengthened, and aged will perform well in marine Weight Loss Deepest Penetration
atmospheres. , 30
(8 Years Exposure) (8 Years' Exposure)
10
25
Atmosphere
» 2!
Co
E 'E 20
In general, the three grades of stainless steels, namely,
c-
martensitic, ferritic, and austenitic, have good to excellent vi
<J) .!:? 15
resistance in marine atmospheres. The austenitic grades are 0
...J ~

-
5
preferred because of their greater resistance to staining. At 4i
.c c
first, a superficial yellow stain develops, but after a few years it 10
may become reddish in color. It can be readily removed with
01
'"
c..
'"
~
metal polish.
5

Corrosion rates for the austenitic grades are low, and (~)(O)(O) I-- No pilllnQ-.l
pitting or crevice attack is not normally experienced in the 0 0
A 8 C E F G A 8 C E F G
atmosphere if simple precautions are taken.

A Type 304 panel exposed at the 800-foot lot at Kure FIGURE 34. COMPARISON OF CORROSION DAMAGE OF
Beach, N. c., corroded at a rate of less than 0.1 mpy. At the STAINLESS STEEL, PHOSPHOR BRONZE, AND LOW-
80-foot lot, Type 304 panels showed somewhat more staining ALLOY STRUCTURAL STEEL IN TROPICAL MARINE
but negligible attack after II years. Type 316 panels have a ATMOSPHERE AT CRISTOBAL, CANAL ZONE(31)
higher order of resistance than Type 304 under the same A - Type 410 SS 03 Cr)
exposure conditions. The results of 8-year atmospheric ex- B - Type 430 SS (17 Cr)
posures at Cristobal, Canal Zone, for these stainless steels are C - Type 301 SS (17-7)
compared in Figure 34. Note that the austenitic grades were E - Type 316 SS 08-13 and Mo)
free from pitting or weight loss. F -- Type 321 SS (17-10 and Ti)
G - Phosphor Bronze
J - Low-alloy steel with Cu, Ni, Mn, Mo
 25
The martensitic stainless steels, as typified by Type 410, Tide
may experience rust after only a few months of exposure to
the marine atmosphere. Type 410 has the minimum chromium Even t hough the tide zone is well aerated a large part of
content (12 percent) required for passivity, and local break- lhc tw:e, tnere are factors present In this environmental zone
down may be experienced. The deepest pit on a panel exposed that interf:re with the maintenance of passiVIty. Marine
at Cristobal for 8 years was 5 mils (see Figure 34); however, lmimals, SUl h as barnacles and mollusks, as well as other types
the weight-loss penetration was only 0.007 mpy. of ioullllg ;eute III the tide zone (and below) and shield the
surfa,:", fron the oxygen needed for passivity. Crevice attack at
Type 430, a ferritic grade stainless steel, becomes rusted structural joints, etc., also is more apt to take place in the tide
over part of its surface after a year or so. The higher chromium zune, when' during the immersed portion of the day, relatively
content (17 percent) as compared with Typc 410, promotes large ar,:as outside the crevice are available to serve as cathodes.
greater resistance to pitting. The general corrosion attack at Fu!thellllof':, the time is too short in the tide zone for
marine sites, such as at Cristobal, is barely measurable on a polarization to take place.
weight-loss basis. (3 I)
Of th,: stainless steels, only the austenitic grades are
normally ec,nsidered for seawater service. However, in the tide
Splash zone, he poor behavior is illustrated by results given in Table
2:'. After 8 years in the Pacific off the Canal Zone, weight-loss
The stainless steels, as a group, usually do well in the penetration for thr~e austenitic stainless steels ranged from 0.02
splash zone. The availability of well-aerated seawater tends to (Type 316) to 0.11 (Type 304) mpy. The deepest penetration
maintain the passivity of stainless steels without difficulty, for the tl1fl:e alloys ranged from 30 to 110 mils in the same
provided crevices and shielded areas are avoided in the design. period.
Since the splash zone is above the point at which marine life
develops on the metal surface, biofouling is not a factor.
Submerged
As with atmospheric exposure, the austenitic grades are
superior to the martensitic and ferritic grades. Special measures are required if stainless steels are to be
employed, withOl.. t failure, under immersed conditions in
The 300 series, particularly Types 304 and 316, have been seawater. fither the surface must be maintained passive or
used with success for small deck-mounted fittings for seagoing cathodic pwtection must be applied.
pleasure boats and other craft. Removal of sea-salt deposits by
hosing with fresh water plus occasional polishing will keep such A hig'l flow rate of seawater by the surface brings
fittings in good condition. pas:;ivating oxygen and promotes repair of breaks in the film.
High velocities also keep the surface free of biofouling. On the
When such deposits are allowed to accumulate, other hand, cathodic protection is essential for corrosion
particularly at crevices, there is a tendency for local attack. control in quiet sC3water, to prevent or eliminate the danger of
This has been observed between the strands of stainless steel crevice atta"k, pitting, tunnelling, edge corrosion, and all forms
rope, in the threads of tensioning screws, and at the point of selective Jttack.
where wire ropes enter swaged ferrules.

TABLE 22. COMPREHENSIVE EVALDAnON OF CORROSION DAMAGE OF STAINLESS STEELS,

EXPOSED TO MARINE ENVIRONMENTS IN THE P,\NAMA CANAL ZONE(3!)
------- ---

Lo",s in Type of
A\t:rag..: ut .~o Dc'cp",,,t Ic'rhlk StrL'ngth(h), C(.)rrO~Jon
Corrosion Rate, mpy Pits(J l. nlll ~l'':'>tP\I(~ll. mil percenr Atlack(C\
Metal Stainless Steel Type of Exposure I Yr 4 Yr 8 Yr I Yr 4 ~ r 8 ,\, I Yr 4 Yr X Yr 4 Yr ---:ry;:-
A Type 410 (13 Cr) Seawater immersion :.98 1.'17 175 61( II) 148 11,1 ~hO( p) 2hO(pl Pf
~_"()( IJ) KQIl
Seawater mean tide 0.50 0.41 0.42 40 67 6"7 h(l 173 152 o JKQ
Seashore 0.040 0.013 0.005 0(0) 0,01 0101 5 0101 o KR
B Type 430 (17 Cr) Seashore 0.0:5 0008 0.004 0(0) 0/01 0,01 0,01 0101 0101 0 KR
C Type 30 I Seashore 0.00 0.001 0.001 0101 0(0) 0,0, 0((11 (hOI OiGl 0 K
(17 Cr, 7 Ni)

D Type 3m Seawater immersion 1.46 0.88 0.69 70( 121 107 140 2t>l 11') 281'(1'1 236 Id) KQ
(l8Cr,8Nl) Seawater mean tide 0.18 D.! 2 0.11 7( 11 I ~h
5., Itl 82 110 a JK
E Type 316 Seawater immersion 0.59 0.07 0.25 44(7) 48 154 245tpl <n 24511'1 0 KQ
( 18-1 3 and Mo) Seawater mean tide 0.06 003 002 5(C) I 7, 121 1(, 2~ 30 I JK
"
Seashore 000 000 000 O(()I 0,0, 0,0, OtOI 0101 010, ] K
F Type 32! Seawater immersion 1.!(, 0.81 0.02 641') ]75 !qJ 2-/U(p) 27311'1 27211' I Id, KQ
(17·IOand Ti) Seawater mean tide 0.13 0.08 0.08 8i III 37 5() 26 hO ()3 tdl JKQ
Seashore 0.005 0001 0.001 O(()) 0101 0(0) 0(01 O((), DiG) I K
-------------
--~-------
~ --------- -
-,------~-
---~--------- -
(a) Pit depths referred to the original surf:.lce of the metal either by meJSUfCllll'nl from :1'1 llncorT{ld,'d 'i\.l1"LJCl' or by cJh:ulation u"ing the original and finel! average
measured thickness of the sample. Average of 20 dl'epe\t pits represents a\ctaj;,' 01 the _' (k:..')~'st Pits Illl'asllr,'d on l'Jch Sid\.' of duplicate SPl'Cllll\.'IlS (Area, 2.25 sq ft
on immersed specimens, and 0.89 sq ft on atrnosphCfl( speCIITICtlSI: VJlu,',> 111 j1Jrcntll.··.,· . . Imll'ltl' t"t:11 tlilmbn ~l\t.'Ll~l'd when k~\ th:11l ~O mc,burablc pllS, PcrforJtJon
of plate by deepest pit is II1dicated by (1'1.
(b) Changes in tensile strength calculatL'd on basis or 1/4-inch-thick ml'tJI CJ\Cf,lgC oj 4 k"t:-, for I'llfiln:ed 'ipeClml'ns. avt.'Llgc or 3 test". on atmospllcrii..· speCImens).
(c) H - concentration cell, J marine fouling contact, K no visibk attack. Q [litting. Jttdck ILl ndolll L R localill'd :JtLlck (random l.
(d) Intensity and distribution of pilting prevenkJ satisfactory !emile t:.'sting
 26
Martensitic stainless steels cannot be effectively main·
tained in the passive conditions in seawater by either high
velocity or cathodic protection. The ferritic stainless steels also
are not amenable to these methods. Both the martensitic and
ferritic alloys are susceptible to hydrogen damage resulting
from the use of cathodic protection. For these reasons only the
austenitic grades are usually specified for seawater service.

Other modes of failure include intergranular attack at the

sensitized zone for some welded assemblies and stress-corrosion 70/30 Copper - Nickel 90/10 Copper - NiCkel
cracking. These types of failure can be readily avoided by Deepelt pit - 18 mill Deepelt pit - 8 mill
selecting the proper alloy heat treatment or method of A.II pit tlepth - 10 mi'l A.II pit depth - 4 mi II
assembly.

An overall summary of the behavior of selected stainless

steels in surface seawaters is presented in Table 23. While all
grades of stainless steel are susceptible to pitting and crevice
attack, those with higher alloy content usually are more
resistant.

TABLE 23. SUMMARY OF THE BEHAVIOR OF

REPRESENTATIVE STAINLESS STEELS
IN SURFACE SEAWATER Type 316 Stainless Steel Type 304 Stainless Steel
= = = =__-=-_-_-_-_-
.. cc -
Deepest pit - 250 mill
Pitting and Cathodic High Deepelt pit - 113 mill
Stainless S~ Cre"ic~~~~~:_:~~.~_~~locitY ._ _C_o~men!~ A.II pit depth - 72 mill (perforated)
Type 410 Very susceptible Not applicable Not used Not suitable for
(martensltic) (hydrogen damage) immersed service

Type 430 Susceptible, but Not applicable Not used Not suitable for FIGURE 35. PITIING ATIACK ON PANELS IMMERSED
(ferritic) longer induction" (hydrogen damage) immers.ed service FOR 3 YEARS IN FLOWING SEAWATER AT LESS THAN
period than
Type 410 2 FPS AT WRIGHTSVILLE BEACH, NORTH CAROLINA
17-4 PH
(martensitic
Susceptible Effective for
control of crevice
Good
performance
1 Used with permission of International Nic.i<e! Company

precipitation 'dnd pitting

hardening)

Type 304 Susceptible Effective for Good Velocity must be

(austenitic) control of crevice performano..:e continuous at Under these conditions some biofouling tends to develop on
and pitting approximately
5 fps or more td the stainless steels and, to a much lesser extent, on the
Type 316 Susceptible; pit Effective for Excellent maintain clipronickels.( 32 )
(austenitic) initiation may control of crevice performance passIvatIOn
be retarded, but and pitting
attao..:k, once TABLE 24. DEEP-oCEAN BEHAVIOR OF
started, often STAINLESS STEELS
equals that for
Type 304
Exposure
Alloy 20 Cb Less susceptible Effective for Excellent Time, ~rev!.£~ Attack ,J.!!i!~ Local
(austenitic) control of crevice performance Type Depth(a) days Water Mud Corrosion
and pitting
410 2,340 197 10 15 Edge and tunnel
attack
5,640 123 Slight Slight Severe tunnel
The austenitic grades, such as Type 304 and 316, are 430 2,340 17 19
197 Tunnel
susceptible to pitting, as illustrated in Figure 35, and crevice 5,300 1,064 25,97 40 Severe tunnel
attack. They will give satisfactory service if the passivity is
maintained by a velocity of 5 fps or more. In quiet seawater, 304 2,340 197 IJ Slight Edge, tunnel
5,300 1,064 21 29 None in water;
cathodic protection is essential to control pitting and crevice tunnel in mud
attack.
304L 2,340 197 8 18 Tunnel
5,300 1,064 27, perforated 0 Severe tunnel
The addition of molybdenum may be of advantage in
high-velocity service, such as a pump impeller. There is some 316 2,340 197 0 0 None visible
indication that the molbydenum provides a longer induction 5,300 1,064 21,12 0 None
5,640 123 0 0 Slight edge
period before pitting or crevice attack commences; that is,
molybdenum additions decrease the probability of local attack. 316L 2,340 197 18 12 None visible
Thus, if Type 316 rather than Type 304 were used for the 5,300 1,064 25,8 20 Ditto
pump, in the example just cited, the passivity would normally 5,640 123 Slight Slight
take longer to break down during an emergency shutdown. Alloy 20 Cb 2,340 197 Slight Slight None visible;
attack at wall
In shallow quiet water, Types 302, 321, and 316 showed of bolt hole
5,300 1,064 0 None visible
high rates of local attack, as shown in Table 22. Deep-ocean 5,640 123 0 0 Ditto
experience for Types 304 and 316 was varied, but local attack
often took place (see Table 24). (a) Oxygen level at 2,340 feet is 0.60 ppm; that at 5,300 feet is about 1.70 ppm.
 Alloy 20Cb has been found superior to Types 304 and Bottom sediments at other areas may behave quite dif-
316 in seawater service, particularly at high velocity. It also ferently. Some of the sediments on the Atlantic floor are
appears to have greater resistance to crevice attack in quiet described as inert, and, when tightly compacted around a
seawater. However, as is the case with the entire 300 se.ies, sample, might stop all attack.
this alloy requires cathodic protection to control pitting and
crevice attack under low-velocity conditions. In deep-ocean
wa ters, the lack of corrosion at the crevice area and the
absence of pitting was noteworthy (see Table 24). After 3
years at 5300 feet, no crevice attack was observed. It is likely, Crevice Attlck and Pitting Corrosion
however, that if crevice specimens of different geometry were
exposed a sufficiently long period, crevice attack would In the discussion, up to this point, the typical failure of
develop. stainless steels by pitting and crevice attack has been
emphasized. Crevice attack or pitting usually starts out as a
Type 410 stainless steel, as with the martensitic alloys in differential aeration cell. In the case of the crevice, for
general, is not suitable for service immersed in seawater. Some example, the slow diffusion of oxygen down into the crevice
form of severe local corrosion is apt to occur both in surface may not be sufficient to maintain passivity. The surface
and deep-ocean waters. For example, panels 0.260 inch thick, external to the crevice, with an ample supply of oxygen,
were completely perforated after I year in the Pacific off the becomes the cathode, whereas the active sites in the crevice
Panama Canal (sec Table 22) although the corrosion, calculated become the local anodes.
from weight loss, was only 1. 75 mpy. Type 410 panels also
showed severe tunnel, edge, and crevice attack in the deep The rate of crevice attack is related to the cathodic area
ocean (see Table 24). available ex ternal to the crevice, and is also a function of the
oxygen solubility. Wheatfall has demonstrated these relation-
At the present time, there docs not appear to be a good ships in experiments conducted in deep ocean and at the
method of controlling the corrosion attack for straight- surface,(34) His results are presented in Figure 36. For each of
chromium stainless steels under immersed conditions. High- three seawater oxygen levels, 0.60 ppm, 1.70 ppm, and 6.77
velocity seawater is not effective for maintaining passivity. ppm, there was an increase in weight loss under the crevice as
Cathodic protection at current densities necessary to achieve the area outside of the crevice, serving as the cathode, was
polarization tends to promote blistering or hydrogen cracking enlarged.
from the hydrogen generated,(33)
For tbe highest oxygen level, the attack was an order of
Type 430, a ferritic alloy, like the martensitic grades, is magnitude ~eater than that for the lowest oxygen level. When
subject to local attack in seawater both in shallow and deep the depth I)f penetration was plotted versus the cathode area,
exposures. At Kure Beach, N.C., the maximum pit depth was the data wne scattered, as might be expected. It is the weight
60 mils in I. 5 years,( 4) In test exposures, occasional panels do loss, not pc netration, which is a direct function of the current
well, i.e., are free of attack for the initial period. While the flowing.
higher chromium content of Type 430 compared with Type
410 may account for longer induction period sometimes From this experiment, it can be seen that reducing the
observed, it cannot be depended upon. In one side-by-side area of the cathode is a method of corrosion control. One
deep-ocean exposure, Type 430 was attacked similarly to Type might, for example, paint the area external to the crevice,
410 (see Table 24). Once attack has started, the rate of
penetration may be extremely rapid. As with Type 410, neither Lenno;" et al.(35) have reported the results shown in
high-velocity nor cathodic protection can be relied upon as a Figure 37. The local attack on stainless steel in surface sea-
means of corrosion control. In view of this, Type 430 and water can he controlled effectively by coupling to an iron or
other similar ferritic stainless steels cannot be recommended for an aluminum anode. Crevice corrosion was markedly reduced,
the immersed conditions in seawater. but the slight random pitting, not associated with crevices, was
only slightly improved.
The 17-4 PH alloy is an example of the martensitic
precipitation-hardening steels. If used with a heat treatment to
provide moderate strength, e.g., with aging at 1025 F or above,
17-4 PH can be used effectively in seawater. As with the
austenitic grades, this alloy will remain passive in high-velocity Stress-Corrosion Cracking of
seawater. In quiet seawater, it can and should be provided with High-Strength Alloys
cathodic protection to control pitting and crevice attack. In
general, corrosion experience has been favorable when the alloy High-strength stainless steels are of particular interest to
is correctly applied. aircraft designers. Since many types of aircraft operate in
marine atmospheres, the performance of these high-strength
Mud stainless materials with high tensile loading is of great
importance. Alloys that can be strengthened to 15o-ksi yield
Bottom sediments vary some in composition and in and higher are of most interest.
marine activity. Sulfate-reducing bacteria have been identified
in the mud zone. Since oxidizing agents are absent, one would Depending on the grade, strengthening is accomplished by
expect stainless steels to lose passivity at local sites and, as a cold rolling. precipitation hardening, and/or phase changes. The
result, to undergo pitting and crevice attack. Such is actually four main grades are the austenitic, the semiaustenitic age
the case. In most cases, as summarized in Table 24, the corro- hardenable, the martensitic age hardenable, and the martensitic.
sion behavior in the mud zone (Pacific off California) is similar
to that observed for the same alloy in the water just above the The characteristic performance of each class in marine
ocean bottom, environments is discussed below.
 28

2.---------------------....., 0.125 , - - - - - - - - - - - - - - - - - - - - - - ,
2340 ft, 197 days 2340 ft, 197 days
Oxygen = 0.60 ppm Oxygen = 0.60 ppm

<It
o "-_.....II..-_--'-_ _-'--_.....JI..-_-'-_ _-'--_.....I Q)
J.: 0
U
<It
E .£:
8.----------------------~ 0.125
~
01 6780 ft, 403 days ..c:: 6780 ft, 403 days
0. 0
Oxygen = 1.70 ppm Q) Oxygen = 1.70 ppm
0
4
-
a::
E
0 ::J 0
E
')(
20 0 0.125
Surface, 238 days ::E S'Jrface, 238 days
Oxygen = 6.77 ppm Oxygen = 6.77 ppm
10 t-
v 0 0

I I I I I
0 0~-....L...--.1.-......I-~~-...L..-.....J.-_._J
7.5 11.5 15.5 19.5 23.5 27.5 31.5 35.5 7.5 35.5
2
Area Outside Crevice, in.

FIGURE 36. RELATION OF WEIGHT LOSS AND MAXIMUM PIT DEPTH IN THE CREVICE TO AREA OF SPECIMEN
OUTSIDE THE CREVICE FOR TYPE 304 STAINLESS STEEL AT VARIOUS DEPTHS(34)
Used with permission of American Society of Naval Engineers
(Specimen perforated at maximum pit depth = 0.125 inch.)

only a few cases have failures been reported for ambient

temperatures. In the solution-annealed condition, the austenitic
stainless steels are not susceptible to stress-corrosion cracking
l!! 50
'E during marine environmental exposure at ambient tempera-
45 C C Crevice corrosion ture.(36) On the other hand, sensitized austenitic grades are
£ P Pitting susceptible to intergranular stress-corrosion cracking in marine
a:: 40 W Weight loss atmospheres.
't:l
c: <It 35 o Max depth
0
E Of the austenitic stainless steels, that most frequently
<It ~ • Avg of 5 deepest
Q)
u
.:;
01 30 pits chosen for high-strength service is Type 30 I (18Cr-7Ni). As
~ vi -.-.. 490 days
shown in Table 25, test samples with an applied stress of 188
u <It 25 C ksi showed no failure at the 8D-foot lot in Kure Beach, N.C.,
0 ~-~-, 649 days

-
-.J
C 20
for 6.7 years. High strengths also can be obtained wi th the 200
..c::
.>t: 01 series alloys containing manganese, such as Types 201 and 202.
u .-
o Q) 15 Table 25 gives performance data for these two steels as well as
;:~
« for a proprietary type containing 15 weight percent manganese
10
'0
..c::
TABLE 25. BEHAVIOR OF STRESSED COLD-ROLLED
5
0.
Q)
AUSTENITIC STAINLESS STEELS IN THE
0 0 MARINE ATMOSPHEREs(a)(37,38)
_~J2.Q.!i~Q.5trcss
Yield Pt:n.;('nt Expo\urc
Heat Stress, of Yield Timc(L"),
FIGURE 37. DEPTH OF ATTACK AND WEIGHT LOSS -,-,-AI",I0:LY_-,Cold Work Treatment(bl. F ksi __ 15~ Strcn~~~ __. _
FOR TYPE 316 STAINLESS STEEL AFTER 490 AND
Type 201 60 1100 141 75 70~ F, 222() F
649 DAYS IN SEAWATER AT KEY WEST, FLORIDA, 60 ROO 171 75 2460 NF
WITH AND WITHOUT CATHODIC PROTECfION(35)
Type 202 60 1100 187 164 R7.5 678 F
60 800 215 161 75 2460 NF

Austenitic. High-strength austenitic stainless steels, as a Type 301 40 1100 151 126 83 2460 NF
40 800 231 188 81 2460 NF
class, are very resistant to marine atmospheres. They derive 60 800 238 178 75 240 NF
their high strength by cold work, which is usually followed by Extra hard 750 271 190 70 347 Fld)
heat treatment to restore some ductility. In the cold-worked
18 Cr· 60 1100 197 8R 2460 NF
and annealed condition, they have remarkably good resistance 15 Mnt e) 60 800 179 75 2460 NF
to stress-corrosion cracking in aggressive marine atmospheres.
This resistance, however, is lost at a joint made by welding. (a) Bent-beam specimens exposed at the 50-fool lot, Kurc Beach, N. r.
(b) Heat treated for 2 hours at temperature indicated.
These steels will also fail at elevated temperatures, such as in (c) F = failure; NF = no failure.
the boiling 42 percent MgCl2 test and in hot seawater,( 12) In (d) One specimen out of eight failed: rest still OK at this time.
(e) Proprietary steel (USS Tenelon) containing small amounts of nICkel and nitrogen.
 29
(USS Tenelon). For certain combinations of cold rolling and The martensitic-type 17-4 PH is found to be quite
heat treatment, samples of each of these alloys withstood immune to stress-corrosion cra<:king if aged at 1000 F or
applied tensile stresses ranging between 161 and 197 ksi for up above. Aging at 900 F makes the alloy susceptible to cracking
to 6.7 years without stress-corrosion cracking. Some combina- in a marine atmosphere. Denhard reported no failure in more
tions of cold work and heat treatment resulted in failures. For than 6.6 years for coupons (I) aged at 1025 F and given an
example, Type 201 was cold worked to 60 percent and heat applied str,css of 140 ksi and (2) aged at 1150 F and given an
treated for 2 hours at 1100 F. An applied stress of 141 ksi (75 applied stress of 105 ksL(36)
percent of yield) resulted in one failure at 702 days and
another at 2,226 days. Slund,~r,(38) in his DMIC review, presented the data for
17-4 PH shown in Table 26. The only failures at that timp
In seawater, the cold-worked austenitic grade stainless were for the 900 F heat treatment.
steels, e.g., Type 30 I, seem to have a great tendency to local
attack such as pitting. Cathodic protection is required if such TABLE 26. STRESS-CORROSION-CRACKING RESULTS AT
local attack is to be avoided. Fortunately, the austenitic grades 80-FOOT LOT, KURE BEACH, FOR 17-4 PH
are not sensitive to hydrogen damage at the potentials required ALLOY IN VARIOUS CONDITIONS OF
to control pitting. One would expect that by cathodically TREATMENT(38)
protecting suitably strengthened Type 301 parts they could be _._--------

Arpli~sL~!~~s5 __ EXPOSllrl' Tlmt:

made to perform under stress with satisfaction in seawater Allo\ Pl'rCl'nt of I\umbef of A... rrage TIme of Linfaikd
equal to that obtained in the marine atmosphere. anJ Yield _~2~l-'}_ryl~il_s__ to FallurC', Spccimens,
CondItion Streq;th KSI Exposed Fdiled days days
- ----------- - .-----_._ .. -

Not Wt,'ld,'J
17-4 PH, H 90(J 90 162.9 -n'
Precipitation Hardening. The precipitation-hardening stain- 7, 1358 322
less steels may be subdivided into two groups: (I) martensitic 17-4 PII.II 10.'5 90 139.9 322
and (2) semiaustenitic. They owe their great strength to the 75 1166 322

finely divided precipitate which develops on cooling from a 17-4PH.H 10'5 90 135 7 0 3"
75 113.1 0 322
supersaturated solution.
17-4 PH. H II ',0 90 101.9 0 322
75 H4.9 0 3cc
In Figure 38, Phelps(37) has summarized stress-corrosion
17-4 PII. II 901' 911 3 2~ 560
behavior of these and other high-yield-strength steels in a
17-4 PII. II 11',0 90 560
marine atmosphere. Most of the failures for the precipitation-
hardening types occurred during the first year in alloys which Wl'Ickd. Tlll'l1 Sclurion Trt'Jll'd
and Agl'd
had been heat treated to yield strengths of 180 ksi or above
(all samples were stressed to 75 percent of their yield strength). t 7-4 PH. II 90() 90 1M3 5 68
75 1370 4 114 322
Even at these high stress levels, some coupons have not failed
17-4 PH, II 10:', 90 143.6 0 322
after more than 4 years' exposure. 75 119.7 0 322
17-4 PIl.1I 10: 5 90 1384 0 322
75 1154 0 322
17-4 PH. II II '0 90 1174 322
7\ 978 322

300 , - - - - - - - - - - - - - - - - - ' - - - - - - , Solution Trl'J!l'l . \\,'ddcd, and Af:t'd

17-4 Pil. 1190e, 90 164.7 cO
7, 137.3 31
17-4 PII. II 10:, 90 1447 322
on 75 120,6 322
-""200
17·4 PII II 107S 90 13,0 3::'::'
7, 11 c.5 3"
17-4 PH. H II '0 90 103.9 0 322
7\ 86.6 0 3"
,---~- ----~--'

• Constructionol olloy steel

100
o Ultrahigh -strength steel This alloy has found application in aircrait exposed to the
t> 5 % Cr hot ·work die steel
• 12 % Cr stainless steel
marine environment, and also in underwater service. Unlike
V Precipitation-hardening stainless steel ordinary martensitic steels, the 17-4 PH stainless can be pro-
Arrows indicate no failure vided with cathodic protection to control pitting and crevice
attack in ,eawater. In addition to stress-corrosion-cracking
resistance, it also has good corrosion fatigue properties. Thus, it
finds application as shafts, hydrofoils, propellers for ice
FIGURE 38. STRESS-CORROSION BEHAVIOR OF STEELS breakers, and various deck-located fittings, etc., where high-
EXPOSED TO MARINE ATMOSPHERE AT 75 PERCENT strength is desired along with corrosion resistance.
OF YIELD STRENGTH(37)
Used with permission ot Elsevier Publishing Company As judged by laboratory investigations, a newly developed
alloy of the martensitic precipitation-hardening type (PH
13-8Mo) appears to have a higher order of resistance to stress-
The precipitation-hardening stainles' steels vary in their corrosion cracking in marine environments than has 17-4 PH.
resistance to stress-corrosion cracking, depending on the treat-
ment employed to obtain the desired strength. The martensitic The semiaustenitic-type stainless steels can be hardened by
type is hardened by heat treatment. Alloy 17-4 PH is one of wId work followed by aging, or they can be given a thermal
the best known of this group. In the solution-treated and aged treatment to produce precipitation hardening. The stress-
condition, a copper-rich phase precipitates which not only corrosion behavior is affected by the type of strengthening
increases harclnpss but also marine resistance. treatment employed.
 30
In general, semiaustenitic precipitation-hardening alloys, Some examples of the behavior of these steels are pre-
with mechanical properties produced by thermal treatments sented in Tables 27, 2S, and 29. Heat treatments are described
show a behavior in marine atmospheres which is similar but in Table 30. It should be mentioned that the So-foot-rack at
somewhat superior to that of the martensitic stainless steels. Kure Beach, N.C., represents a much more severe exposure
When the strengthening is produced by cold working, the aged than the SOo-foot rack. Thus, the time to failure in Tables 27
semiaustenitic alloys more closely resemble the austenitic stain- and 2S cannot be compared directly with those in Table 29.
less steels in their resistance to stress-corrosion cracking.
TABLE 27. STRESS-CORROSION-CRACKING BEHAVIOR AT THE SO-FOOT RACK, KURE BEACH,
N. C., FOR SEMIAUSTENITIC PRECIPITATION - HARDENING STAINLESS STEELS(3S)

Applied Stress Average Exposure Time

Perccnt---- Number of Time to of Unfailed
Alloy and of Yield Specimens Failure, Specimens,
Condition Sirength KSI b'p'osed-- - FallCct days days Direction

PH 15·7Mo, TH 1050 75 140 12 9 16 240 Longitudinal

60 In 5 182 Transverse
60 125 4 7.1 466 Transverse
60 124 71 466 Transverse
40 85 0 466 Transverse
40 84 0 466 TrJllsvnse
40 82 0 466 Transverse

PH 15-7Mo. RH 950 90 182 12(J) Longitudinal

75 152 12 12 16 Longitudinal
50 101 0(3) 175 Longitudinal
60 1.11 5 2H.2 Transverse
60 1.12 5 22.1 TrJllsversc
60 1.11 5 19 Transversl,'
40 X7 4 17.1 466 Transverse
40 88 4 74 466 Transverse
40 87 I 8' 466 Transverse

PH 15-7Mo. RH 1050 60 1.11 4 140 466 Tr:Jllswrsl'

60 129 4 3.19 466 frJnSVl:rSl'

40 8R 0 4(,6 Transverse
40 S6 0 466 Transvt:fSl.:

PH 15-7Mo. BOlT 60 140 24.2 Transverse

60 140 44.2 Transverse
40 93 49.6 Tr;.Jllsvcrsc
40 94 61.6 Tr<Jl1sversc

17-7 PH. Til 1050 75 110 27 21 .120 Lnngitlililnal

17· 7 PH. TIl 'l50 90 181 ! (J I Longitudinal

75 151 4 4 I Longitudinal
50 101 S(J I Longitudmal

17-7 PH. RII950 90 18.1 ~(a l Longitudinal

75 152 .10 ~ I 5 .1XO LongitudlllJI
50 102 !()(a) Longitudinal

A~1 .155. CRT X50 10 ~3.8 0 68 Longitudmal

35 R.1.4 0 .121 Longitudinal
50 119.1 66 LongjtuJinJI
70 166.H 112 LongitudInal
.15 73.4 0 .121 Longitlh..linal
50 104.~ 0 .121 Longitudinal
70 146.X 0 321 LongitudinJI

AM .155. SCCRT X50 10 .10.4 0 6X Longitudinal

.15 106.4 0 461 Longitudinal
50 152.0 I .119 461 Longitudinal
70 21 ~.8 21 Longitudlllal
----------~--~ ----------------_._-------------------- ~

(a) Average of thr~(' or more spc('imeJls.

TABLE 2S. RESULTS OF EXPOSURE AT SO-FOOT LOT,

KURE BEACH, N. C., FOR SEMIAUSTENlTIC
PRECIPITATION-HARDENING STAINLESS
STEELS(36)
---------- ----------_
----- - - - - - - - - - - - - -
.. _ - - - - - - -----
,---._---------

Yield AppiJed Time to

Stress. Stress, Failure. Test
Alloy Condition kSi ksi days Direction{a)
17-7 PH RH 950 20.1 181 1 L
PH 15-7Mo RH 950 202 182 12 L
PH 14·8Mo SRH 950 255 180 >1100 T

(a) L = longJtudmal coupons

T = transverse coupons.
 31

TABLE 29. STRESS-eORROSION-eRACKING PERFORMANCE AT THE 800-FOOT RACK, KURE BEACH,

N. c., FOR SEMIAUSTENITIC PRECIPITATION-HARDENING STAINLESS STEELS(38j

Applied Stress Average Exposure Time

Alloy Percent Number Time to of Unfailed
and of Yield of Specimens Failure, Specimens,
Condition Strength KSI Exposed Failed days days Direction
PH 15-7Mo, TH 1050 75 161 5 3 103 746 Transverse
75 164 5 5 39.8 Transverse
60 127 5 0 466 Transverse
60 125 5 0 466 Transverse
60 124 5 0 466 Transverse
50 107 5 0 746 Transverse
50 109 5 0 746 Transverse
40 85 5 0 466 Transverse
40 84 5 0 466 Transverse
40 82 5 0 466 Transverse
PH I 5-7Mo, RH 1050 60 131 5 0 466 Transverse
60 129 5 0 466 Transverse
40 88 5 0 466 Transverse
PH I5-7Mo, RH 950 75 174 5 5 68.8 Transverse
75 175 5 5 14.2 Transverse
60 131 5 4 179 466 Transverse
60 132 5 4 126 466 Transverse
60 131 5 4 164 466 Transverse
50 116 5 5 169.4 Transverse
50 117 5 5 98.8 Transverse
40 87 5 I 346 466 Transverse
40 88 5 0 466 Transverse
40 87 5 0 466 Transverse
PH I 5-7Mo, BCHT 60 140 5 5 236.2 Transverse
60 140 5 5 101.4 Transverse
40 93 5 0 466 Transverse
40 94 5 3 333 466 Transverse
PH I 5-7Mo, CH 900 75 196 5 0 746 Transverse
50 131 5 0 746 Transverse
17-7 PH, TH 1050 75 151 5 2 100 746 Transverse
75 134 5 0 746 Transverse
50 101 5 0 746 Transverse
50 89 5 0 746 Transverse

17-7 PH, RH 950 75 168 5 5 7.4 Transverse

75 165 5 5 51.6 Transverse
50 112 5 5 30.2 Transverse
50 110 5 I 116. 746 Transverse
17-7 PH, CH 900 75 214 5 0 746 Transverse
50 143 5 0 746 Transverse
AM 355, CRT 850 10 23.8 2 0 68 Longitudinal
35 83.4 2 0 321 Longitudinal
50 119.1 2 0 321 Longitudinal
70 166.8 2 2 152 Longitudinal
AM 355, CRT 850 35 73.4 2 0 321 Longitudinal
50 104.8 2 0 321 Longitudinal
70 146.8 2 I 177 321 Longitudinal
AM 355, SCCRT 850 10 30.4 2 0 68 Longitudinal
35 106.4 2 0 461 Longitudinal
50 152.0 2 0 461 Longitudinal
70 212.8 2 0 461 Longitudinal
 32
TABLE 30. HEAT TREATMENT OF THE SEMIAUSTENITIC PRECIPITATION-HARDENABLE
STAINLESS STEELS(38)

Austenite Conditioning Age or Temper

Temperature, Time, Tem perature, Time,
Alloy Condition F minutes Transformation F hours
17-7 PH TH 1050 1400 90 Cool to 60 F within I hr, hold 30 min 1050 1-1/2
TH 950 1400 90 Cool to 60 F within I hr, hold 30 min 950 1-1/2
RH 950 1750 10 Hold 8 hr at -100 F 950 I
TH 1075 1400 90 Cool to 32-60 F within I hr, hold 30 min 1075 1-1/2
TH 1050 1400 90 Cool to 60 F within I hr, hold 30 min 1050 1-1/2
RH 950 1750 10 Hold 8 hr at -100 F 950 I
CH 900 Cold rolled at mill 900 I
PH 15-7Mo TH 1050 1400 90 Cool to 60 F within I hr, hold 30 min 1050 1-1/2
RH 950 1750 10 Hold 8 hr at -100 F 950 I
RH 950 1750 20 Hold5hrat-IIOF 950 I
BCHT 1625 20 Cool to 1000 F in 45 min, air cool to 900 8
room temp,S hr at -100 F
TH 1050 1400 90 Cool to 60 F within I hr, hold 30 min 1050 1-1/2
RH950 1750 10 Hold 8 hr at -100 F 950 I
CH 900 Cold rolled at mill 900 I
BCHT 1675 20 Cool to 1000 F in 45 min, cool to room 900 24
temp, 8 hr at -100 F
AM 350 SCT 850 1710 20 3hrat-IIOF 850 3
BCHT 1675 20 Cool to 1000 F in 45 min, cool to room 900 24
temp, 8 hr at -100 F
AM 355 SeT 850 1710 20 3 hr at -110 F 850 3
BCHT 1675 20 Cool to 1000 F in 45 min, cool to room 900 24
temp, 8 hr at -100 F
CRT 850 Cold rolled 850
SCCRT 850 Subzero cooled, cold rolled 850

As shown in Table 27, specimens of 17-7 PH in three AM 355, which resembles 17-7 PH and PH 15-7Mo in the
types of heat treatments and at applied stresses ranging from CRT 850 treatment, withstood more than 321 days at the
101 to 183 ksi showed failure at the 8D-foot rack in I to 21 80-foot rack at Kure Beach with 146.8-ksi applied stress.
days. Not all samples had failed in the period reported. Seven
out of 27 specimens stressed to 116 ksi failed, whereas the
other 20 were still alright after 320 days. At the 80D-foot rack, Martensitic Straight Chromium Stainless Steels. Martensitic
samples in the CH 900 treatment did not fail in 746 days and stainless steels are susceptible to stress-corrosion cracking in
gave superior performance to samples of the same alloy in two marine atmospheres. The degree of susceptibility varies with
other conditions (see Table 29). These results suggest that this alloy content and/or variations in the thermal treatment used
alloy, as strengthened by cold rolling, is much more resistant to to develop their high strength.
stress-corrosion cracking. Note also that none of the thermal
treatments produce such high yield strengths as is the case Martensitic stainless steels, tempered between 650 F and
when this alloy is cold rolled, e.g., 270 ksi for CH 900 and 217 1000 F, are quite sensitive to stress-corrosion cracking. A stress
ksi for RH 950. relief below 650 F often is beneficial, but for marine service,
tempering above 1000 F gives better resultsJ36)
Although not evident from the data presented in Tables
Phelps, in a summary of his results presented in Figure 38,
27 and 29, more recent experience indicates that PH 15-7Mo is
shows the stress-corrosion cracking behavior of the 12 percen t
more resistant, on a comparable basis, to stress-corrosion
chromium, high-yield-strength stainless steel.(37) This alloy is
cracking in the marine atmosphere than is 17-7 PH. Although
representative of the martensitic stainless group under
the TH condition is more resistant than the RH, the CH
discussion. Each point on the chart represents the average time
treatment is preferred in the PH 15-7Mo alloy for highest
to failure for five or more specimens. While a few failures are
strength, e.g., 200 ksi or more. (36)
noted in the yield-strength range of ISO to 180 ksi, the great
majority of the failures occurred above 180 ksi.
A relatively new alloy of the semiaustenitic type, PH
14-8Mo, exhibits superior resistance to both the 17-7 PH and Nickel and Nickel-Base Alloys
PH I 5- 7Mo alloys to stress-corrosion cracking in the marine
atmosphere. As shown in Table 28, no failures occurred in PH Nickel is resistant to marine atmospheresJ39) Its per-
14-8Mo specimens exposed for 1100 days (more than 3 years), formance in seawater on the other hand, is variable. Passivity
whereas the 17-7 PH and PH 15-7Mo failed in only a few can be maintained in flowing seawater, but in quiet seawater
daysJ36) All the alloys were heat treated to develop nickel tends to lose its passive film at local sites and pitting
comparable strength levels. ensues. (40)
 33
The main contribution of nickel in the marine field is as Nickel-Copper. Typical alloys in the IlICKeJ-COpper senes
an alloying constituent. A series of alloys with copper, includ- contain 60 to 70 percent nickel, up to 2 percent iron, and
ing Monel-400 and the cupronickels, are all resistant to marine around I percent or less manganese, with the remainder
environments and find extensive use. copper. Th~ best known and most widely used in the marine
field is M'mel-400. Another alloy, Monel-K500, is a harder
Nickel-rich iron alloys behave much like nickel, and are compositio'l by virtue of the 2.S percent aluminum addition.
not outstanding in their resistance to marine environments.
The nickel-copper alloys, as typified by Monel-400, have
The nickel-chrome alloys, such as Inconel 600 with IS good resis1 ance to marine atmospheres, although they will
percent chromium, are very resistant to the marine atmosphere. tarnish and show weathering,(4) For example, after 7 years at
As with austenitic stainless steels, the nickel-chrome alloys are Kure Beach, N.C.. a light green patina, darker at the edges of
susceptible to local attack such as pitting under immersed tht' panel, had developed on Monel-400.( 41) These specimens
conditions. show low rates of corrosion, e.g., 0.014 mpy after 7 years at
Kure Beach(41) and after 16 years at Cristobal'c40) The rates
Among the most resistant metals available for seawater at the ASTM sites shown in Table 31 are even lower than those
service are nickel-base alloys containing large percentages of mentioned above.
molybdenum and chromium. These alloys, of which Hastelloy
C is the best known, are completely resistant to all common This good behavior is borne out by experience. Monel-400
marine environments. has given :'ears of excellent service as a material of construc-
tion in marine applications, such as deck-mounted fittings,
corrosion r.leks, etc.
Atmosphere
Monel-400, like stainless steels, is susceptible to oxygen-
concentration-cell corrosion. Thus, crevices and other areas
Nickel. Nickel corrodes at rates of the order of 0.0 I mpy where sea-:,alt solutions may be trapped and set up local cells
or less in the marine atmosphere,(39,41) Its main useful field should be ~:voided in designing.
of application is not as a structural metal but as a coating, such
as an electroplate. Specially tailored combinations of electro-
deposits of copper, nickel, and chromium provide years of Nickel-Chromium. The nickel-base group of alloys known
economical protection to steel or zinc-base die castings exposed as the Inconels owe their excellent resistance to corrosion
to marine atmospheres. primarily to the presence of 15 to 22 percent chromium. The
compositions for a variety of these and other nickel alloys are
Nickel panels have been exposed to the marine atmo- grouped according to their relative corrosion behavior in Table
sphere to establish rates of penetration. At the SO-foot lot in 32.
Kure Beach, N.C., the weight-loss penetration for a 7-year
exposure was 0.0095 mpy and the deepest pit was 1.4 mils.(41) The performance of Inconel 600 is typical of what can be
At Cristobal, Canal Zone, the rate for 16 years' exposure was expeckd from this compositional range. At the SO-foot lot at
0.0075 mpy with negligible pitting.( 40) These examples with Kure Beach, a wrrosion rate, calculated from weight loss, of
nickel sheet confirm the good experience with nickel coatings. 0.0016 ml'y was obtained after 7 years, with a maximum pit
TIle resistance of nickel to marine atmospheres is of the same depth )f 1 3 mils.c 41)
order as that found for rural atmospheres,( 42) Compare, for
example, the results of ASTM exposures, as reported by TABLE 32 CLASSIFICATION OF NICKEL ALLOYS WHICH
Copson(39) in Table 31. Note also the effect on nickel when MAY FIND SPECIAL APPLICATION IN MARINE
the marine atmosphere becomes polluted, as at Sandy Hook. ENVIRONMENTS
The corrosion rate at this marine site near New York is an Allov Remarks
order of magnitude higher than that at unpolluted marine sites ClJs~ I. ~h),,-t _Rl'SI'ltJl]l
and reOects the presence of sulfur products in the atmosphere. Ha..,tcl1o'y ( 571'.i-16Cr-17Mo-plus Fl'", W, Co Compktcly resIstant
l'Xct'pt at welds
ifJstclloy C-~16 57NI-16Cr-17?\1o-plus Fe, W, Co Low cHbon «O.O~ C)
TABLE 31. ATMOSPHERIC CORROSION BEHAVIOR OF C:.tll be wt'ldcd

In~nncl 6~S 61 ~i-22C'r-9~1o plus Fe. Cb Approa..:hcs Hastelloy C

NICKEL AND MONEL-400 AFTER 10 AND 20
III total re'cllslance
YEARS IN THE MARINE ATMOSPHERE(39) MP35N 35:\i·3SC()-~OCr-10Mo fx..:dknt. so far, In
prellmlnaryexpcrlments
Chlllflmt,.'L' 60~J-l ~Cr-18Mo plus Fe. Si Cast alloy; excellent for
Corrosi~nYate,-!J1..l'Y.- pumps. etc
Metal Site 10 years 20 years Exposure Rl'I1l' 41 56Nl-IICo-19Cr-1 OMo-3. 1Ti Good-to~xcl'lknt rcsis-
Lmce 10 fllttlng
Nickel Key West, .0050 .0041 Marine
Hastellov X 52NI-22Cr·9Mo-19Fe rlus \1,", Co DItto
Florida
La Jolla, .0047 .0056 Marine (lass, I I.. \~c_ry _Resl."ta~t
California HJ"kllo~' F 46NI-C!C,-7Mo-, I Fe }
State College, .0066 .0085 Rural 'bstl'l]ovG 451\1-21 Cr-7Mo-20Fc-2Cu-2.5Co
Pennsylvania llliunl R 6g~i-21 Cr-SMo-3Cu Usually sJtisf<ictory;
incnncl 700 46r\i-28Co-lSCr-4Mo plus Ti, AI molybdenum content
Sandy Hook, N. J. .0313 Polluted marine
Llplo} I 5NI-4OCo-20Cr-7Mo-lSFe-2Mo proVIdes resIstance 10
!!1l'ollel 71 X 53NI-19C,-3~lo-lol, plus Cu. TI. AI p,ttlng
Monel-400 Key West. .0065 .0045 Marine
Florida CJ.'!_.:<;~_!lL__ F-_~~SJ!cI~L~g_~_~ J) t.t I ~
La Jolla, .0077 .0064 Marine lrHoncl ~)OO 7M"_I-J6Cr-7Fe
California lnl'onl'l \750 7J1'1-15Cr-'Fe plus Cb. TI. AI May be some pitting
lnl'l)!oy 800 32~i-21 Cr-4oFl' at sites where
State College, .0050 .0067 Rural lJh'O!Oy 825 421'\ i-2 2Cr-30Fl'-3Mo-2Cu seawater IS stagnant
Pennsylvania Monl'J-400 66r'<1-32Cu-2Fe }
Sandy Hook, N. J. .0266 Polluted marine \1onel-K500 651'1-30Cu-1 Fe-3AI
 34
Nickcl-Chromium-Iron. Nickel-rich iron alloys containing for thc new "Hoy, MP35N, indicate it to be equal to Hastelloy
C in marine performance. It should be mentioned that it is not
about 30 to 45 percent nickel, 20 to 30 percent chromium,
and iron are much more passive than nickel and are very susceptible to stress-corrosIOn cracking. IIlium Rand Elgiloy
also arc corrosion-free in marine atmospheres.
resistant to marine atmospheres. The combination of these
amounts of nickel and chromium increases the range of condi-
tions in which these alloys will remain passive. In marine
Splash
atmospheres contaminated by industrial pollution. i.e., sulfur
compounds, some tarnishing may occur but the corrosion
As mentioned earlier, nickel and its alloys require well-
attack should be insignificant.
aerated conditions to maintain the surface passive. In the splash
zone these requirements arc readily met. Frequent splashing
After 7 years at Kure Beach, N.C.. panels of Incoloy SOO
wl11 keep even the Class 1II alloys of Table 32 passive, as long
and Incoloy S25 at the SO-foot lot showed weight-loss penetra-
as the surface is clean and free of deposits and pockets where
tions of only 0.006 mpy. The deepest pits were 0.9 and 0.7
seawater can collect. This usually can be accomplished by
mil, respectively. (42) Because of other experience, one might
proper design, and is facilitated by the fact that no biofouling
expect the 3.0 percent molybdenum content of Incoloy 825 to
takes place in the splash zone.
confer some benefit. TIlis alloy tends to remain bright longer
than the molybdenum-free Incoloy SOO in marine exposures.
However, on prolonged exposure, both alloys tend to develop a
Tidc
thin ntst stain, usually in association with edges or minor
pits.c 41)
Nickel alloys will become covered with marine fouling,
such as barnacles and shell fish, in the tidc zone and below.
TIlliS, passivity is difficult to maintain on nickel, the nickel-
Nickel-Chromium-Molybdenum. The nickel-base alloys
copper, nickel-chromium-iron, and the nickel-chromium alloys.
listed in Table 32 with 16 to 22 percent chromium and <) to
TIle nickel-chromium-molybdenum alloys, however, will remain
I c: percent molybdenum are the most resistant of the structural
passive in spite of the biofouling at the tide zone.
metals to all known marine environments in general. The
titanium-base metals alone have comparable resistance.
Half-tide behavior, reported for nickel and Monel-400 in
the Pacific Ocean off the Panama Canal Zonc. is summarized in
Alloys of this type now in common use include Hastelloy
Table 33. After 16 years, nickel showed a weight-loss penetra-
C, Hastelloy C-276, Inconel 625, and Chlorimet-3 (casting
tion of only 0.27 mpy. However, the maximum pit penetration
alloy). All have outstandingly good resistance to the marine
was 121 mils, and the pits were wide and deep. Thus, nickel
atmosphere. For example. a Hastelloy C mirror is still bright
has no particular advantage as a cladding or plating material in
and shiny after about 20 years' exposure at Yure Beach. Where
this cxposure environment.
the cost can be justified, any of these ail"ys will provide
corrosion-free performance in marine atmospheres.

The composition and general performance of another

series of nickel-bearing alloys with higll chromium and molyb-
denum contents are also prcsented in Table 32. Early reports

TABLE 33. CORROSION OF NICKEL AND MONEL-400 IN MARINE ENVIRONMENTS AT

PANAMA CANAL ZONE(40)

Type of
Weight-Loss _ .. Dcrtll..ot]j.ttil1brnlls __ ~ __ Corrosion
--.!'~IJ~tratio n,_I11J.lL ;\Y1L()L 2Q DeeJ.l_e~tCa)_ P~.st Pellelr~!i9~ Attack(b)
~----~----

Metal Exposure I Yr 4Yr 16Yr I Yr 4 Yr 16 Yr I Yr 4 Yr - 16 Y-;: 16 Yr

Nickel Seawater
(99%) Immersion 2.40 1.30 1.21 125 121 142 245 248 249 JQHK
Mean tide 0.35 0.33 0.27 (0) 47 61 o 105 121 JQ
Atmospheric
Marine 0.01 0.01 <0.01 (0) (0) (0) o o o K

Monel-400 Seawater
(cold Immersion 1.64 1.04 0.54 17 27 33 42 41 55 RJ
rolled) Mean tide 0.10 0.12 0.17 (0) (0) 14 o 00 21 JR
Atmospheric
Marine 0.04 0.02 0.01 (0) (0) (0) o o o AK

Monel-400 Seawatcr
(hot Immersion 2.09 1.0 I 0.52 43 53 56 90 82 80 RJ
rolled) Mean tide 0.11 O.IS 0.16 (0) 16(15) 24 o 20 36 JR

(a) Numbers III parentheses ll1dlcate number of mcasur,ible plts when less than 20. A measurable pillS>5 nuls.
(b) A ul1lform attack. H concentratlOn cell, J foulIng contact, K - no VISible attack, Q - plttll1g (randomly
distributed). R - local attack (randomly located).
 35
Monel-400 showed a weight-loss penetration of 0.17 mpy TABLE 34. HIGH-VELOCITY SEAWATER IMPINGEMENT(a)
and a maximum pit depth of 24 mils during the J()-year
period. It is evident that the copper addition has provided Velocity 135 fps (91 mph)
some improvement in pitting resistance over that of nickel. Duration 30 days
General experience indicates that the pit depth on Monel-400 Exposed Area 3.5 sq in.
rarely exceeds 50 mils in the tide zone. Pits develop slowly and
do not increase appreciably in depth after the eighth year.
Cupronickels, which are discussed elsewhere, are more resistant Weight Loss, Corrosion Rate,
in this environment and tend to show only slight pitting in the -.M!Jter~ g_r~~_~ m--"p--"y,-
same exposure condition.
Inconel718 0.007 0.2
Inconel X-750 0.008 0.2
Monel-400 has been used with success as a cladding over
Inconel600 0.010 0.3
steel to protect piling at the tide-splash zone area of off-shore
Incoloy 825 0.011 0.3
structures. An allowance for corrosion of, say, 50 mils would
Monel-400 0.016 0.4
be desirable in view of the pitting that will take place.
Monel-KSOO 0.017 0.4
Ni-Al bronze 1.223 31
At the half-tide exposure, nickel-chromium and nickel-
Naval brass 1.676 42
chromium-iron alloys will tend to show pitting and other forms
HY-80 steel 2.113 57
of local attack. (40) As with stainless steels, the areas under
Medium C steel 6.518 176
fouling such as barnacles and at crevices are subject to attack.
High-tensile steel 8.167 220
However, as a class, these alloys are somewhat more resistant
Cast iron( b) 6.788 600
than the austenitic grades of stainless steel.

Alloys in the nickel-chromium-molybdenum group, as (a) Data provided by The International Nickel Co., New York,
represented by Hastelloy C, have outstanding resistance to the N. Y.
tide-zone environmental conditions. Since the alloys listed as (b) In test only 10 days.
Class I in Table 32 are particularly resistant to the attack of
the chloride ion, they could be used in the half-tide zone under
conditions where no corrosion at all could be tolerated. On the other hand, in quiet seawater, Monel-400, Monel-
K500, and similar alloys have a tendency to pit or to expe-
rience local attack at screened areas. For example, in Pacific
surface-seawater tests, Monel-400 showed a weight-loss penetra-
tion of only 0.54 mpy after 16 years and only 0.29 mpy
during the last 8 years. However, during the 16-year exposure,
Submerged pits up to 56 and 80 mils deep were encountered on samples
of cold-rolled and hot-rolled panels, respectively.( 40) As shown
Nickel can be maintained passive under immersed condi- in Figure 39. most of the pitting takes place during the first
tions in rapidly flowing seawater. Corrosion rates range up to 5 year after which the pits tend to spread out rather than
mpy.(4) In quiet seawater, nickel becomes covered with bio- deepen.
fouling and passivity is lost under these deposits as well as at
crevices. As shown in Table 33, nickel exhibited a weight-loss
penetration of I. 21 mpy after 16 years in the Pacific.(40)
Panels 0.250 inch thick were completely perforated by local Points are average of 20 deepest penetrations
pitting as early as the first year. In deep-ocean exposures, Numbers indicate maximum penetration, mils
weight-loss penetrations varied from <0.1 to 1.8 mpy.(43) P indicates perforation of 1/4 in. - thick panel
Crevice attack tended to cause perforation for exposures as 150 99Ni p
short as 197 days. There was very little general surface corrO-
sion, practically all of it being pitting. The edge penetration p
p p
also observed was attributed to microcracks formed during the !!!
shearing of the panels. 'E
~IOO
c
From this discussion it is evident that nickel, itself, does .2
not have good resistance to seawater, especially under low- ~
Q;
velocity conditions. Should it become desirable to use nickel in c
CIl Monel-400
a seawater application, cathodic protection could be applied 11.

with a sacrificial metal such as zinc. Pitting corrosion can be 50

controlled by the application of sufficient cathodic current to

polarize the nickel surface.
eu - 30Ni - I Fe 10
Nickel-Copper. In high-velocity applications, the nickel
copper alloys as represented by Monel-400 and Monel-K500 I 2 4 8 16
have excellent resistance to seawater. Passivity can be main- Exposure Time, years
tained, and the water motion tends to prevent fouling. Results
of hydrofoil tests are presented in Table 34 which shows that FIGURE 39 PITTING BEHAVIOR OF NICKEL, MONEL,
both of these Monel alloys arc greatly superior to copper-base AND 70Cu-.30Ni-1 Fe ALLOY IMMERSED IN PACIFIC
alloys and steels. . SEAWATER FOR 16 YEARS(40)
 36
A comparison of a few other well-known metals with
Monel-400 is shown in Figure 40. From the standpoint of 2.0
weight-loss penetration, Monel-400 corrodes at about the same o NCEL, 5,500 ft
• NCEL, 5,500 ft
order of magnitude as zinc. TIle 6061 aluminum alloy shows (partially In bottom sediment)
much less attack, but experiences deeper pits in the same '"0.
E
1.5 o NRL, 5,600 ft, Atlantic
exposure.c 40) Cupronickel and aluminum bronze are found b INCO, 5,500 ft
superior to Monel-400 in respect to both pitting and weight- ~ x Surface, Port Hueneme, Calif.
loss penetration. Corrosion rates in quiet seawater for Monel
0
a: o Surface, Kure Beach, N C
1.0
and stainless steel are compared in Table 35. Note that the pits c
0
on the Monel alloys are broader and less deep. Monel was less 'in
susceptible to crevice attack than were the stainleso; steels. ~
::; 05
U

o0l-~:::2~0~O==:4~OO~==6;O;O;::=:;:80;O;:::==I:::;OO~0J--lj20C
Pitting Penetration, mils
el0 Monel (B)
-! Ave ra ge JL..Q....2- J:L --!L .lS.-
20 Deepest 40 12 <5 23 28 62 Exposure Time, days
1: 8
.t::» Deepest 56 37 21 79 48 107
~ '" FIGURE 41. CORROSION OF MONEL-400 ALLOY
E IMMERSED IN SEAWATER AT SHALLOW AND
0
It DEEP OCEAN SITES(1)
"0
6
~
.2 N ickel-Chromium-Molybdenum. Before discussing the
::J
.!e individual alloys for which information is available, one can
0
u cite some general effects of alloy composition on the corrosion
.'!'. behavior of nickel-chromium-molybdenum alloys. Nickel, itself,
4
'E is prone to pi tti ng. When ChrOITliurn is added to nickel, as
represented by the 80Ni-20Cr compOSItion (Nichrome) or by
c

-
.'2
~ Cu - 30Ni -I Fe (D)
Inconcl 600, the passive film is strengthened greatly but not
sufficiently to prevent crevice and pitting attack in seawater.
Thus, the nickel-chrome and nickel-chrome-iron compositions
'"c 2
c't can be used in seawater only where the velocity will be such as
5% AI bronze (G) to maintain the passive film or if cathodic protection is used.
'"OJ In general, these alloys are much more resistant to local attack
~
'">
<t
6061 AI (H) than nickel. local breakdown may take years to develop under
some conditions.
4 8 16
Exposure Time, years
When molybdenum is added to nickel, the tendency to
FIGURE 40. COMPARISON OF VARIOUS METALS AFTER local attack is virtually eliminated, as is the case with Hastelloy
16 YEARS' IMMERSION IN LOW-VELOCITY PACIFIC B (which contains 28 percent molybdenum and 5 percent
SEAWATER OFF THE PANAMA CANAU40) iron). When the nickel is modified with suitable amounts of
Used with permission of National Association at Corrosion both chromium and molybdenum, the extremely good resis-
Engineers
tance of such alloys as Hastelloy C, Inconel 625, etc., is
As shown in Figure 41, the weight-loss penetration of obtained. Thus, each of these additions contributes to the
Monel-400 in deep-ocean environments. is typically about I improvement of tile corrosion behavior of the nickel-base
mpy or less. However, Monel-400 is subject to severe pitting composition.
attack in the deep ocean, as illustrated in Figure 42. Under
these conditions, the weight-loss penetration typically ranged
from 0.3 to 1.1 mpy and crevice attack ranged from negligible lnconel 600 and X750 alloys will remain passive in flow-
to complete perforation or 125 mils.( 43) ing, well-aerated seawater, but will be attacked at crevices.
Pitting also occurs. Both these alloys do well with cathodic
To control the tendency for pitting in quiet seawater, it protection in quiet seawater and both are resistant to chloride-
would be desirable to provide cathodic protection, as by ion stress-corrosion cracking. Deep-ocean crevice-attack results
galvanically coupling a Monel item to a large steel surface. As for Inconel 600 are presented in Figure 43. It is to be noted
with nickel, if impressed current is used. it may be necessary to that the crevice attack has led to perforation in one case.
polarize just to the pitting potential, since the general corrosion
is not excessive.
lnconel 71 k is much more resistent to crevice attack. no
MonclAOD and MOJ!c'I-K500 arc' used mainly In high- doubt because of the" percent molybdenum adeJition. It is a
velocity applications in the immersed condition. These applica- good alloy for erosion corroslon and strength. Recent applica-
tions include such items as pump impellers and small tions in the marine field include hydrofoils, bolts, and
propellers. propelkrs.
 37
TABLE 35. CORROSION RATES AND DEPTH OF ATTACK ON SPECIMENS EXPOSED
FOR 3 YEARS IN QUIET SEAWATER(a)

(Specimen dimensions, 4 x 12 inches)

Weight Corrosion Localized

Thickness, Fouling Loss, Rate, Attack, mils
Material inch Rate(b) grams mpy Max Avg(c) Remarks

Monel-400 0.062 2 36.6 (d) 41 36 Numerous broad pits

0.062 2 34.2 (d) 52 48 Numerous broad pits, single
perforation from opposing pits
Monel-K500 0.125 2 33.0 (d) 39 30 Numerous broad pits, 5-8 mils;
deeper attack in large areas on
back side
0.125 2 32.6 (d) 55 33 Numerous broad pits, 5-8 mils;
deeper attack in large areas on
back side
304 stainless steel 0.125 2 16.8 (d) Perforated Crevice corrosion beneath
barnacles and at sheared edges
0.125 2 17.4 (d) 119 42 Crevice corrosion beneath
barnacles and at sheared edges
31 6 stainless steel 0.125 2 4.0 (d) 72 50 Crevice corrosion beneath
barnacles and at sheared edges
0.125 2 4.8 (d) 60 45 Crevice corrosion beneath
barnacles and at sheared edges
Incoloy 825 0.125 0.2 0.1 7 Crevice corrosion beneath
barnacles
0.125 0.2 0.1 Crevice corrosion beneath
barnacles

(a)Data from joint test program - Los Angeles Department of Water and Power and The International Nickel
Company, Inc.
(b) 10 = free of fouling, 0 = completely fouled.
(c) Average of five deepest pits.
(d) Weight loss due to localized corrosion.

Exposure Time
o Corrosion rote Depth
• Crevice corrosion, woter

123 Days
• Crevice corrosion, sediment

T
P Perforat Ion

403 Days

751 Days
6 000ft

1064 Daysf~!~:::::: ••••

197
2500 ft
402

o 5 10 Rate,
Corrosion
20
mpy
25
o 10 20 30 40 50 60
Crevice Corrosion, mils
FIGURE 42. PITTING CORROSION OF MONEL 400
AFTER 1,064 DAYS OF EXPOSURE AT A DEPTH FIGURE 43. CORROSION RATES AND DEPTHS OF
OF 5300 FEET(43) CREVICE CORROSION OF INCONEL 600(44)
Used with permission of U. S. Naval Civil Engineering Laboratory
 38
Incoloy 800, as shown in Table 36, does well in deep- Hastelloy C and Inconel 625 are the best known of the
ocean environments. This excellent behavior is unexpected and nickel-chromium-molybdenum alloys. Under immersed condi-
is not consistent with its composition, since it is closely related tions, their corrosion resistance is equaled only by that of
to the pit-susceptible austenitic-grade stainless steels. titanium materials.

TABLE 36. DEEP-oCEAN BEHAVIOR OF Ni-er-Fe, Ni-er, An example of the resistance of Ineonel 625 in snallow
AND Ni-er-Mo ALLOYS(43) seawater environments is given in Table 37. No corrosion of
Crevice any significance was observed in any of these aggressive
Exposure CorrosIOn Rate, Corrosion,
Time, Depth, --------.!!l2L mils Notes on
environments after exposures of up to 3 years. Circular welds
Alloy day:__ ~t ~_B_~d ~~~ Attack on material annealed at 1800 F prior to welding also showed
Inconel600 123-1,064 2,340--6,780 <0,1-0.5 <0.1-0.3 4-51 3-10 Mostly local crevice, no significant attack after I year of exposure.
some pitting
Inconel X750 123·1.064 2.340-6,780 <01·0.4 <0.1 0-47 0-9 CrevIce attack In
water and mud
TABLE 37. DESCRIPTION OF SEAWATER CORROSION
Inconel718 402 2,370 <0.1 <0.1 Sligh t crevice in
TESTS ON INCONEL 625 IN WHICH
mud zone NEGLIGIBLE ATTACK WAS OBSERVED(a)
localoy 800 123-1,0642,340--6,780 <0.1 <0, I 1-6 Trace of crevice in
mud zone; most
samples OK (I) Tests with 0.25 inch diameter 7 x 19 wire rope at
Incolo,' 825 123-1,064 2,340-6.780 <0.\ <D.l 0-22 0-8 Most samples OK Wrightsville Beach, North Carolina, in ambient seawater.
Inconel 625 402 2,370 <0.1 <0.1 None None
Exposures: (a) trough at 2 fps, (b) water line, (c) tidal
Hastelloy C 123·1,064 2,340-6,780 <0.1 <0.1 None None
zone, and (d) partial mud burial.
Under immersed conditions, Incoloy 825 may be locally
(2) Tests with 4 x 12 panels with plain crevice (1.25-inch fiber
attacked in quiet seawater under fouling and at crevices. How-
washer), and welded configurations (2-inch-diameter
ever, its resistance to pitting and crevice attack is much greater
circular weld ground t1ush).
than that of the austenitic-grade stainless steels. The rate of
attack after 3 years was 0.018 mpy for the totally immersed Exposures: (a) quiet seawater and (b) trough at 2 fps.
condi tion, as well as in the half-tide and the splash zones. In
these particular exposures, local attack did not develop in the (a) Data provided by The International Nickel Company, New
well-aerated splash zone, nor under the totally immersed condi- York, N. Y. (1968).
tion. In the latter condition, pitting may eventually take place,
unless the surface is continuously provided with well-aerated
Hastelloy C has been tested in a great variety of seawater
seawater. (See Table 35 for shallow-water results for Incoloy
environments and found extremely resistant. A few selected
825.) In hot seawater, this alloy is resistant to stress-corrosion
examples are presented in Table 38. Note that Hastelloy C will
cracking and thus finds application in seawater heat-exchanger
withstand high velocity, elevated temperatures, stagnant
service.

TABLE 38. CORROSION OF HASTELLOY C IN SEAWATER ENVIRONMENTs(a)

Seawater Conditions
Temp, Velocity, Oxygen, Corrosion(b) ,
Type of Test Site F pH fps ppm Duration mpy Notes

Spool Curacao 82 6.6 (Pump 3.5 3 yr 0.4 No pitting

suction)

Spool 325 0.5 3.3 yr <0.1

Coupon Wrightsville 51 8.0± 128 Sat'd 30 days 0.2

Beach, N.C.

Sandblasted Ditto Ambient 8.0± Low Sat'd 10 yr 0.016 No pitting or crevice

plate attack

Sheet tensile Navy Laboratory 350 10 1080 hr (Weight gain)

rotating in at Annapolis, Md.
autoclave

Navy erosion Wrightsville 86 8.0± 20 Sat'd 60 days 0.63

test Beach, N.C.

(a) Taken from literature supplied by The International Nickel Company and Union Carbide Corporation.
(b) Weight losses were so small that cleaning and weighing errors may be the major factor, especially for plate samples,
 39
conditions, etc. In other tests it has withstood seawater tem- Monel-400, and lncoloy 825. When any of these alloys are
peratures as high as 550 F. Hastelloy C, in other words, is coupled to alloys higher on the list, such as the copper-base
completely resistant to conditions involving impingement alloys, there is a tendency for galvanic corrosion. For example.
attack, crevice attack, heat transfer, etc. It also does not fail by Inconel 625 WIre cable performs well in seawater. Cupronickel
stress-corrosion cracking in seawater at tensile strengths close to (70Cu-30Ni) also does well. However, the corrosion attack on
the yield. cupronickel fittings tightly clamped to lnconel 625 cable has
been excessive and has led to their failure.
It should be mentioned that welds in Hastelloy C tend to
fail by intergranular attack in hot seawater. Carbide formation Another example is provided by the Navy results illus-
at the sensitized zones is evidently responsible. By using a trated in Figure 44. COllpling of Monel-400 to phosphor bronze
modification of Hastelloy C (Hastelloy C-276) with less than resulted in a greatly accelerakd attack on the bronze, even
0.02 percent carbon, this welding problem can be avoided. with partial galvanic protection of the Monel-400. Coupling of
stainless steel (which in the passive state has a potential close
Chlorimet-3, a cast alloy, is related in composition to the to that of Monel-400) to bronze did not cause nearly so great
above two alloys. All evidence would suggest that it also is an increase in the attack on bronze as did coupling bronze to
entirely resistant to seawater environments. Monel-400. The explanation is that Monel-400 polJrizes less
readily than stainless steel.
In line with the discussion of the need for adding both
chromium and molybdenum to nickel, in order to provide
passivity and resistance to local attack, deep-ocean results have Seawater Seawater
shown that Hastelloy X, F, and G have negligible crevice attack 70 Continuous Immersion Mean Tide
and good resistance to general attack in seawater. Rene 41,
judging from its composition, should be excellent in seawater. 60
corrosion (bimetollic couple)
Elgiloy has been known for some years as a resistant alloy .!!!
'E 50 25 25
for special applications involving seawater. As a spring material
it can be used in seawater without risk of failure. 0:
.;:
40 20 20
IIIium R has excellent resistance to seawater, although it is Vi
not quite the equal of Hastelloy C. '0
30 15 15
c:
.2
Similarly, the new multiphase, MP35N alloy has shown no 1/1
~ 20
attack after 4 years' exposure in seawater, and the behavior of 0
10

this alloy in seawater is expected to be similar to that for U

Hastelloy C. 10 5

Galvanic Coupling. Part of the galvanic series is shown in

2x9xl,.ll"
Table 39 for reference purposes. Note that some of the nickel- strips
bearing alloys are among the most cathodic, e.g., Hastelloy C,
9x9x1/4"
Cu- Ni Monel Cu-Ni Mone'
plotes

TABLE 39. PART OF GALVANIC SERIES OF METALS IN Q)

'0
FLOWING SEAWATER SHOWING METALS 0:: 2
AT THE MOST NOBLE END( 45)
O~
c: 'E
0 4
Copper (Least Noble) 1/1

Silicon bronze ~
Red brass U
0
6
Aluminum brass
G Bronze FIGURE 44. GALVANIC EFFECTS WITH SEMINOBLE
Admiralty brass METAL COUPLES IN TROPICAL SEAWATER(40)
Cupronickel 90Cu-lONi Used with permission of National Association of Corrosion
Engineers
Cupronickel 70Cu-30Ni Average penetration (calculated from weight loss for
Nickel 8 years' ex posure).
Inconel600
Nickel-aluminum bronze
Silver Mud
Titanium
Type 304 stainless steel (passive)
Both nickel and nickel-copper alloys show localized attack
Inconel625
when exposed to bottom sediments. For example. in deep-
Hastelloy C ocean experiments, some panels of nickel were perforated in
Monel-400
the water and also in the mud exposure'(43) Some experience
Type 316 stainless steel (passive)
with nickel-copper alloys. such as Monel-400. suggests that if
Incoloy 825
either of these materials is to be used in the mud zone, local
Graphite
attack must be controlled by cathodic protection, combined,
Platinum (Most Noble)
where feasible, with a protective coating.
 40
For the nickel-base alloys with chromium, iron, molyb- chloride.(49) In addition to the sulfate and chloride, a small
denum, and other additions, the behavior in the mud zone quantity of basic copper carbonate may be present, as well as
tends to follow that in the quiet ocean (see Table 36). An layers of cuprous oxide next to the metal.(50)
alloy of 80Ni-20Cr (Nichrome), for example, showed crevice
attack in both the mud zone and in the water just above the The patina developed on the bronze Statue of Liberty has
bottom, Alloys like lnconel 625 and Hastelloy C were com- been analyzed and represents the situation for a polluted
pletely free from attack in the mud zone. lncoloy 825 marine atmospherl·. It consists of 95 percent basic copper
occasionally showed crevice attack both at the sea bottom and sulfate! CuS04·3Cu(OH)2 J and 5 percent basic copper chloride
m the mud.(43) lCuCI23Cu(OH)2] .(51)

It is concluded that the loss of passivity at local sites can Copper and copper alloys exhibit low rates of attack in
occur almost as readily in the mud zone as in quiet seawater. marine atmospheres. Typical exposure data for both temperate
TIle degree of penetration may be eventually as deep, but and tropical marine exposures are presented in Tables 40
probably will require much more time. As shown in Table 3(J. through 42. Some differences in the rate of attack between
lneonel 718 and lneoloy 800 showed more tendency to crevice exposure sites and between various alloys will be noted: how-
at tack in the mud zone than in deep-ocean water. In all otlier ever. these dilTercnces are slIlall ~md in general have little or no
cases for susceptible alloys, the reverse was true. practical significance On the basis of weight-loss mcasuremcnts.
corrosion rates over periods of up to 20 years are 0.0 I to 0.17
mpy. As would be expected. rates of attack experienced in
Cobalt tropical zoncs arc higher than those in temperate exposures.
From the standpoint of alloy additions. slight beneficial trends
are indicated for aluminum. nickel. and zinc, whereas those
Cobalt has a very low rate of attack in the marine atmo- alloys containing silicon and tin tend to be somewhat less
sphere. At Kure Beach, North Carolina, a corrosion rate of 0.1 resistant than copper alone. As previously pointed out, these
to 0.2 mpy was cstablished at both the 80- and 800-ft lots.(46) trends are not so significant as to dictate the use of onl' alloy
Cobalt as an electroplate may corrode more readily than nickel. over another except for an extremely critical application.
The corrosion products tend to give a reddish cast to till'
surface. A comparison of composite electroplatl's of chromium TABLE 40. SUMMARY OF ATMOSPHERIC CORROSION
with (I) cobalt, (2) cobalt-nickc'l. and (3) nickel Ul1lkrl'Cl~lls RESULTS FOR COPPER ALLOYS AFTER
shows that each givl's roughly the same prCltl,ctiCln to steel in 16 YEARS' EXPOSURE AT CRISTOBAL,
marine atmospheres.(47) Cobalt can be classed as a resistant PANAMA CANAL ZONE(52)
metal in the marine atmosphere. As with nickel. some local
attack may be expected where salt and deposits sd up corro- Loss in Tensik
sion ce'lls. Currosion kate LI ). Strcngth tb ),
mEL____ _percent
In seawater, electrolytic cobalt is reported to have an 4Yr 8Yr 16Yr_ - -8Yr 16Yr
Metal - - - - - - - - - _ .. _---- ---------
average corrosion rate of 0.7 mpy after an exposure of 2 ---~-------_ ..

years.(46) In 4 percent sodium chloride, cobalt is readily Copper 0.095 0.071 0.048 3.7 4.5
passivated, but is inferior to nickel in this respect. It would Silicon bronze 0.162 0.136 0.116 0.0 3.9
Phosphor bronze 0.100 0.076 0.060 6.6 2.4
appear that cobalt in quiet seawater would tend to pit.
Aluminum bronze 0.038 0.029 0.024 1.5 2.4
Commercial bronze 0.055 0.037 0.031 2.3 3.3
Cobalt alloys such as Haynes Stellite No. 30 and Haynes
Low brass 0.040 0.029 0.023 4.8 3.2
Stellite No. 21 (cobalt-base Cr-Mo alloys) are very resistant to
Cartridge brass 0.028 0.023 0.021 5.3 3.6
seawater.
Naval brass 0.033 0.026 0.024 2.7 6.8
Muntz metal 0.035 0.029 0.028 4.3 8.4
Manganese bronze 0.075 0.041 0.038 6.0 8.0
Copper and Copper-Base Alloys

(a) The corrosion rate, as measured by the tangent to the curve

Copper alloys find application in a wide variety of marine at each time interval, is given here. This rate is lower than
environments.(49) For some types of service, such as ship that obtained by taking the mils penetration from weight
propellers or surface condensers. special alloys have been loss, and dividing it by the total number of years.
developed to provide the optimum combination of corrosion (b) 1/16-inch-thick sheet samples.
resistance and desired physical properties.
The high-zinc brasses (naval brass, Muntz metal, and
An essential feature of the behavior of copper and its manganese brass). although exhibiting low rates of penetration
alloys in marine environments is the development of a pro- on the basis of weight loss, were found to have lost consider-
tective film. The films developing in the atmosphere and in ably more strength than other alloys in the series (see Tablc
seawater differ in composition. In general. a grcater number 01' 40). These materials exhibited dezincification as a result of
~i1loys develop protec'tivc films in the atmosphere than in exposurl' to the marine l'nvironment. In general, copper alloys
s-.?awatl'r. with 15 percent or more zinc are susceptible to c1ezincification
in marinc atmospheres. For single-phase brasses, the attack can
be controlled by small additions of arsenic. antimony, or
AtmosphL'fe phosphorus. About 0.02 percent arsenic is very effective. Note
that Muntz metal. which contained 0.19 percent arsenic,
In marine' atmospheres, part of the basic copper sulfate showed loss of strength because of dezincification. In this
whil'h comprises the major portion of the patina that normally two-phase alloy, the inhibitor is not effective in preventing
forms in 'I urban atmospherl' is replaced by the basic copper dezincification.
 41

TABLE 41. MARINE ATMOSPHERIC RESULTS FOR COPPER ALLOYS

AFTER 2 AND 7 YEARS(41)

Penetration, mpy (Calculated

Commercial From Weight Loss)
CDA Designation or 2 Years 7 Years Appearance After 7 Years at
No.(a) Composition A(b) C(c) A C Kure Beach, N.C.

110 Tough Pitch Cu 0.072 0.065 0.065 0.025 Brown film, smooth, slight patina near edges

Tin

505 Phos. Bronze, 0.083 0.042 0.069 0.017 "Mink brown", slight patina
1.25% Sn

510 Phos. Bronze, 0.150 0.088 0.099 Maroon film, heavy etch
5%Sn

Aluminum

637 Alum. Bronze 0.017 0.009 0.013 Light tan film, smooth

Nickel

1.85 Ni, o. I 34 0.145 0.044 0.036 Dark brown, mottled with green at edges
0.03 Fe

704 6.34 Ni, 0.069 0.052 0.033 Dark brown, plus patina streaks on panel face
0.01 Fe

707 9.16 Ni, 0.052 0.039 0.038 Uniform maroon with patina at edges
0.18 Fe

711 22.76 Ni, 0.036 0.024 0.031 Greenish brown, green near edges, slight etch
0.04 Fe

42.75 Ni, 0.018 0.012 0.019 0.005 Greenish brown, slight green near edges
0.30 Fe

Zinc

420 Tin brass 0.058 0.042 0.024 Dark maroon, smooth

230 Red brass 0.05 I 0.038 0.033 0.026 Brown-maroon film, smooth

260 Cartridge 0.034 0.023 0.030 0.017 Brown-maroon film, smooth, very slight patina
brass

Nickel-Zinc

745 10% nickel- 0.030 0.020 0.024 0.010 Brown with slight patina film in center, green
silver near edges, smooth

752 18% nickel- 0.030 0.020 0.021 Brown film in center, green near edges, smooth
silver

(a) Copper Development Association number; see Appendix, Table A-I, for nominal alloy compositions.
(b) A = 8D-foot lot, Kure Beach, N.C.
(c) C = Point Reyes, California.
 42

TABLE 42. CORROSION RATES OF COPPER AND COPPER

ALLOYS IN MARINE ATMOSPHERES BASED ON
LOSS IN WEIGHT AFTER 10 AND 20 YEARS'
EXPOSURE(53) )
___ Corrosion ~~.l,_IJ1..P.Y _
Sandy Hook, La Jolla, Key' West,
CDA New J~!~~_ California Flq!:j~ __
:\oJal Alloy 10 Yr 20 Yr JO~OYr 10 Yr 20 Yr
-_._-----------
110 Electrolytic tough pitch copper 0028 0.056 0.050 0022 0025
122 Phosphorized copper 0.028 0.046 0.055 0.021 0.020
655 Silicon bronze, 3.1 % Si, 1.1% Mn 0.045 0.078 0.05.1 0.040
521 Phosphor bronze, 89t Sn, 0.1'7,- P 0.050 0089 0.092 0.031 0028
614 Aluminum bronze, 89r. Al 0056 0.047 0.008 0.006 0.012 0.002
High-tensile brass 0.113 0.178 0.078 0.089 0.068 0.078
20-24(/( Zn, 2.5-50/( Mn,
3-TkAI, 2-4'7r Fe
230 Red brass, J 5% Zn 0.047 0,023 0.011 0.020 0.017 a. High - Copper b. a - Phose C. a + {3
260 70-30 brass, 30(;;, Zn 0.039 0.011 0.006 0.015 0009 Bronzes Cu- Zn Brasses
Alloys
442 Admiralty metJL :?9C:;, Zn, 0039 0.011 0.006 0015 0.009
1% Sn
732 Copper-nilkel-zint.:, 0.042 0.01.1 0.016 0.012 0.010
75(Jr Cu, lOt);, Ni, 5\'1( Zn FIGURE 45. CORROSION WEIGHT LOSS AS A FUNCTION
Copper-nickel-tin. 0.045 0.011 0014 0.014 0.011
OF TIME FOR COPPER ALLOYS EXPOSED AT MEAN-
7Cflr Cu, 29% Nl, jtX Sn TIDE HEY ATION IN TROPICAL SEAWATER(52)
(3) See Appendix, Table A-I, for nominal alloy compositions
(b) Dash denotes 20-year specimens lost
40
Splash and Tide ~ AI bronze l> 70Cu-30Zn
o P bronze o 8OCu-20Zn
X 5i bronze X 90Cu-iOZn
The corrosion behavior of copper alloys in the splash zone --- Copper
more nearly follows their performance in the atmosphere than
in immersed conditions. As a general rule, any copper alloy
~ 20
that has good resistance to a severe marine atmosphere, such as o
Cristobal, Canal Zone, will also do well in the splash zone. -l

Alloys exposed at mean tide show corrosion rates ranging

from about 20 to 60 percent of those observed for alloys
under fully immersed conditions. Thus the behavior under fully
024 8
immersed conditions can be used as a guide for the selection of
a resistant alloy in a half-tide application. The resistance of an
isolated panel of copper in the tide zone is superior to that in a. High - Copper b. a - Phose c, a + {3
the fully immersed condition, and is in marked contrast to the Bronzes Cu - Zn Brasses
Alloys
relatively poor behavior of an isolated steel panel at the half-
tide level. Weight-loss curves for the half-tide performance of
copper alloys after 16 years is given in Figure 45.(52) Note the
FIGURE 46. CORROSION WEIGHT LOSS AS A FUNCTION
lower rates obtained as compared with the same alloys under
OF TIME FOR COPPER ALLOYS CONTINUOUSLY
fully immersed conditions in Figure 46.
IMMERSED IN TROPICAL SEAWATER(52)

Submerged, Corrosion Factors

Film Formation. Although copper is a noble metal, the
main reason for its satisfactory performance in a seawater
There is extensive application of copper-base alloys under
application is that a protective film of cuprous oxide fOnTIS
submerged conditions. In seawater, copper alloys behave
directly on the metal surface. Often products deposit on top of
somewhat differently from some other metals such as steel and
this film and may contribute to the protection. These may be
aluminum. Before presenting corrosion data, the fadors
cupric oxychloride, cupric hydroxide, or basic copper
involved in the attack by seawater and typical failure
carbonate and calcareous materials.(54)
mechanisms for copper and its alloys are reviewed.

The factors which affect the performance in seawater In condenser-tube practice, especially resistant films are
include film formation, oxygen content, velocity, temperature, often produced in the presence of iron. Cupronickels
metal-ion concentration, and biofouling. Galvanic couples with containing iron develop a dark, resistant film,(55) In a recent
copper more often have an adverse effect on the behavior of patent, iron has been added to aluminum brass to promote film
the other metal in the cOllple by causing it to corrode more formatlOn,(56) Ferrous sulfate has also been added to seawater
rapidly. Dezincification is a common form of failure for flowing through aluminum-brass condenser tubes to form the
high-zinc brasses, whether coupled or not. The factors listed iron film with considerable benefit. More recently,(57)
above are interrelated and their relative order of importance laboratory studies suggest that ferrous ions are oxidized to
may change with the specific conditions in each situation. lepidocrocite by dissolved oxygen, which forms a colloid and is
 43
deposited electrophoretically at the cathode. This film acts as a In completely oxygen-free seawater, such as is used in
cathodic or safe inhibitor by polarizing the reduction of some sections of distillation-type desalination plants, there is
oxygen. evidence that velocities somewhat higher than those listed in
Table 44 probably can be tolerated.
Polluted seawater often has hydrogen sulfide or other
sulfides present. The copper sulfide film formed on the metal
surface in polluted seawater is more cathodic than the corro- 20
sion film developed in clean seawater. If there are breaks in the • COA number
sulfide film, local attack is stimulated greatly by the large area ,.,
a.
of active cathode. Some alloys show much less tendency to E 15
develop such films. Cupronickels and aluminum-copper alloys, .,
for example, are more resistant to polluted seawater than say '0
0::
copper and ordinary brass, as shown in Table 43. 10
c Temp. - 225 F
0
·iii pH - 7.2 -7.5
C02 - < 10 ppm
TABLE 43. BEHAVIOR OF COPPER ALLOYS IN SEAWATER
t
0
5 Vel. - 6 Ips
Time - 15 to 30 doys
L)
UNDER VARIOUS CONDITIONS(58-60) Once through system

Resislant:e to Indicated Factors(a)

80 90
Alloy Dezincification Turbulence Biofouling Pollution

Copper NA E Velm:ity sensitive

Red brass G G Beller than copper, but

FIGURE 47. EFFECT OF DISSOLVED OXYGEN IN
velocity sensitive SEAWATER ON THE CORROSION RATE OF
Arsenical admirality G G Poor impingement, as COPPER ALLOYS~54A)
brass compared with othl'T
alloys

Arsenical aluminum G G G Good 10 excellent

brass resistance to high TABLE 44. RECOMMENDED MAXIMUM VELOCITY TO
velocity REDUCE TENDENCY TO IMPINGEMENT
90-10 cupronickel NA G+ F G Good to excellent in AND TO OTHER VELOCITY EFFECTS IN
plus iron high velocity
CLEAN SEAWATER(32,61)
70-30 cupronickel NA G Excellent in high vclm:ity
plus iron more tendency to pit
in stagnant seawater Alloy CDA No. Maximum Velocity, fps
than 90-10 alloy

Copper 110 3
(a) E - excellent
G good
f - fair
P poor
Arsenical admiralty brass 443 6
NA nol applicable.

Arsenical aluminum brass 687 lO(a)

Oxygen Content. On clean metal surfaces, the most 90Cu-IONi (1.5 Fe) 706 12(a)
important factor influencing the corrosiveness of seawater to
copper alloys is the seawater oxygen level. The corrosion 70Cu-30Ni (0.7 Fe) 715 15(a)
reaction can be affected in at least three ways: (I)
depolarization of cathode areas, (2) oxidation of cuprous ions (a) Typical condensers are run at 8 fps or less.
to the more corrosive cupric state, and (3) the promotion of a
protective film on the metal surface, as discussed above. In
recirculating systems, when all oxygen is removed from the Temperature. The corrosion rate for copper alloys usually
seawater, the rate of attack on copper alloys may be of the is higher, other factors being the same, as the temperature is
order of I percent of that observed with fully aerated seawater. raised. Pump impellers, condenser tubes, valves, etc., tend to
The same effect can be obtained by completely deaerating the corrode at higher rates in seawater at summer temperatures at
seawater as shown in Figure 47. For copper or an alloy with a Wrightsville Beach, N. c., than at winter temperatures. Copper
protective film, the oxygen must diffuse through the film for alloys also show higher rates of attack in the warm waters of
corrosion to continue. Corrosion rates tend to decrease with the Pacific Ocean near the Panama Canal Zone as compared
time during the formation of such protective films. The oxygen with those obtained in water off the coast of California.
level then becomes of much less significance in the rate of
further attack. When seawater is heated to higher temperatures, both the
reduced oxygen content and the greater tendency to form
mineral scale tend to make the environment less aggressive, and
Velocity. Copper and some of its alloys are sensitive to corrosion rate decreases, as illustrated in Figure 48.
velocity effects. On the other hand, copper can withstand
stagnant seawater better than many other metals. The usual
recommended maximum velocity for copper in seawater is Metal-Ion Concentration. Copper enters seawater as
about 3 fps. Alloying with such elements as nickel or cuprous ions. Oxygen in the seawater tends to convert the
aluminum greatly improves the resistance to impingement cuprous ions to cupric ions. Since cupric ions can attack
attack. Recommended maximum velocities for other alloys copper to form more cuprous ions, copper ions and oxygen in
based on condenser-tube experience in clean seawater are given solution increase the attack. This is observed in piping systems
in Table 44. and recircula ting system.
 44
m:lss may show growth rings of dense copper layers inter-
spersed with bands of cuprous oxide,
6
Continuous exposure - 156 days
Dissolved O2 level - 40 to 600 ppb I Related processes occur less frequently on (1) copper-
pH - 6.2 to 7.8
>- Bri ne cone. foetor - 0.8 to 1.1 a:uminum alloys (dealuminification) and (b) copper-nickcl
a.
E Turbulence - moderate to low at 250 FI alloys (denickelifieation l. In recent years, the terms dealloying
• 2 % aluminum brass i and parting have been introduced to refer to the general
£ o Admiralty brass i plie no menon.
0
a:: 3
• 90/10 and 70/30 Cu - Ni (avg) I
c: Submerged, Stress-Corrosion Cracking
.2
'"
~
2
(:; Copper alloys sometimes fail by stress corrosion in sea-
U I wakr service. Mangancse bronze propellers, with high rcsidual
stresses, have failed by stress-corrosion cracking. Roller-
expanded copper-alloy tubes in tube sheets, especially when
0
130 150 170 190 210 230 c'xpanded beyond tlie back face of the tube shcet, have failed
Temperature I F during shutdown, Seawater algae slimes, high in nitrogen com-
pounds. arc considered responsiblcJ53) Most of tlie stress-
FIGURE 48. EFFECT OF TEMPERATURE ON CORROSIOl\: corrosion failurc~s of copper alloys rcported in thc literaturc
RATE OF COPPER-BASE HEAT-EXCHANGER TUBE have identified thc presence of ammonia in the environment or
MATERIALS IN DEAERATED NORMAL SEAWATER some nitrogen compound such as amines or nitric acid which
AT FREEPORT PLANT(62) could convert to ammonia, Since contaminated seawater may
contain ammonia, alloys susceptible to stress-corrosion cracking
should not bc uscd at high tensile-stress levels (residual or
A higher concentration of mctal ions tends to form undcr
appliccl),
a crcvice, whereas any copper ions formed outside the crevice
are swept away by the current. Under these circumstances,
local attack takes place on the copper just outside the crevice. In general, high-zinc brasses and certain aluminum brasses
arc particularly susceptihle to stress-corrosion cracking, whereas

Copper ions also promote pitting and local attack of less cupronickels, copper, and high-copper alloys, in gcncral, are less
noble metals such as aluminum or steel. susceptible.

Biofouling. The corrosion behavior of copper alloys

Submerged, Corrosion Data
influences their tendency to biofoul. Normally the presencc of
copper ions in the watcr film adjacent to the corroding metal
surface is toxic to marine life. At a corrnsion rate of (,
COPPl'L Coppcr l'olTodes typically at ratcs varying from
mg/dm/day, no fouling occurs in a typical situation. Thl\
0,5 to 2 mpy in shallow and deep-ocean environments, A
amounts to about 1 mpy for copper. If the copper or coppcr-
summary of recent information is presented in Figure 49,(54)
rich alloy surface is provided with cathodic protection as, for
example, when coupled to steel, aluminum, or another anodic
metal, the copper-alloy corrosion may be reduccd or cease
altogether. Under the latter condition, biofouling will appear 3r-----------------------,
on the surface, 6,000 Feet
o NCEL
t> INCO
Galvanic Attack. Since copper is cathodic to most other • MEL
metals in seawater, galvanic attack is usually a factor affecting QlI NCEL
>-
the other metal in the couple rather than the cOpper. In a. Surface
E 2
general, copper alloys may be safely coupled to each other in ~ NCEL, Pacific
seawater. Therc are cascs where the proper galvanic relationship OJ
c::::J INCa, Pacific

results in longer life. Tube sheets of copper alloy are usually a

a::
selected so as to be slightly anodic to the tubing alloy, C.g., c:
naval-brass tube sheet with aluminum-brass tubes. 2
'"o
~ I
Dezincification. Corrosion by dczincification usually o
U
occurs on high-brass alloys in seawater and in other cnviron-
ments. The first step in dezincification is now considered to bc
the dissolution of both the copper and thc zinc. Thc COppLT
ions are then reduced to copper close to the point where
dissolution took place.

Dezincification may takc scwral forms, C.g.. thc' plug type

whcrc a mass of coppcr displaces thc original hrass, or thc Iayn
FIGURE 49. CORROSION RATES OF COPPER IN
type where a cross section shows an even layer of porous
SEAWATER(54)
copper underneath which the metal is not attacked. The copper Ij sed with perm 11 () f U. S N av die i v i I F n q In e (~r i n 9 L d b 0 rill 0 r y
 4S
After 16 years at shallow depths in the Pacific off of the Brasses. The copper-zinc alloys vary widely in their resis-
Panama Canal Zone, copper showed a rate of attack of 0.20 tance to seawater. High-zinc alloys tend to fail by dezincifica-
mpy. The deepest pit, as recorded in Table 45, was 57 mils tion, especially those with two or more phases present. Alloys
(since pitting often is most rapid during the first few years, an with 15 percent zinc or less are not so likely to fail by this
average pitting rate is without significance). Single-phase brasses mechanism. An excessive loss in strength after exposure to
as well as silicon and phosphor bronze corrode at about the seawater is a good indication that dezincification has taken
same rate as copper. In the slowly moving seawater involved in place. After 16 years at shallow depths in the Pacific Ocean,
these exposures, copper is relatively insensitive to the amount alloys of 30 percent or more zinc show strength losses ranging
of oxygen present. from 20 to 60 percent (Figure 50).
TABLE 45. SUMMARY OF FULL IMMERSION RESULTS FOR
COPPER ALLOYS AFTER 16 YEARS IN THE
PACIFIC OFF THE PANAMA CANAL ZONE(52) 60
Deepest Loss in
Corrosion Rate, Pit, Tensile Strength.
Metal mpy mils pcn:ent Notes
Copper 0.376(') 01()(b) 57 1.1 Local attack; resistant [0
50
fouling

Silk-on bronze 0.365 0.20 36 35 Ditto

C
B
Phosphor bronze 0.342 0.18 19 7.0
Ditto
8. 40
Aluminum bronze 0079 0.053 2\(c) 3.2 Fouling atta.:k: pitting not
&.
signifiLant
C.
<:
Commercial bronze 0.308 0.18 51 5.1 local and fouling aft.Kk ~ 30
Low bra!>s 0.233 0.10 46 3.3 Delin.:ifkation: random
iii
.!:
Cntridgc brass 0.244 0.10 (dl :::0.0 Ditto
en 20
en
Naval brass (511) 0.779 041 (dl 57.6 Dezim:ifi<.:ation, uniform
.3
Muntz metal (As) 0.5 II 0.31 (dl 45.5 Dezincification. nonuniform

Mang<mcsc bronze 1.072 080 36 45.8 Ditto 10

(a) Valut's in this column are totill penetration divided by 16 (years)
(bl V:llucs in this column were estimated graphically at [6 years.
(c) Eight-year pimel; no deep pit on lo-year pilnel.
(d) Not applicable: dczincification damage
0
0 10 20 30 40 50
Zinc Content, percent
High-Copper Alloys. Alloys of commercial importance, as
far as seawater is concerned, include beryllium-eopper, iron- FIGURE 50. EFFECT OF ZINC CONTENT ON LOSS IN
modified copper, and phosphorized copper. The addition of 2 STRENGTH FOR BRASSES AFTER 16 YEARS' SUB-
percent beryllium (Table 46) is slightly beneficial as compared MERSION IN THE PACIFIC OCEAN NEAR THE
with the corrosion rate of unalloyed copper. Welded specimens PANAMA CANAL ZONE(52)
showed rates similar to those of specimens in the unwelded
condition, Deep- and shallow-ocean experience with red brass (CDA
No. 230) is summarized in Figure 51. Note that corrosion rates
TABLE 46. CORROSION OF COPPER AND BERYLLIUM- range from 0.5 to 2 mpy, which is similar to the rates for
COPPER IN SEAWATER copper. Red brass can be used for undersea service where a
material with more strength than copper is required.
Corrosion Rate,
mpy (Calculated
Depth, Time, From Weight 2
0 Solid points obtained in 6,000 Feet
CDA No.(a) Metal feet days Loss) sediment; the others
~ obtained in water /),.INCO
102 Copper 5 181 1.4 0 MEL
>.
Q. 2,500 Feet
E V INCO
102 Copper 2370 402 0.9, 1.4
or Surface
172 Be-copper 5 181 0.1 (O.I)(b) e
ll:
o Pacific, INCO
o KBNe, Aftontic, MEL
<: /),.
0
172 Be-copper 2370 402 0.6 (O.5)(b) '0;
g
0
(a) See Appendix, Table A-I, for nominal alloy composition. u
~
(b) These values for chain specimens. ~

Phosphorized copper and copper behave very similarly in oo~--I.;:="";;:~+':'--~600~--~-~~--I...J200

seawater. The corrosion rate of the iron-modified copper alloy,
Exposure Time,
e.g., CDA No. 194 with 2.3 percent iron, is considerably lower
than that of copper, judging from preliminary reports on the
ability of this alloy to form protective films in seawater. It is FIGURE 51. CORROSION RATES OF RED BRASS(54)
Used with permission of U. S. Naval Civil Engineering Labora-
performing well as welded tubing in saline waters. tory
 46
Dezincification of both admiralty brass and aluminum Deep- and shallow-Dcean experience for silicon bronze is
brass in seawater can normally be inhibited by small additions summarized in Figure 54. Note that corrosion rates range from
of arsenic, antimony, or phosphorus. The behavior of arsenical 0.5 to 2 mpy for seawater exposure. The corrosion rates of 5
admiralty brass is summarized in Figure 52 for both deep- and and 7 percent aluminum bronzes are presented in Figure 55.
shallow-ocean environments. No dezincification was observed in The rates for the 5 percent alloy are all I mpy or less, For the
any of these exposures. Since this alloy is readily available, it, 7 percent alloy, shall('w-water rates as high as 2.9 mpy are
like copper, can be specified for ordinary construction. reported, compared with a rate of 1.4 mpy at 6000 feet. An
examination of the 7 pt:rcent aluminum alloy showed
dt'aluminification on about half of the specimens.(54lOn the 5
2r--------------::-=~_::_-_, percent aluminum alloy, corrosion was uniform. Thus, for ser·
Sol id points obtained in
6,000 Feet
o NCEL vict: in st:awater, the 5 percent aluminum alloy would be
sediment; the others
obtained in water t:. INCO recommended.
2,500 Feet
'"'0-
E o NCEL 3% Silicon Bronze Silicon Bronze A
V INCO 6,000 Feet 6,000 Feet
Q)

'0
4,250 Feet t;. INCa o NCEL
Cl:: X Atlantic, NASL 2,500 Feet V INCO
Surface, Pacific 3
c
o f:1a NCEL--- o INCa ,2,500 Feet
'iii DINCO Surface, Pacific d NCEL
2 o INCO

<3 '"'
0.
E X
X PCZ, NRL
c::::J INCO Surface, Pacific
~ NCEL
~ INCa
Q)

OL..._...J.::.jI-=:::::_l.-_ _L....._ _L....._--IL....._ _ '0

Cl::
2
Solid points obtained in
o 200 400 600 BOO 1000 1200
c- sediment; the others
Exposure Time, days o obtained in water
VI
2
(;
FIGURE 52. CORROSION RATES OF ARSENICAL u
ADMIRALTY BRASS(54)
Used with permission of U. S. Naval Civil Engineering Laboratorv

In the brass family, the alloy most resistant to seawater is

aluminum brass. It is normally fortified with arsenic (CDA No.
687). The corrosion behavior for this alloy is summarized in
Figure 53. Note that it corrodes at a rate of about 0.8 mpy or
ol-_..L:oJ:_ _.L._--l._ _...J-_ _~ _ ~ ~ ~
less. o 200 400 600 BOO 1000 1200 1400
Exposure Time, days

2 6,000 Feet
Solid points obtained in
sediment; the others t:. INCO
obtained in water 2,500 Feet 5% Aluminum Bronze 7% Aluminum Bronze

'"'E
0- V INCO 6,000 Feet 6,000 Feet
4,250 Feet t;. INCO V INCO
Q) X Atlantic, NASL o NCEL o NCEL
'0 Surface, Pacific 3- 2,500 Feet 2,500 Feet
Cl::
CJ INCO o INCO d INCa
c
Q Surface, Pacific
o NCEL

'"2 '"'
0.
E X PCZ, NRL
Surface, Pacific

0 + PHH c:::J INCO

u ~INCO rZZZI NCEL
oJ
'0 2
Cl:: Solid points obtained in sediment;
the others obtained in water
c
0 0
0 200 400 600 BOO 1200 'iii
2
Exposure Time, days 0
U

FIGURE 53. CORROSION RATES OF ALUMINUM I~

BRASS(54)
Used with permission of U. S. Naval Civil Engineering Laboratory ~ c»
Ii " ~+-
•
0 A
• ~ .-=:--::::.=+::+,_--~n---_
Bronzes. The corrosion rate after 16 years in the Pacific !"L
......~QPO::-'-::-~----~- _
~
oOI-_..L2I.00---4-l5'O--6.J00---B~00~-~1~0001:-:---1~2-:-00=---:1~400
I
near the Canal Zone is given for several bronzes in Table 45.
Note the low rate of 0.05 mpy for an aluminum bronze. Both
Exposure Time, days
silicon bronze and phosphor bronze show a rate of about 0.2
mpy, which is similar to that for copper. The depth of the FIGURE 55. CORROSION RATES OF WROUGHT
deepest pit in these bronze alloys ranged from 2 I to 36 mils as ALUMINUM BRONZES(54)
compared with 57 mils for copper. Used with permission of U. S. Naval Civil Engineering Laboratory
 47
Cupronickels. The cupronickels are perhaps the most use- reported by May(65) in Table 47 also indicate that the cupro-
ful of all commercially available copper alloys in seawater.(63) nickel alloys are superior to admiralty brass in both cold and
Corrosion rates for three of these alloys in both shallow- and hot seawa ter.
deep-ocean waters are summarized in Figure 56. These rates
range from a maximum of 1.3 mpy for a short-time exposure
12r-----------------------,
to 0.8 mpy after several years.
10
Aluminum -brass
2 r--------------------,
6,000 2,500 Surface,

,.,
a.
E
Cu- Ni Alloy 90-10
Cu-Ni Alloy 70-30, 5 % Fe
0
A
Feet Feet
'\1
o
Pcciflc

-'"
c:
~
6

Cu-Ni Alloy 70-30, 0.5 % Fe 0 <> '"

ll.
Solid points obtained in sediment; 70-30 copper- nickel
the others obtained in waler
40 60 80 100 120
c:
.Q Service Hours, thousands
V>
~
o
u FIGURE 57. COMPARATIVE PERFORMANCE OF
CONDENSER TUBES AT THE HARBOR STEAM
• PLANT, LOS A:'oIGELES. CALIFORNIA(64)
o0~-.....L-::2~OO::----:-4-:!-OO':""""----:6~O-::O--~8~OO~--10~OO~--12~OO
Exposure Time, days
TABLE 47. COMPARISON OF CORROSION DATA ON
FIGURE 56. CORROSION RATES OF COPPER-NICKEL NORMAL SEAWATER AND SEAWATER
ALLOYS(54) BRINE AT COLD AND ELEVATED
Used with permission of U. S. Naval Civil Engineering Laboratory
TEMPERATURES( 65)

Submerged, Heat-Exchanger-Corrosion Cold Hot

Seawater
----
Seawater
-----
The three most commonly used copper-base alloys for Temperature 80 F 187 F
heat-exchanger service are 70 Cu-30Ni-0.5Fe, 90Cu-IONi-IAFe,
and arsenical aluminum brass, 76Cu-22Zn-2AI-O.02As. Arsenical pH 8.2 8.2
admiralty (70Cu-29Zn-1 Sn-0.02As) brass formerly was recom- Oxygen, ppm 8.5 7.l'>
mended for seawater service but is not now favored. A new Salinity: gil 35 59.3
copper-iron alloy (97.7Cu-2.3Fe-0.03P) is showing promising
results in seawater and is expected to compete with the above Materials
_.---- COif-p_~on B-.il~M
three alloys for heat-exchanger applications. Because it can be
Monel-400 0.0003 0.0004
used in the hard-{)rawn condition, thinner tube walls can be
employed. This, plus the fact that this alloy has higher conduc- Type 304 stai nless steel 0.0030(a) 0.0001
tivity than presently used alloys, should result in a red uction in Carbon steel 0.0290 0.0220
the cost of a heat exchanger of a given capacity. 70-30 copper-nickel 0.0015 0.0014

An overall comparison of the relative behavior of the 90-10 copper-nickel 0.0028 0.0011
cupronickels, aluminum brass, and several other copper mate- Aluminum brass 0.0019 0.0025
rials is given in Table 43. These heat-exchanger alloys and their Admiralty brass 0.012 0.0019
general characteristics are briefly discussed below.
==--=~---==:======~===
(a) Severe pitting under insulator.
Arsenical Admiralty Brass. Admiralty brass without arsenic
tends to dezincify and become a porous mass of copper with Admiralty brass could be used in a distillation plant
little strength. The use of arsenic-modified admiralty brass in during the lower temperature stages. Admiralty brass corrodes
marine condensers dates back to the 1920s. The arsenic- more rapidly in aerated heated seawater. Mattson and
modified alloy, however, is not so resistant to impingement Fuller(62) reported that at temperatures up to 126 F, unmodi-
attack as the cupronickels and aluminum brass. Admiralty brass fied admiralty brass dezincified after 4 years in deaerated
is susceptible to impingement attack particularly at the tube seawater.
entrance zone, near the tube sheet. More resistant condenser-
tube alloys have been available for some time. Generally,
admiralty brass is not used for condenser tubes in cases where Arsenical Aluminum Brass. Arsenical aluminum brass has
seawater velocities are above 5 or 6 fps. been very successful in many applications involving seawater
service. As with admiralty brass, arsenic is required to prevent
Todhunter(64) has compared the performance of four dezincification. The iron-modified aluminum brass, mentioned
condenser-tube alloys at the Harbor Steam Plant, Los Angeles on page 42, would seem to have promise in view of the
Department of Water and Power. The percent failures of tube benefit of iron additions to copper and copper-nickel alloys in
bundles of each alloy since 1950 is shown in Figure 57. seawater service.(56) The aluminum content promotes a type
Admiralty brass is definitely the poorest performer of the four of protective film which is more resistant to impingement than
alloys under these service conditions. Experimental n~sults is the case wit h ordinary brasses.
 48
TABLE 48. RESULTS OF CORROSION TESTS AFTER 156
Aluminum brass is shown to be superior to admiralty DAYS IN MISCELLANEOUS ENVIRONMENTS
brass, but inferior to cupronickel (see Figure 57). The Los AT FREEPORT(62)
Angeles harbor waters are polluted, and under these circum-
Spool 24 25 26
stances, aluminum brass does not perform so well as the 70-30
cupronickel alloy. In clean seawater, aluminum brass often Location Plant-effluent Distilled fresh Down stream
djscharge Pit(a) water from condensate from
gives service equal to that given by the 90 copper-IO nickel- Effect 12(bl Effect I(C)
iron alloy, and is selected because of its lower cost. The results
Dissolved Oxygen Almost normal Deaerated Deaerated
for a variety of seawater conditions, under which the aluminum for Seawater
brass alloy showed corrosion resistance similar to that of the
Temperature (Avg), F 105 130 261
90Cu-IONi+Fe alloy, are given in Tables 48 through 51.
pH 7.5-7.8 7.5 8.5

Turbulence Moderate Moderate Moderate

90-10 and 70-30 Cupronickels. Both the 90-10 and 70-30
cupronickels, with iron additions (see Table 51) have outstand- Corr. Max. Carr. Max. Carr. Max.
ingly good resistance to seawater. Seawater velocities can be Ratdt·), Pitting(O, Ratc<e), Pitting{f), Ratd e ), Pi tting(f) ,
higher with the cupronickels than with most other copper ~~1.'9~e.~_~J~_~~ _1"!!Qi'_- -~--- -~ -_!!!~-- _J!!£L_ _ _~i~ _
Carbon steel 26 Perf{g) 14 None 0.6 None
alloys. However, because of the excessive pumping costs in- Type 304 stainless steel(h) 2.1 PerJ1'il-Pl' <0.1 4P 0.3 None
volved in actual practice, advantage of tlJis velocity charac- Type 316 stainless steel(h) 0.1 17C <0.1 None 0.3 None
Cast alloy 2()(h) 0.3 6l' 0.4 None
teristic is not normally employed to the fullest extent.
\Ionel-40O<h) 0.5 15l' 0.3 5P 0.9 None
70-30 copper-nickel 1.0 24l' 0.2 None 0.3 None
Navy experience with 70-30 cupronickel alloys on 20 90-10 copper-nickel 0.7 None 0.2 Trace-P 0.4 NOflc
destroyers showed that, on the average, 0.37 percent of the 2% aluminum brass 0.8 ~one 03 None 0.4 None-

condenser tubes plugged after 20 years of service. Some of the Cast iron 31 None 27 None 2.9 None
tubes failed on the steam side. Coastal plants using clean Ni-Rcsist iron Type I 5.5 None 13 None 0.9 None
~i-Resist iron Type D-2 63 None II None 1.0 None
seawater show even better performance. In polluted seawater,
the rate of plugging for cupronickel is about nine times higher, (a) Specimens continuously submerged in mixture of cooling seawater from Condens\~r 312 and
seawater brine from Effect 12.
but it is still much superior to that of other copper alloys. (h) In discharge line from Pump P-42.
(c) In discharge line from Pump P-31.
(d) Near Seawater intdke pit
(e) Avrrage corrosion calculated from weight loss
(f) Attack in 156 days. P == surface pitting. C == crevice attack.
(g) Specimens 0.040 inch thick failed by general corrosion and thinning.
(h) Corrosion is limited largely to localized attack producing pits
(i) Specimens 0.038 inch thick.

TABLE 49. RESULTS OF CORROSION TESTS AFTER 90 DAYS IN DEAERATED SEAWATER BRINE(a) AT SAN DIEGO(62)
(In-heat exchanger circuit prior to evaporators)

Spool
Location(b) Inlet WB Inlet WB Inlet WB Inlet WB Inlet WB OutletWB
Slage 34 Stage 24 Stage 16 Stage 8 Stage 1 Brine Heater

Temperature (Range 85-95.90 105·115.107 t29-148.133 163-178.166 191-215.196 200-225.205

and Avg). F

Corr'<CI Max(d) Corr'<C) Max(d) Corr3c) Max(dl Corr'<c) Max(d) Cordc) Max(d) Corr.<cl Max(d)
Rate, Pitting, Rate, Pitting, Rate, Pitting, Rate, Pitting, Rate, Pitting, Rate, Pitting,
_':I}py mils mp~__ mils mpy mils _r:':l2Y__ mils r.!1py_. mils __!!'J?L mils
Carbon steel 6.2 None 10 None 13 None 21 None 14 None 22 Peri(e)

3% nickel steel 8.4 None 14 None IS None 20 None IJ None 15 None

Type 316 stainless <0.1 3C <0.1 4C <01 4C <0.1 2C <0.1 6C <0.1 8C

steel
Wrought Alloy 20 <0.1 2C <0.1 IC <0.1 Trace-{~ <0.1 4C <0.1 IC <0.1 3C
Incoloy 825 <0.1 2C <0.1 IC <0.1 frace-C <0.1 2C <0.1 5C <0.1 2C

MoneJ-400 0.5 None 0.5 None 0.4 None 0.3 None 0.3 Trace-P 0.3 None

70-30 copper-nickel 0.8 None 0.7 None 0.6 Tracc-P 0.5 None 0.4 None 0.4 None

90-10 copper-nickel 0.7 None 0.8 None 0.7 None 0.6 None 0.5 None 0.6 None

2% aluminum brass 0.9 None 0.7 None 0.6 None 0.6 None 0.5 None 0.7 None

Admiralty brass 1.0 None 1.0 None 0.9 None 0.8 None 0.5 None 1.1 None

10% AJ-S% Ni bronze 0.8 None 0.6 None 0.5 None 0.4 None 0.4 None 0.6 None

Muntz metal 0.8(0 None 0.9(1) None 0.8(1) None 0.9(1) None 0.9(1) None 17(f) None

Cast iron II None 14 None 15 None 23 None 15 None 22 None

Ductile iron I1 None 16 None 18 None 22 48(g) 17 None 27 None

3% Ni-l % cast iron 11 None 12 None 16 None 20 None 12 None 16 None

Ni-Resist iron 3.3 None 4.4 None 2.9 None 3.2 None 2.7 None 3.1 None
Type I

Ni-Resist iron 2.7 None 3.2 None 2.7 None 3.7 None 2.7 None 3.2 None
Type D-2

(a) Dissolved oxygen 5 ppb, brine concentration factor 1.5 to 2.0, pH 7.0 to 7.5, moderate turbulence.
(b) End plate of water box of condenser of stage indicated, except Spool 9 1Il direct path of brine healer discharge. WB water box.
(c) Average corrosion calculated from weight loss.
(d) Attack in 90 days. P == surface pittlOg. C;:: crevice attack
(e) Very rough surface, failed by general corrOSlOn.
(f) Dezincification was observed.
(g) Maximum erosion at spacer.
 49
TABLE 50. RESULTS OF CORROSION TESTS AFTER 90 DAYS IN FLASHING DEAERATED HOT
SEAWATER BRINE(a) AT SAN DIEGO(62)
(In flash chambers of evaporator stages)

Spool 10 II 12 13 14 15 16
Location(b) Stage I Stage I Stage 8 Stage 16 Stage 24 Stage 31 Stage 36
Near Inlet Near Outlet Near Outlet Near Outlet Near Outlet Near Outlet Near Outlet
Temperature (Range and 196-218,200 196-218,200 169-192,174 141-158,144 116·128,118 102-106, 103 90-92,90
Avg),F
Brine-concentration factor 1.5-2.0 1.5-2.0 1.6-2.1 1.7-2.1 1.7-2.2 1.7-2.2 1.7-2.2

Corr.(c) Max(d) Corr.(c) Max(d) Corr.(c) Max(d) Corr'<c) Max(d) Corr,<cl Max(d) Corr'<c) Max(d) Cordc) Max(d)
Rate, Pitting, Rate, Pitting, Rate, Pitting, Rate, Pitting, Ra te, Pi t ting, Rate, Pitting, Rate, Pitting,
Exposed Metals mpy mils --"'~ mils --"'1'X_ mils _!!'1'X_ mils ~L. mils _mpy mils ---"'!'L mils
Carbon steel 15 None 16 None 14 None 10 None 7.0 None 7.0 None 5.8 None

3% nickel steel 8.2 None II None 12 None 9.4 None 7.5 None 6.7 None 5.1 None
Type 3 I 6 stainless steel <0.1 3C <0.1 8C <0.1 2C <0.1 4C <0.1 IC <0.1 4C <0.1 Trace-e
Wrought Alloy 20 <0.1 2C <0.1 6C <0.1 2C <0.1 2C <0.1 Trace-C <0.1 Trace-C <0.1 2C
Incaloy 825 <0.1 2C <0.1 4C <0.1 Trace-C <0.1 Trace-C <0.1 Trace-e <0.1 IC <0.1 Trace-e
Monel-400 0.2 Trace-PC 004 IP 0.2 Trace-P 0.1 Trace-P 0.1 Trace-CP 0.1 None <0.1 None

70-30 copper-nickel 0.3 None 0.5 None 0.2 None 0.2 None 0.1 None 0.2 None 0.3 None
90- 10 copper-nickel 0.5 None 0.6 None 0.3 None 0.3 None 0.3 None 0.3 None 0.4 None

2% aluminum brass 0.5 None 1.0 2P 0.4 None 0.3 None 0.3 None 0.4 Trace-P 0.3 None
Admiralty brass 0.8 None 1.0 None 0.5 None 0.5 None 0.6 None 0.6 Trace-P 0.5 None

10% A1-5% Ni bronze 004 None 004 4P 0.3 None 0.3 None 0.3 None 0.4 None 0.3 None
Muntz metal 0.9(e) None 1.3(e) None 0.5 None 0.5 None 0.5(e) None 0.6(e) None 0.6 None

Cast iron II None 13 None II None 8.8 None 8.6 None 6.4 None 5.7 None

Ductile iron 15 None 17 23(f) 14 None 10 None 9.6 None 8.0 None 6.4 None
3% Ni-l % Cr cast iron 9 None 14 None 8.6 None 8.9 None 5.9 None 6.4 None 4.8 None

Ni-Resist iron Type I 2.2 None 3.0 None 2.1 None 2.1 None 1.5 None 2.3 None 1.9 None

Ni-Resist iron Type 0-2 3.2 None 2.5 None 2.3 None 2.0 None 2.2 None 2.4 None 1.8 None

(a) Dissolved oxygen 5 ppb, pH 7.0 to 7.5, moderate turbulence except at Spools 10 and II.
(b) Submerged near inlet or outlet of flash chamber of evaporator stage indicated.
(c) Average corrosion calculated from weight loss.
(d) Attack in 90 days. p; surface pitting. C; crevice attack.
(e) Dezincification was observed.
(f) Maximum erosion at spacer.

TABLE 51. CORROSION OF CONDENSER TUBES IN

In recent years, the 90Cu-IONi-1.4Fe alloy has re-
POLLUTED AND CLEAN SEAWATER(66)
ceived much wider application in both condensers and heat
exchangers for desalination plants. Recent cost studies indicate
Velocity, 7.5 fps
that a 20-gauge 90-10 cupronickel tube is competitive with an
Duration, 64 days
l8-gauge aluminum-brass tube. Because of the better per-
formance of the 90-10 cupronickel, it should last longer in
Corrosion Rate, mpy spite of the thinner gauge.
Polluted
CDA Clean Seawater
Some corrosion results from Office of Saline Water plants
Alloy No.(a) Seawater (3 PPM H2S) as reported by Fuller(62) are given in Tables 48, 49, and 50. It
90/10 Cu-Ni 706 3 34 can be seen that, for oxygen-free seawater, the advantage of
the cupronickels over other copper alloys is not too significant.
70/30 Cu-Ni 715 5 26
However, during excursions from normal operating practice,
2% Al brass 687 3 22 there would be an advantage to having cupronickel-alloy con-
struction. A plot of data from the Freeport, Texas, plant,
6% Al brass 608 5 21
shown in Figure 48, shows the cupronickel alloys to be slightly
As admiralty brass 443 13 35 superior to admiralty brass and aluminum brass.
Phosphor copper 122 14 105
A survey of heat-exchanger tubes used in 55 multistage
flash distillation plants was conducted by E. H. Newton and J.
(a) See Appendix, Table A-I, for nominal alloy compositions.
D. Birkett.(67) Most of the tube failures resulted from pitting
perforation on the seawater side. Some failures also resulted
Of the two alloys, 70Cu-30Ni alloy is usually preferred for from distillate corrosion and were ascribed to poor venting of
more extreme conditions because of its superior corrosion oxygen and carbon dioxide. In the heat-reject stages, seaweed
resistance. However, in stagnant seawater, it has a greater and shells frequently lodged on the tube wells, causing impinge-
tendency to pit than does the 90Cu-IONi alloy. ment or cavitation attack.
 50
A summary of Newton and Birkett's results for the Office Normally the oxidizing conditions present in typical
of Saline Water is given in Table 52. It is to be noted that the marine environments promote the passivity of titanium.
tube performance of 70Cu-30Ni is superior to that of arsenical Mechanically or chemically damaged surfaces are repaired
aluminum brass or 90Cu-IONi. A further breakdown of the almost instantly, as shown by studies of potential.
performance of arsenical aluminum brass tubes compared with
that of 90Cu-lONi tubes is shown in Table 53. From this During the last decade, a number of high-strength titanium
study, it is evident that the cupronickel tube is superior at the alloys have been made available commercially. While these
place of highest temperature, namely the brine heater. The alloys have extremely attractive strength-to-density ratios, a
arsenical aluminum alloy would be chosen on a performance knowledge of their corrosion behavior is needed to insure their
and cost basis for the reject and recovery stages and for all correct application for service in marine environments.
tubes. Designers of these plants have frequently installed
90Cu-lONi in those areas where the temperature and other
factors were more severe. In an experimentally controlled side- Atmosphere
by-side comparison, the behavior of the two alloys probably
would be more similar than indicated here. Titanium and its alloys have outstanding resistance to
marine atmospheres. At ambient temperatures, they are
TABLE 52. COPPER-ALLOY-TUBING PERFORMANCE IN 55 immune to crevice attack, pitting, and general corrosion.
MULTISTAGE FLASH DISTILLATION PLANTS(67)
Titanium alloys have been used in a variety of forms
Arsenical including wire rope, bolted joints with crevices, weldments.
Aluminum 90/1 0 70/30
etc., with no significant attack by seawater mist or marine air.
- -Brass
---- C:ufliL Cu/N, Titanium
In marine atmospheric rack exposures, titanium alloys, regard-
Number of Units Usmg Alloy
less of type, show no signs of local attack. A slight discolora-
Tubes(a) 37 ]8 ]6 tion is sometimes observed.
Number of Units Wltb Failed
Tubes 14 0 0 Corrosion rates of other selected materials are compared
Percent of UOlts With Failed with titanium in Table 54 for a severe marine environmentJCJ9)
Tubes 38'7< 44% 0 0
Service Times (All Tubes), months 9-96 9-79 14-124 26 (If Hastelloy C or one of the related nickel-chromium-
Average Range 45 39 71 26 molybdenum alloys had been included in the comparison it
Service Time (Failed Tubes), months 10-88 12-79 0 0 would have shown negligible weight loss similar to titanium.)
Average Range 50 48 0 0

Total Inside Arca of Tubes, sq ft 2,415,051 290,416 006,473 71,810

TABLE 54. CORROSION RATE OF MATE-
Inside Area of Failed Tubes, sq ft 9,089 2,779 0 0 RIALS EXPOSED TO THE
Percent Failed 0.38 0.96 0
-----~----
0 ATMOSPHERE FOR 5 YEARS
AT KURE BEACH, N. c.(69)
(a) Some of the 55 plants used more than one alloy.

TABLE 53. TUBE-AREA FAILURE ACCORDING TO Corrosion Rate(a), mpy

SECTION OF MULTISTAGE FLASH PLANT Materials
-_.~~--~- -
80-ft Lot
~~~--~~~---~~~
800-ft Lot
Titanium Nil Nil
Failure, percent A1clad 24S-T3 0.0197 0.0034
Section of Plant Arsenical Aluminum Brass 90Cu-lONi Alclad 75S-T6 0.0278 0.0034
Type 302 stainless 0.0009 Nil
Reject Stage 0.52 1.00 Type 316 stainless 0.0013 Nil
Recovery Stage 0.34 0.25 Inconel 0.0014 0.0003
Brine Heater 1.67 0.93
All Tubes 0.38 0.96 (a) Average corrosion rates from three specimens.

Titanium and Titanium-Base Alloys Galvanic Attack. When titanium metals arc coupled to
common metals like steel or aluminum and exposed to the
atmosphere, local acceleration of attack on the anodic member
Of presently known materials, titanium and its alloys are of the couple will take place at or close to the joint, during the
among the most resistant to marine environments at ambient period when a wet salt film is present. Coupling of titanium to
temperatures. In most marine applications, a thin oxide film copper results in some increased attack of the copper, but with
forms on titanium materials and provides complete protection. stainless steels the galvanic effect of titanium is minimal.
Under rather special conditions, this passive film will sometimes Atmospheric galvanic-couple results are summarized in Table
break down. In spite of titanium's excellent corrosion behavior, 55.
three problem areas pertaining to marine environments have
been en.:ountered:(68) (1) the corrosion pitting observed at
oxygrn-starved crevices when the seawater is heated to 250 F Splash and Tide
and above, (2) stress-corrosion cracking in the presence of
tensile stresses and a surface flaw, and (3) stress-corrosion Titanium and its alloys show excellent resistance in the
cracking when stressed, salt-contaminated titanium is heated to splash and tide zones. The well-aerated seawater in the splash
500 F or higher. Alloy modification and heat treatment can, zone is conducive to passivation. Although fouling organisms
however, effectively reduce the sensitivity of titanium materials settle on titanium in the tide zone, there is ample oxygen
to these types of premature failure. present to maintain titanium passive. At ambient temperatures,
 51
TABLE 55. EFFECTS OF GALVANIC COUPLING OF TITANIUM TO SELECfED METALS EXPOSED TO THE
MARINE ATMOSPHERE IN THE 80-FOOT RACKS AT KURE BEACH, N.CJ69)

360-Day Exposure 4 Years and 8 Months' Exposure

Coupled Corr. Rate, mpy Coupled Corr. Rate, mpy
Metal Coupled Uncoupled Corr. Metal Area Metal Area Uncoupled Corr. Metal Area Metal Area
to Titanium Rates(a), mpy 7 X Ti Area(b) 1/7 X Ti Area(C) Rates(a), mpy 7 X Ti Area(b) 1/7 X Ti Area(C)

FS-I magnesium 1.26 2.50 5.5 0.88(d) 1.17(d) 3.52(d)

Alclad 24S-T3 0.06 0.277 0.86 0.0549 0.2130 0.291
52S-I/2H 0.05 0.056 0.199 0.0845 0.0362 0.0813
Alclad 75S-T6 0.10 0.460 0.99 0.0525 0.0786 0.393
Copper 0.12 0.022 0.42 0.0852 0.1350 0.241
Steel (low carbon) 6.13 9.82 Lost
Monel Nil 0.020 0.032 0.0152 0.0197 0.0320
Inconel 0.011 0.006 0.003 0.0025 0.0029 0.0032
Type 302 stamless Nil 0.009 0.023 0.0083 0.0091 0.0015
Type 316 stainless 0.004 0.004 0.003 0.0035 0.0029 0.0058

(a) Average of one 6 x 1.5-inch specimen and two 0.75 x 1. 5-inch specimens.
(b) One 6 x 1.5-inch specimen.
(c) Average of two 0.75 x 1.5-inch specimens.
(d) Three years and 160 days of exposure.

the rate of attack is so extremely low that only a trace of Velocity Titanium has the ability to withstand extremely
oxygen is needed to maintain passivity. Thus at crevices or high seawater velocities with negligible attack_ Numerous inves-
under barnacles, titanium is found completely resistant. tigators have established that titanium and 'many of its alloys
Titanium does not pit in the splash and tide zones. will withstand seawater at all velocities of current technical
interest. For example, Danek(71) exposed five alloys for 30
days in seawater at 120 fps (see Table 58). All alloys showed
Shallow and Deep Ocean very low rates of attack, as did Hastelloy C and Alloy 20.

Titanium also has excellent resistance to shallow- and Titanium also has excellent resistance to impingement
deep-ocean environments. It is one of the few metals that is attack and to cavitation attack in seawater. Hohman(72) has
completely resistant at all depths. The susceptibility of certain reported the jet erosion-corrosion rates shown in Figure 58. In
alloys to stress-corrosion cracking is discussed separately as are this comparison, titanium alloys Ti-6AI-4V and Ti-8AI-2Cb-1 Ta
galvanic couple effects with metals either anodic or cathodic to were superior to other candidate materials. Thus, for applica-
titanium. tions like hydrafoils. the combination of excellent resistance to
seawater at all velocities and high strength, makes titanium
A comparison of titanium with other metals after 4.5 alloys an idea1 choice.
years in flowing seawater is given in Table 56. Corrosion rates
are calculated from the weight loss. In the case of titanium the
loss was so small that it was at the extreme limit of accuracy Galvanic Attack. Current marine practice is to select
for the analytical balance used in the experiment,(69) Expo- titanium only when its higher cost, compared with that of steel
sures have now been expanded to include numerous alloys at or aluminum. can be justified. A complete design of a marine
shallow- and deep-ocean environments. As shown in Table 57, facility in titanium does not yet exist. Normally titanium is
titanium alloys are found to be completely resistant in a wide associated with other metals in the structure. When titanium is
variety of ocean environments. electrically coupled to a common metal, it acts to increase the
total cathodic area available to the local anodes on the other
TABLE 56. MATERIALS IMMERSED IN SEAWATER
metal. Since the corrosion of steel and aluminum, for example,
FLOWING AT 3 FPS IN TROUGH AT
is cathodically controlled, increasing the cathodic area by
KURE BEACH, N. c.(69)
coupling with titanium allows increased corrosion of the more
483 Days 4-ill~ __ anodic member. Passive titanium is more noble than practically
Corr. Rate, Max Face Max Edge Corr. Rate, Max Face Max Edge
Materials(a) mpy Pitting, in. Pitting, in. mpy Pjttlng, in Pitting, i~..:. all other common metals as shown by the galvanic series in
-----
Titanium NI1 None None 0.00003 None None Table 6.
Alclad 24S-TJ 1.10 None None 117 0.03S(b) O.OSO
Alclad 7SS-T6 1.21 None None 0.781 O.D3S(b) 0.20
Type 302 stainless 0.08 0.031 0.060 0.088 0.060 0.20 The extent of the accelerated attack on the other metal in
Type 316 stainless 0.16 0.020 0.10 0.061 OOSO 010 the couple is governed by the difference in potential between
Inconel Nil 0.008 None 0.094 O.D3S(b) 0.10
the two metals in seawater, the resistance of the electrical
(a) Three specimens of each. circuit, and the polarization effects resulting from the passage
(b) Specimens perforate with pits.
of electric current.
Not only is titanium completely resistant to seawater
environments, but it also is resistant to (I) polluted seawater, These factors are strongly influenced by the relative areas
(2) diluted seawater found in some harbors, and (3) to sea- of the titamum and the other metal of the couple. A small area
water containing such gases as chlorine, ammonia, hydrogen of titanium coupled to a large area of an anodic metal such as
sulfide, or excess carbon diOXIde, and (4) to hot seawater. steel, for example, will not greatly accelerate the corrosion of
 52
TABLE 57. SUMMARY OF CORROSION OF TITANIUM AND TITANIUM
ALLOYS IN SEAWATER(70)

Number of Exposure Time, Exposure

Alloy Exposures days Depth, feet Type of Corrosion Observed

Unalloyed Ti (grade unknown) 10 123-1,064 2,350-6,780 None visible «0.1 mpy)(a)

Unalloyed Ti (Grade 4 90-199 4,250-4,500 None visible «0.1 mpy)(a)

RC 55)

Unalloyed Ti (Grade 8 123-751 5-6,780 None visible (0.0 mpy)

75A

Ti-5AI-2.5Sn 12 123-751 5-6,780 None visible «0.1 mpy)

Ti-7 AI-12Zr 123 5,640 None visible (0.0 mpy)

Ti-7AI-2Cb-1 Ta 2 181 5 None visible (Fouling stains)

Ti-8Mn 402 2,370

Ti-4AI-3Mo-I V 3 402-1,064 2,370-330 None visible (0.0 mpy)

Ti-6AI-4V 20 123-1,064 5-6,780 None visible «0.1 mpy, mostly O.o)(a)

Ti-13V-IICr-3AI 12 123-751 5-6,780 None visible «0.1 mpy, mostly 0.0)

(a) One panel was reported as 0.19 mpy.

TABLE 58. EFFECT OF VELOCITY ON TITANIUM

ALLOYS IN SEAWATER(71)

Corrosion Rate,
at 120 FPs(a),
lnconel 718
~._Alloy mpy
K Monel
Commercial Ti 0.29
17-4PH IH 1025)
Ti-6AI-4V 0.44
17-4PH (H 1075)
c:J Un welded
Ti-13V-IICr-3AI 0.38
Ti-SAI -4V _ Welded
Ti-5AI-2.5Sn 0.22
Ti -8AI-2Cb -ITo
Ti-7Al-2Cb-1Ta 0.16
Berylco 25
Hastelloy C 0.19
Co 4M Cu (IO-Doy Test)
Alloy 20 0.38
AM 355 (IO-Doy Test)

HY 100 for Cladding

~===========JoI25 (a) Calculated from weight loss per unit area.
Hostelloy C for Cladding
on HY 100 the latter. Increased attack on a small area of steel will result
from coupling it to a large area of titanium.
Titanium (A-70) for Cladding
on HY 100 (IS-Day Test),

AlSI 4330 M for Cladding

Hostelloy C for Cladding on

t============Jo-325 Some idea of the galvanic corrosion resulting from an
anodic to cathodic area ratio of (a) I to 10 and (b) 10 to I in
seawater can be gained from Figure 59. For carbon steel, the
AlSI 4330 M (IS-Day Test)
actual increment of extra attack is off-scale for the unfavorable
Titanium (A-70) for Cladding on rdtio of I (steel) to 10 (titanium).
AlSI 4330 M (IS-Day Test)

AlSI 4330 M Coated with No weight loss determined, cooting lost

during test, severe pitting and/or cavitation Because of the polarization characteristics of titanium,
Polyurethane
coupling it to steel results in less galvanic corrosion than if the
Uncoated } No weight determined
Epoxy Gloss Laminate Coated Minor visible damage titanium in the couple were replaced by copper, even though
the open-circuit potential of a steel-to-copper couple is actually
o 5 10 15 20 25
200 mv less than that for a steel-to-titanium couple. The
Erosion - Corrosion Rate, mpy
polarization characteristics for these two couples are shown in
Figure 60.(74) The weight loss on the steel, in this experiment,
FIGURE 58. RATES FOR JET EROSION-CORROSION IN was 7 times greater for coupling to copper than for coupling to
SEAWATER FOR 30 DAYS AT 90 KNOTS(72) titanium.
 53
Mud Zone
rur- 28.5
Ocean-bottom sediments vary according to their ongm.
10 Oenotes extent of
galvanic attock Some are formed by mechanical deterioration of rocks and
9 Denotes extent of minerals, such as by rivers and glaciers. Another ty pe consists
crevice attack of the shells and skeletons of animals. Typically, these sedi-
8
ments contain organic matter. Although the mud zone can
Anodic; cathodic Anodic; calhodic
7 area ralio area ratio present special corrosion problems to common metals, chiefly
>-
0- approx. I: 10 appro•. 10: I because of the presence of sulfides produced by the action of
E 6 sulfate-reducing bacteria, this is not a factor in the case of
.; 5
titanium and its alloys. Titanium and its alloys are found to be
0
:;: completely resistant in both shallow- and deep-ocean sediments.
~ 4 However, titanium alloys found to be susceptible to stress-
Q;
c corrosion cracking in seawater are also susceptible to this type
'"
a.. 3 of failure in he sediment.
2

Stress-Corrosion Cracking

Early exposure tests on titanium materials included

stressed specimens in both seawater and atmospheric environ-
ments. On the basis of the results of simple U-bend or four-
point loaded ,pecimens, the passive film on smooth surfaces of
titanium and its alloys gives complete protection to marine
environments even under high tensile stresses. The lack of
stress-corrosion cracking was considered to be related to the
fact that no local corrosion, such as pits, which could act as
stress raisers md stimulate the formation of cracks, developed
on the titanium surface.

In recent years there has been serious concern that the

results of such exposure tests on stressed panels of titanium
FIGURE 59. BEHAVIOR OF METAL-TO-TITANIUM materials in marine and other chloride-ion environments did
GALVANIC COUPLES EXPOSED FOR 2,500 HOURS not permit full evaluation of the susceptibility to stress-
IN AERATED SEAWATER(73) corrosion cracking. Surface defects are often present in actual
Used with permis~ion of Institute of Marine Engineers structures, which may arise from weldments, fabrication
damage such as force-fitting, etc. Brown(76) considered this
situation and first presented, in November 1964, a stress-
-c'" corrosion test to evaluate the susceptibility of titanium mate-
",~
-0 cathodic rials in chloride solutions while under stress in a cantilever-
0>
.... :.=
::J- beam test machine. The key to the method is obtaining a
~'E notch of sufficient acuity to allow stress-corrosion cracking to
",4i proceed in a susceptible alloy. With this test, and other
~O developments. the mechanism of stress-corrosion-cracking
"'- failure is now better understood. Essentially, the fracture
>0
:I: toughness of the alloy, with the surface defect, is reduced by
0_ 200 the presence of the chloride ion.
~Q)

~g
lf8 00~----~----,",,:,,!:------::l;:-----~ 40 The nature and size of the defect or critical flaw can be
expected to play a significant role in whether or not stress-
corrosion cracking failure will take place.

FIGURE 60. CATHODIC POLARIZATION OF COPPER AND Judy and Goode(77) have studied the critical flaw depth
TITANIUM AND THE ANODIC POLARIZATION OF STEEL for a whole series of titanium alloys in 3.5 percent sodium
IN SEAWATER(74) chloride using the cantilever-beam method. While sodium
chloride solution is not equivalent, for most purposes, to sea-
Titanium is readily passivated not only as the cathode in a water, in the present test it should give an order of merit
couple but also as the anode. Platinized titanium is widely used which is indicative of seawater behavior. Even though a number
as an impressed-current anode with complete success. In this of alloys are relatively insensitive, most of them, as shown in
example, the anodically polarized titanium is not corroded to Figure 61, can be made to stress-corrosion crack at some
any great extent. combination of flaw geometry and applied stress.
 54
Preliminary screening tests indicate the following alloys to
be insensitive to seawater crack propagation for the conditions
Titanium Alloy Composition used:
• 7AI-2Cb -ITa (C) X 6AI-2Ma
o SAI-2Cb -I Ta (C) e 7AI-IMa-IV Ti-2AI-4Mo-4Zr*
t> 6AI-4V (C) <D IIMa-55n-5Zr
'7 7AI -12Zr (C) " 6AI-4V-2Ma Ti-4AI-3Mo-I V
• SAI-IMa-IV (C) o 6AI-4Zr-2Ma Ti-5AI-2Sn-2Mo-2V*
IllI 10Ma -5.45n • 7AI-2.5Mo
~ 6AI-4V-25n !l 7AI - 3Cb-25n
Ti-6AI-2Mo*
"i 5AI-25n-2Ma-2V + 7AI-3Mo Ti-6AI- 2Sn-1 Mo-I V*
o 6AI-3V-IMa • 5AI- 2.55n (C) Ti-6Al-2Sn-1 Mo-3V*
o 6AI-25n-IMa-IV <] 6AI-45n - IV
Ti-6AI-2Cb-1 Ta-O.SMo
Il 6AI-25n-2Ma -2V • 6.5AI-5Zr -I V
() 6AI-6V-25n-ICu-0.5Fe (C) CiII 13V-IICr-3AI (C) Ti-6.5AI-5Zr-1 V*
o 6AI-4Zr -25n-0.5Ma -05V <II 6AI-6Zr -1"10 Ti-7Al-2.5Mo* (as received and beta annealed + WQ +
140 (C) Cammercial alloy Critical Flaw Depth 1100 F, aged 2 hr).
IllI
120 In general, all alpha alloys and near-alpha alloys are
susceptible, whereas alpha-beta alloys are resistant. The effect
of seawater on titanium alloys is summarized in Table 59. At
the present time, the Ti-6AI-4V alloy with low interstitials (low
0.1 in. oxygen) is considered one of the best of the more insensitive
commercial alloys for seawater service.

One of the alloys listed in Table 59 is the super-alpha

• -e~
• 0 •• <]
alloy Ti-SAI-2Cb-ITa. When first developed, it was found
metallurgically unstable and highly susceptible to stress-
• t> 0
001 in. corrosion cracking in seawater. Lowering the aluminum content

20 • I percent did not alter the susceptibility to cracking. Research

has since established that the presence of an embrittling con-
stituent in the structure of the metal probably is an essential
0 f eat u re 0 f t he seawater stress-corrosion susceptibility.
100 110 120 130 140
Titanium-aluminum alloys with Ti3Al present are apt to be
Yield Strength, ksi
prone to stress-corrosion cracking. This constituent tends to be
present in alloys with 4 percent or more of aluminum, In
FIGURE 61. STRESS-CORROSION-CRACKING RESISTANCE addition to the aluminum content, other elements are found to
INDEX FOR TITANIUM ALLOYS IN 3.5 PERCENT SALT playa role. Oxygen contents higher than O.S percent decrease
WATER(77) the tolerance for aluminum. Isomorphous beta stabilizers such
as molybdenum, vanadium, or columbium increase the
Alloys which have shown some degree of susceptibility are tolerance for aluminum, although higher oxygen contents
listed below, but not necessarily in order of susceptibility(78): decrease their effectiveness.

Unalloyed titanium (with high oxygen content, i.e., On the basis of this concept, the excellent stress-corro-
0.317 percent) sion-cracking characteristics of the Ti-6AI-2Cb-1 Ta-O.SMo,
Ti-SMn Ti-6.5AI-ICb-ITa-1.2Mo, and the Ti-7AI-2.5Mo alloys are
Ti-2.5AI-IMo-IISn-5Zr-0.2Si (IMI-679) explained. In each case, the beta stabilizers, particularly the
Ti-3AI-IICr-13V molybdenum content, allow the employment of higher
Ti-4AI-4Mn aluminum contents in the alloy.
Ti-5AI-2.5Sn
Ti-6AI-2.5 Sn* The thermal history of an alloy will alter its degree of
Ti-6AI-4V (standard grade) susceptibility. The Ti3AI formation is dependent on the aging
Ti-6AI-3Cb-2Sn * time of the alloy in the alpha plus Ti3AI field which extends
Ti-6AI-4V-I Sn* up to 1100 F-1300 F for aluminum contents of 4 to 8 percent.
Ti-6AI-4V-2Co* By rapid quenching through this temperature range, TiAI3
Ti-6AI-6V-2.5Sn* formation can be prevented and the sensitivity to stress-
Ti-7 AI- 2Cb-1 Ta corrosion cracking in seawater can be reduced.(SO)
Ti-7 AI-3Cb (as received and beta annealed)*
Ti-7AI-3Mo* Methods other than adjustment of composition and heat
Ti-7 AI-2Cr-1 Ta* treatment have been studied for the control of stress-corrosion
Ti-7 AI- 3Cb- 2Sn * cracking. Cathodic current will, under some conditions, arrest
Ti-8AI-I Mo-I V the metal dissolution at the root of a crack. Once the
Ti-8AI-3Cb-2Sn *. polarizing current is removed, the dissolution will resume. A
rapidly moving crack will not be arrested by cathodic current.

* ;: : ExrL'ril11l'ntal compositions.
 55

TABLE 59. EFFECT OF SEAWATER ON TITANIUM ALLOYS(78)

Test Conditions to Cause Failure(a)

----~-----

In Air
Slow-Notch In Seawater
Bend Test Static Load Static-Load Cantilever Test
Nominal Cantilever Test Nominal
~ - - - -
Fracture
Bending Bendinf Bending Appearance
Stress, Stress, Time, Stress, Time, Seawater
Alloy Condition ksi ksi min ksi min Embrittled?

Alpha Alloys
Unalloyed Ti Alpha rolled 182 157 45 64 3 Yes
(RS-70) Alpha rolled + 1400 F, 104 I Yes
16-hr AC
Ti-5AI-2.5Sn Alpha-beta rolled 170 65 3 Yes
Ti-6AI-2.5Sn Beta rolled 233 181 40 110 3 Yes
Alpha-beta rolled 221 166 760 109 6 Yes

Near-Alpha Alloys
Ti-8AI-2Cb-1 Ta Beta rolled 186 129 Immed Yes
Ti-7AI-3Cb(b) Beta rolled 232 110 10 Yes
Ti (0.06 02)(b) Alpha-beta rolled 193 166 70 125 3 Yes
Ti-7AI-3Cb(b) Beta rolled 235 144 Immed Yes
Ti (0.1 02)(b) Alpha-beta rolled 256 131 4 Yes
Ti-7 AI-3Cb- Beta rolled 200 III I Yes
2.5Sn(b) Alpha-beta rolled 213 114 9 Yes
Ti-6AI-3Cb-2Sn(b) Beta rolled 220 120 Immed Yes
Ti-7 AI-3Cb-2Sn(b) Beta rolled 233 158 Immed Yes
Ti-8AI-3Cb-2Sn(b) Beta rolled 110 126 Immed Yes
Ti-6~5AI-5Zr-1 V(b) Alpha-beta rolled 222 186 180 186 200 No

~Ipha-Bet~Alloys

Ti-6AI-2Sn- I Mo-I V(b) Alpha-beta rolled 209 196 9 180 1430 No

Ti-6AI-4V Alpha-beta rolled 180 Immed No
(low 02)
Ti-6AI-4V Alpha-beta rolled 101 135 15 103 150 No
(high 02)
Ti-6Al-2Mo(b) Alpha-beta rolled 165 180 No
Alpha-beta rolled + 1750 F, 191 I No
I-hr AC + 1100 F, 2-hr AC
Ti-7AI-2.5Mo(b) Alpha-beta rolled 209 198 500 169 Immed No
Alpha-beta rolled + 1735 F, 216 192 ISO No
l-hrWQ
Alpha-beta rolled + 1735 F, 205 166 25 135 13 No
I-hr WQ + 1100 F, 2-hr AC
Ti-5AI-2Sn-2Mo-I V(b) Beta rolled 242 190 6 177 105 No
Alpha-beta rolled 185 171 I 143 110 No
Ti-6AI-2Sn-3V-IMo(b) Beta rolled 211 115 1845 120 342 No
Alpha-beta rolled 192 106 1780 140 2 No

(a) All specimens were fatigue cracked to a total notch depth of 25 to 35 percent.
Immed = Immediate.
(b) Experimental compositions.
 56
Cathodic current also can be provided by applying a coating of resulted in a marked drop in the pitting potential. especially at
a sacrificial metal such as zinc. However, metallic (and organic) lower temperatures. Thus, titanium alloys with 4 percent or
coatings are more difficult to apply on titanium than on, say, more aluminum can be expected to have less resistance to
aluminum. Most of the coatings that have been tried are not pitting as the temperature is raised beyond 60 C (130 Fl.
successful. Other experiments demonstrated that as little as I percent
molybdenum markedly increased the pitting potential at
elevated temperatures r above 125 C (275 F) 1.(1' I)
Pitting Attack
Tilis experimental investigation of pit susceptibility of
At ambient temperatures, titanium and its alloys are com- titanium and the effect of temperature agrees well with the
pletely free from pitting attack in marine environments. In limited information available on the behavior of titanium in
general, the potentials of titanium alloys in saline solutions at hot seawater. The largest desalination plant using titanium heat
room temperatures are considerably more noble than the spon- exchangers has been operating at St. Croix Island for almost 4
taneous corrosion potential. However, pitting can be induced years. Inspections made so far indicate no pitting on any of the
by the passage of anodic current. titanium components for seawater temperatures ranging from
200 F to as high as 250 F, see Tahle 52.
Since titanium and its alloys are excellent candidate
materials for applications involving handling of hot seawater in
desalination and hot brines in the chemical industry, it is of
interest to establish whether there is a greater susceptibility to
pitting at elevated temperatures.
Crevice Corrosion
Posey and Bohlman(81) conducted an electrochemical
Crevice corrosion all titanium materials has beer, expe-
investigation of pitting in saline solutions. The effect of tem-
rienced in hot saline solutions, including seawater. The attack is
perature on the pitting potential of titanium and several alloys
more likely to develop with increase in (I) temperature. C)
with aluminum present was measured in 1M NaCI. As shown in
salt concentration. and (3) time. Lown pH solutions also lc'nd
Figure 62, titanium has a very high pitting potential (more
to be more active. Crevices that are rl'stricted show a t:re;l1n
than 9.0 volts) at ordinary temperatures, but as the tempera-
tendency to be attacked. In seawater and its brines. the attack
ture is elevated to 200 C (392 F), the pitting potential drops
has been observed at as low as 250 F.
to a low value. A small addition of I or 2 percent of aluminum
had little effect, while additions of 4 percent and higher
Crevice attack may be considered a form of pilllllg at till'
restricted interfacl's between mating surfaces. One of (he sur-
faces may be other than titanium. for examp1l', Tellon or othn
10
gasket material. Although the mechanism involved in crl'vice
0 Ti (commercially pure)
corrosion appears to be similar to that involved in pitting. for
9 •
I'!.
Ti-I% AI
Ti-2%AI titanium there may be differences. The e1l'ctrochemistry of
... Ti-4%AI crevice corrosion on titanium has been invc'stigated by
Griess.(82) Polarization studies were made of the effects of
"'l Ti-6 % AI
8 T Ti-8 % AI temperature. pH, and chloridc' ion concentration. As shown in
Figure 63, a higher critical current dl'nsity is required for
passivity as the temperature is increased. Similarly. ;IS thl' pH
7

-
u>

0
>
6
of the chloride solution. using hydrochloric acid. was
decreased, the critical current density also increased. At low pH
values, increasing the chloride concentration also raised the
W critical current density required for passivation.
U
(f)
5
u>
::J
u>
-0.15
~
>

C
0
4
-
u>

0
>
-025

4> 3 w-
0 U
-0.35
Cl.. (f)

2 u> -045
::J
u>

~
-055
0
C -0.65
4>
0
Cl..
-0.75
I 2 5 10
Current

FIGURE 63. THE EFFECT OF TEMPERATURE ON THE

ANODIC POLARIZATION OF TITANIUM IN
FIGURE 62. EFFECT OF TEMPERATURE ON PITTING 0.9 M NaCI-O.I M HC1(82)
POTENTIALS OF TITANIUM-ALUMINUM ALLOYS U sec! with perm f' U f N J 1 ion lJ I A I;-Jl n of Corrosion
IN I M NaC1(81) E nqinccrs
 57
From this and other experimental evidence, certain aspects marine-based aircraft or on decks of aircraft carriers are known
of crevice attack on titanium can be explained. As with other to ingest salt air or salt spray into their air-compressor intakes.
metals, a differential aeration cell 'will initiate the action. At Fuel for these engines may also be contaminated by seawater
ordinary temperatures this cell does not operate, since the getting into the ship's tanks from seawater ballasting. Salt-
amount of oxygen required to maintain passivity in the crevice contaminated external titanium surfaces on present and future
is so low that it is not consumed. At elevated temperatures the supersonic transocean aircraft might be expected to fail because
oxygen required to repair breaks in the passive film may be of development of high temperature on leading edges during
insufficient and local active sites may develop, lowering the flight.
potential in the crevice. To maintain electrochemical neutrality,
cWoride ions migrate into the crevice and sodium ions migrate Actually, there have been no reported failures of titanium
to the outside. This results in increased acidity and accelerated components in any of these applications from hot-salt cracking
local attack.(S2) Once initiated, the corrosion can continue as a in service. However, an intensive study has been conducted in
differential concentration cell, whether oxygen is present or recent years in order to find alloys resistant to this failure
not. mode and to establish methods of prevention.

This mechanism seems to fit the salient facts of crevice All of the commercial alloys, with the possible exception
attack. For titanium materials, attack will not take place unless of unalloyed titanium, are susceptible to some degree to hot-
the crevice is sufficiently restricted and temperature and con- salt cracking. The temperature range of greatest susceptibility is
centration are favorable. An approximation of crevice attack in 550 to SOO F, although failures are occasionally reported out-
actual practice as related to salt concentration and temperature side these limits.
is shown in Figure 64. Attack on unalloyed titanium (Grade
Ti-50A) is not to be expected in seawater until the temperature Susceptibility to attack varies with composition. High
is about 250 F, or, say, 300 F with the Ti-0.2Pd alloy. The aluminum content is particularly undesirable, e.g., the
superior corrosion resistance of the Ti-0.2Pd alloy is attributed Ti-SAl-l Mo-l V alloy is very susceptible to hot-salt
to enrichment of palladium on the crevice surface by the initial crackingJS5) Alloys with 6 percent or less aluminum generally
attack and its promotion of cathodic passivationJS4) Alloys have more resistance to hot-salt cracking. For example, the
containing molybdenum or nickel also should be more resistant widely used Ti-6Al-4V alloy has intermediate resistance to
to crevice attack.(S2) hot-salt cracking. Among the most resistant alloys are
Ti-4Al-3Mo-l V and Ti-2.25Al-I Mo-Il Sn-5Zr-0.25Si.

Under present conditions of marine service, titanium

1i-5OA alloys apparently do not experience the temperature, stress,
25 and time combination which leads to hot-salt cracking. The
cyclic temperature of the service may inhibit the conditions
U which cause cracking at constant temperature in the laboratory.
0
Z 20 However, it is conceivable that the new use of jet engines on
\ Pilling the decks of seagoing vessels, where they may run continuously
0~ \
15 \ ~ for several hundred hours at a time, could duplicate the time
C \ and temperature conditions that cause hot-salt cracking in the
:S
0
\
\ laboratory.
~ 10 \
c
Q) \
u \
c \ Aluminum and Aluminum-Base Alloys
8 5 \
\
• Seawaler - - - -=~-d:;.::::::~ra;:::":k::::.:~t:=
Aluminum alloys are finding ever-increasing application in
0 .....~----::2~OO::----~30~0----4~0.,..0--...J marine environments. For marine structures, the 5086*-H32 or
Exposure Temperature, F -H34 alloy has been widely used. It has excellent resistance to
corrosion, is weldable, and can be strain hardened to provide
moderately high strength. Other 5000 series alloys which also
FIGURE 64. IMMUNITY OF TITANIUM (AND ITS 0.2 Pd
find use are 5083 and 5456. For applications requiring higher
ALLOY) FROM CREVICE CORROSION IN SALT
strength, the corrosion-resistant 6061-T6 has often been
SOLUTIONS(S3)
selected. The welding of 6061 causes loss in ductility, but the
alloy can be heat treated to provide higher strength than is
available with 50S6-H32.
Hot-Salt Cracking

During the early period of development of titanium, hot Alloys with relatively poor corrosion performance in
forming of sheet materials and creep testing in the laboratory marine environments include the 7000 series (zinc and mag-
sometimes resulted in an unexpected loss of properties. These nesium), the 2000 series (copper), and the 4000 series (silicon).
failures were traced to salt contamination on the metal surface,
and the phenomenon has since been known as hot-salt crack- Since the corrosion resistance depends on the maintenance
ing. This type of failure has been repeatedly demonstrated in of the passive oxide film, aluminum and its alloys generally are
laboratory experiments by applying a thin layer of salt to a most resistant in those marine environments where the metal
surface is freely exposed to well-aerated seawater or to the
heated sample and maintaining a high temperature with a high
stress for time periods ranging from a few to several thousand atmosphere. Failures by local attack such as by pitting, crevice
hoursJ79) corrosion or exfoliation, or stress cracking are characteristic of
many alloys, particularly the high-strength alloys.
In the marine field, there are several applications of
titanium materials where the service conditions involve a com-
bination of sea-salt contamination and elevated temperature, *For the readers' convenience, the compositions of the alumi-
which at first appearance seem to be similar to the require- num alloys cited are listed according to alloy designation in
ments for hot-salt cracking. For example, jet engines as used in the Appendix, Table A-2.
 58
A discussion of the behavior of aluminum alloys in each Corrosion rates for Alloys 1100 and 6061, exposed at
type of marine environment and some examples of successful Cristobal, Canal Zone, are given in Table 62. The attack was
application are given in the following sections. uniform (pits less than 5 mils deep) for the entire 16 years,
with an average penetration of 0.007 mpy for each alloy.c S8 )

Atmosphere For atmospheric service, the aluminum-magnesium alloys,

e.g., 5050, 5052, 5086, and 5154, are considered among the
Alloys which exhibit good behavior when exposed to most suitable. Alloy 6061 is also highly satisfactory.
marine atmospheres include 1100, 3003, 3004, 5052, 5056,
5083, 5085, 5154, 5456, and 606 I. When aluminum alloys are Because of its resistance to attack, aluminum is usually
exposed to an aggressive marine location, the initial corrosion exposed without added surface protection. However, anodizing
rate, based on weight loss, may be as high as 4 mpy. After a may be used to enhance the resistance of the natural oxide
year or so, the rate usually tapers off to a low value film. Even better results are achieved with a protective coating.
approaching 0.1 mpy. Paint adheres well to aluminum and a suitable marine formula-
tion will provide long-lasting additional protection. Marine
The good performance of Alloy 1100 is illustrated in experience with aluminum structures has shown that repainting
Table 60, which summarizes I ().. and 16-year exposure data is required only about half as often as would be the case for
from widely different marine sites. Even at La Jolla, California, the same marine paint system applied to steel construction.
where the mist-laden air and high wind combine to bring a
heavy deposit of salt to the metal surface, the total loss in
thickness in 10 years was only 0.56 mil. Pitting Attack. Since many aluminum alloys tend to pit in
marine atmospheres, this behavior must be considered in a
specific application. Five-year results at three marine sites for
alloys 1180, 3003, 6061, and 5086. are presented in Figure 65.
TABLE 60. TEN-YEAR WEATHERING RESULTS FOR
1100 ALUMINUM IN MARINE
ATMOSPHERES(86) • Kure Beach, 8oo-foot lot
12
o Kure Beach, 80-foot lot
(Panels 9 x 12 x 0.035 Inch) o Arenzano
• Bohus -Melman
Corrosion Rate(a), Tensile Loss. o
Site mpy percent 8

Sandy Hook, N. J. 0.002 3.1

Key West, Fla. 0.004 1.7
4
La Jolla, Calif.
Cristobal, C. Z.cb)
0.028
0.007
14.1 •
Alloy 1180-H14
01L._ _--'...._ _....J ....L ......L .....l...J

(a) Calculated from weight loss.

(b) Sixteen-year exposure.( 88 )

Corrosion rates at three marine sites for Alloys 1100,

1180, 3003, 5050, 5052, 5154, 5086, and 6061, as sum- E 4
marized by Ailor(87), are presented in Table 6 I. After 5 years,
the highest rate observed for any of the alloys was 0.025 mpy. .J::.

For the heat treatments indicated in the table, all the alloys are Ci.
Q) o~ _ _.....l-_ _......I .J__ _.....J. ..l..I
Cl
resistant and show very low rates of attack.

TABLE 61. MARINE-EXPOSURE RESULTS FOR

ALUMINUM ALLOYS(87)

12,------------------{)-----,

IIOO-HI4 0.009 0.002 0010 0.035 0.027 0.028 0.018 0,021 0.022 O.OOQ 8
1180-H 14 0008 0003 0.006 0.024 0.024 0.023 0.025 0.020 0.018 0.009

3003-H 14 0.009 0.003 0009 0,036 0.037 o.on 0.018 0.022 0.021 D.DOC!

0.023 0.026 0.022 0.015 0,020 0.014 0.007

4
5050-H34 0009 0003 0007

5052-H34 0.008 0.006 0.007 0.020 0.028 0.021 0.010 0.018 0.014 0.009
Alloy 5086-H34
5154-H34 0009 0004 0.007 0.023 0.023 0.020 0.013 0.018 00[4 0,007 OC- I--_ _- - '...._ _....L ......L .....l...J

5086-1134 0007 0.001 0.007 0.OC3 0.OC3 0.019 0.010 0.018 0_013 0.010 o 2 3 4 5

6D61-T6 0.011 0.012 0.041 0,033 0.027 0,0 19 0.034 0.021 0,0 II
Exposure Time, years

(a) H14 = strain hardened: H34 = strain hardened. then stabliizt'J: T6 = solution heal treated. then
artitlcallyaged FIGURE 65. MAXIMUM MEASURED PIT DEPTHS FOR ALU-
(h) Values renee! insufl1cient cleaning after t:'xposure MINUMALLOYS IN SELECTED MARINE ATMOSPHERES(87)
 59
TABLE 62. CORROSION OF ALUMINUM ALLOYS EXPOSED 16 YEARS IN THREE TROPICAL
ENVIRONMENTS IN THE PANAMA CANAL ZONE(88)

Depth of Pitting(b!~ll~_ _ _ Tensile Type of

Average Penetra- Average of 20 Strength Corrosion
tion(a), mils Deepest Pits __I?.!.q.est Pits_ _ Loss %(c), Attack(d),
I Yr 8 Yr 16 Yr I Yr 8 Yr 16 Yr I Yr 8 Yr 16 Yr 8 Yr 16 Yr

Alloy 1100
Immersion

Seawater 0.28 0.61 0.97 9(13) II 17 IS J9 33 2 J

Mean Tide 0.06 0.31 0.53 11(9) 14 39 29 37 67 I JQ

Atmospheric

Marine 0.01 0.02 0.11 N N N N N N 0 A

A!!2Y~Q§~
Immersion
----

Seawater 0.28 0.73 0.91 N 23 14 N 49 79 0 J

Mean Tide 0.04 0.13 0.29 N N 17 N N 41 0 J

Atmospheric
Marine 0.03 0.03 0.11 N N N N N N A

(a) Calculated from weight loss and specific gravity.

(b) Represents depth of penetration from original surface; N - measurable pits; number in parentheses
gives number of measurable pits when less than 20.
(c) Percent change in tensile strength calculated on basis of 1/4-inch -thick metal and average of four
tests for underwater specimens, and 1/16-inch-thick metal and average of three tests for atmospheric
specimens.
(d) A - uniform attack; J -- marine fouling contact; Q -- pitting attack (random).

In this comparison, Alloy 6061 showed the best performance, immersed condition. Pitting attack on the other hand may be
with maximum pitting ranging from 3 to 7 mils. Note that the quite similar, regardless of the exposure condition. A com-
pitting tends to taper off with time. In an ASTM exposure test, parison of the mean-tide and submerged conditions in the
the maximum depth of pitting after 20 years' exposure was Pacific off the Canal Zone is shown in Figure 66 for Alloys
found to be 14 mils for Alloy 110G-H14 and 10.2 mils for 6061-T and 1100. The mean-tide loss is only half that resulting
Alloy 3003-H 14. The maximum penetration was higher than from continuous immersion. The weight-loss attack was similar
usually experienced. Other experience suggests that 3003 is for both alloys in the mean-tide condition but the pitting was
superior to 1100 as regards pitting resistance in the atmo- more severe for the 1100 alloy. After 8 years' exposure, the
sphere. Since the rate of pitting decreases with time, designers loss in strength at mean-tide exposure was 0 percent and I
can allow for it in structural applications such as storage tanks, percent, respectively, for these two alloys. While either alloy
where penetration would mean failure. In marine service, pits
are observed both on the skyward and groundward faces of
boldly exposed surfaces.
Seawater Seawater
Continuous Immersion Mean Tide
In general, alloys such as 5083, 5086, 5154, 5052, and
6061 are being used for applications involving resistance to 16 - Year
. Pitting Penetration, mils
marine atmosphere. Typical applications include deck houses ~
and superstructure on ships and off-shore structures, and en 0 .!J.90 6061-T 1100 6061-T
:=....J
E Average
towers and buildings on shore-based marine establishments. 20 Deepest 17 14 39 17
Deepest 33 79 67 41

Splash and Tide 1100 2 1100

6061-T 6061-T
Alloys suitable for atmospheric service also do well in the
splash zone. Well-aerated seawater splashing on the aluminum
surface tends to maintain passivity. As with other environ-
8 16 00 ~:Jl1~2~4~:38~===~16
mental zones, crevices and pockets where seawater can collect
should be avoided. Although there may be less tendency for Time, years Exposure Ti me, years
pits to initiate in the splash zone, once started the rate of
attack may be quite high. FIGURE 66. COMPARISON OF ALUMINUM ALLOY
6061-T WITH COMMERCIALLY PURE 1100 ALU-
The corrosion rate can be expected to be higher in mean- ~lINUM FOR 16 YEARS OF EXPOSURE IN
tide exposure than in the splash zone but less than in the fully SEAWATER ENVIRONMENTS(88)
 60
could be used, Alloy 6061 normally would be selected. As comparative sensitivity of aluminum alloys to pitting could be
shown in Table 62, after 16 years the weight-loss penetration established by measuring their electropotential in seawater.
was 0.29 and 0.53 mil and the deepest pits were 41 and 67 Alloys with relatively electronegative potentials (i.e., -0.69 to
mils, for the 6061 and 1100 alloys, respectively. -0.89 volt versus the Ag/AgCl reference electrodes) tended to
be more susceptible to pitting and crevice attack than alloys
with more electropositive potentials. These results, plotted in
Submerged Figure 68, show the high-strength alloys of the 2000 and 7000
series to be particularly susceptible to pitting, whereas alloys in
For service in seawater, certain alloys are found to have the 5000 series are relatively immune. It is interesting to note
superior corrosion resistance. In some cases, special heat treat- that a heat treatment for a given alloy which results in a
ments as well as carefully controlled composition are required less-negative potential also increases the susceptibility to
to achieve the best results. Alloys which find application in pitting, compare 5052-H32 with 5052-H34 or 6061-T6 with
seawater include 1100, 1180, 3003, 5050, 5052, 5456, 5083, 6061-T651.
5086, and 6061.
4Or----:.-:2;:;0::::2::4--:;:T~35;:1--------------.,

Pitting Attack. Aluminum alloys tend to pIt In seawater.

This type of localized breakdown is accelerated greatly by the .2219 -T87
chloride ions present. Pitting is often associated with metal- ~

lurgical factors such as grain boundariesJ89) One should expect E 30

.7178 -T6
a lower rate of penetration as the oxygen content of seawater
is increased, although other factors may mask this effect in ~
a:: Pits 6-39 mils -+- Pits 0-3 mils
practice. Oxygen content, rather than depth, affected the pit- .....o
ting behavior in Pacific Ocean experiments as Reinhart(90) has 20 I-
3OO3-HI4.
shown. He finds the pitting attack of several aluminum-
magnesium (5000 series) alloys at three oxygen levels to be the 7079-T6·
7075- T7351 •
highest at the lowest oxygen level (see Figure 67). c 1-3 mils: 5050-H34, IIOO-HI4,
:il 101- 2014-T6. 11~-FI{5052-H34'5154-H38
::::;; 606I-T6 •
X7002-T6. < I mil: 7106-T63,6061-T651,
5086-HI12, 5083-0, 5Q52-H32,
• 5456-H321, 5086-H32, 5086-H34,
Ocean Depth ~~OO5-T63, 5Q52-H32, 5257-H25
X 5ft °Q~5:---"""":'0~.7:---"""":'0~.9!"""""~IJ:.I~-&...:I.l:.3:-------_.J
5
Mean Potential Negative, Ag/AgCI

FIGURE 68. RELATION BETWEEN PITTING CHARACTER-

ISTICS AND ELECTRODE POTENTIALS OF ALUMINUM
4 ALLOYS EXPOSED IN SEAWATER AT KEY WEST,
"- FLORIDA<91 )
E Used with permission of lJ. S. Naval Research Laboratories

c Pitting data for aluminum alloys are more difficult to

--'"
.2 compare because of the large variation in the behavior of
~ 3 replicate panels. A pit, once started, may deepen at a very high
c rate, after which it may attenuate or stop altogether. Some
u
c trends can be observed, however, among alloys for long periods
o
U of exposure and for heat treatments for a given alloy. The
pitting resistance of Alloy 6061 in the T4 heat treatment, for
example, is superior to that in the T6 condition (Table 63).

TABLE 63. MAXIMUM PITTING DURING 10-YEAR

EXPOSURE OF PLATE SPECIMENS(89)

Pitting Depth, mils

Alloy Harbor Island, N. C. Halifax, N. S. Equimalt, B. C.

1100-H14 40 32 30
o0~-----!5:------1~0----.....i151.----~20
Average Pit Depth, mils 3003-H14 21 22 20

6061-T4 14 33 50
FIGURE 67. RELATION BETWEEN AVERAGE PIT DEPTHS
OF ALUMINUM-MAGNESIUM ALLOYS (5000 SERIES) AND 6061-T6 95 54 116
OXYGEN CONCENTRATION OF SEAWATER(90)
7072-p(a) 56 ISO 26
The pitting rate is highest during the first year or so of
exposure, after which it attenuates to much lower rates. For 7075-T6 66 p(a) p(a)
some alloys, pitting is not a serious problem, at least in well-
aerated surface water. Groover, et a1.(91) found that the (a) P = perforated.
 61
Godard and Booth( 89) summarize the results for five alloys decrease as the velocity of the seawater increased from I to 5
after 10 years' exposure at three marine sites. Alloy 7075-T6 fps. Beyond 5 fps, the pitting rate again increased.(89)
showed poor resistance to pitting attack, whereas Alloys
IIO(}-HI4 and 3003-H14 were somewhat less severely attacked. The depth of pitting tends to be higher in the deep ocean
than in surface waters. Even resistant alloys such as the 5000
In pipe experiments with an aluminum alloy containing series show severe pitting. An overall picture of the relative
O.02Cu, O.2IFe, O.IISi, and 0.016Ti, pitting was shown to pitting tendency in deep Pacific waters is shown in the bar
graph in Figure 69.

} 123 days 5,640 It

3003 - HI4

f. ·. ·.........:·Iiiiiiiiiii.·
~~!~S~·}
91• • • • : :::}
1- 122 } 1,064 days -5300 It

197 days -2,~40 It

Alclad
3003 -H12

1' }~
P===[3]'--'·}
}
123 days - 5,640 It
1,064 days - 5,300 It

197 days - 2,340 It

123 days 5,640 II

-
c :::J
(, \
Deepest

Average, mud
pi t
Average, water

i
~ Surface
_ _ _ } 1,064
2219-T81 days - 5,300 " p = perforated
1 x 6" piece
} 197 days - ;',340 It

7178-T6 len ,days 5,640 It

[
I x 6" 1,064 days - 5,300 "

7039 - T6 {:'. __ } 123doys - 5,640 ft} 197 days

2,340 II

{
} 23 days - 5,640 It

7079 - T6 } 97 days - 2,340 It

- ill days
5,600 It, AtlantiC Ocean

} Welded 123 days - 5,640 It

5454 - H32 } Welded, 197 days - 2,340 It

} Unwelded, 197 days 2,340 II

tE=============::lI_. }23 days - 5,640 It

5456-H321
---} 1,064 day'> :: ,300 ft

} 19,' daf 2,340 It

Welded, 123 days - 5,640 ft

5083 - H113 } Welded, 197 jays - 2,340 It

} 1,064 days - 5,300 It

5086-H34

"0 I } 123 days 5,640 II

No 2

--
No : } 1,064 days - 5,300 It

6061 -T6 No I } 197 days - 2,340 It

III days
5600 fl AtlantiC Ocean
1,050 days } '

-r------
365 days
730 days Panama Canal, PaCific Ocean
}
1,460 days

o 10 20 30 40 50 60 70 80 90 100 120
Pit Depth (MaXImum and Average), mils

FIGURE 69. PITTING OF ALUMINUM ALLOYS IN THE PACIFIC OCEAN OFF PORT HUENEME, CALIFORNIA( I)
Used with permission of U. S. Naval CIVil Enqlr1cnill\l Laboratory
 62
Crevice Attack. A rather common form of attack on In deep-ocean waters, crevice attack as well as pitting
aluminum alloys is crevice attack. While practically all alloys attack can be expected to be more severe. There is evidence
are susceptible, there are differences. Usually, an alloy's rela- that pitting is more severe with depth because of the lower
tively high susceptibility to pitting attack is indicative that it oxygen content, as discussed earlier, but for crevice attack the
will also tend to be susceptible to crevice attack, and vice information is scanty. Alloy 110Q-H14 showed negligible
versa. crevice attack in a surface experiment, but was perforated at
the crevice (62 mils) in less than 200 days in the deep ocean.
Since there are no standard crevices, the amount of attack Similarly, Alloy 6061-T6 showed 8 mils at the surface and 42
depends largely on the geometry of the crevice and the ratio of mils in deep water. Alloy 5052-0 showed no crevice attack at
anode (under the crevice) to cathode (external area). As might the surface, but complete perforation at the crevice (more than
be expected, information on crevice-attack behavior in seawater 65 mils) in deep-ocean tests running less than 200 days. These
is scattered and usually not comparable. and other results are presented in Table 65.

The 5000 series of alloys as a group have a relatively high TABLE 65. CORROSION OF ALUMINUM ALLOYS IN
resistance to crevice attack in seawater. Table 64 summarizes SEAWATER AT SURFACE AND IN DEEP OCEAN
the I-year results obtained by the Navy at Key West.(91) There WEST OF PORT HUENEME, CALIFORNIA(92)
is a close correlation between these results and the pitting
characteristics versus electropotential plotted in Figure 68. For Crevice-
Exposure Corrosion Corrosion
example, Alloys 3003-HI4, 6061-T6, 1100 F, 7075-T7351, and Depth, Ratd a ), Pit Depth Depth, Corrosion
Alloy Days feet mpy Max Avg mils Type(b)
7079-T6 all have electropotentials corresponding to pit suscep-
tibility, whereas the 5000 series have potentials indicating rela- l100-H14 181 5 1.4 sc
197 2340 5.6 62(PR)(b) SC
tive immunity to pitting. Since the crevice-attack results in 123 5640 1.9 39 P
Table 64 are similar to the pitting characteristics, Figure 68 can
3003-H14 181 5 1.1 33 17.6 P
be used to predict sensitivity to either type of attack. 3003 197 2340 1.4 40(PR) C·
3003-H14 197 2340 2.7 48 21.5 28 SE,P.C
3003 123 5640 0.6 28 C
3003-H 14 123 5640 0.5 27 19.5 32 E,P,C

Alclad 3003 181 5 1.0 P

TABLE 64. COMPARISON OF ATTACK OF SELECTED Alclad 3003-H 12 181 5 1.0 IP
ALUMINUM ALLOYS TO CREVICE Alclad 3003 197 2340 2.3 G
Alclad 3OO3-H 12 197 2340 2.2 15 14.3 13 P,C
CORROSION AFTER I-YEAR EXPOSURE Alclad 3003 123 5640 2.7 G
TO SEAWATER AT KEY WEST, Alclad 3OO3-H 12 123 5640 0.2 18 14.6 15 SLE,B,P,C
FLORIDA(91) 5052.Q 181 5 1.2 IP
197 2340 1.8 65(PR) SC
123 5640 3.7 65(PR) SC
Deepest Attack, mils
Alloy 2 3-5 6-10 11-20 5083 181 1.0 E.
5083-H113 181 1.2 C,IP,IG(c)
5083-H 113, welded 181 0.9 Et
llOOF X
5086 181 5 1.2 IP
5086-H32 181 5 1.0 IP,IG(c)
110Q-H14 X 5086-H34 181 5 1.2 6 P,IG
197 2340 0.7 29 SLE-P
123 5640 0.1 SLE,SLC
3003-H14 X 5086-H 112, angle 181 5 1.1 IP

5454 181 1.0 IP

5050-H34 X
5456·H321 181 5 1.2 12 7 P
197 2340 2.7 17 11.7 P
5052-H32 X 123 5640 0.1 SLE,SLC
5052-H34 X 6061 181 5 1.2 P
6061-T6 181 5 1.0 8 IP,C,IG
197 2340 1.1 47 44.1 42 C,P
5083-0 X 123 5640 0.1 IP

(a) Calculated from weight loss.

5086-H32 X (b) B - blistering, C· crevice, E· edge, Et . etched, G . general, I - incipient, IG - intergranular.
5086-H34 X p. pitting, PR - perforated, S - severe, SL· slight.
(c) Intergranular corrosion on edges of specimens.
5086-H112 X
Galvanic Coupling. Aluminum corrosion is affected by
5 I54-H38 X galvanic coupling to other metals. The corrosion rate is
accelerated greatly by contact with copper-base alloys. Even
5257-H25 X copper alloys corroding in the vicinity of aluminum, but elec-
trically isolated, can stimulate pitting attack as a result of the
5456-H321 X
copper ions migrating to the aluminum surface, depositing as
6061-T6 X metallic copper, and setting up local galvanic cells. Thus,
6061-T65I X copper-alloy construction should never be combined with
aluminum in seawater applications, whether coupled or not.
X7002-T6 X X
Galvanic coupling can be beneficial. Anodes of aluminum
X7005-T63 X or zinc galvanically coupled to aluminum alloys will reduce the
pitting and corrosion attack. Recent Navy results are sum-
7075-T735I X marized in Table 66. Pitting for susceptible alloys was reduced
from as much as 40 mils to 3 mils in I year by use of a
7079-T6 X suitable sacrificial aluminum (or zinc) anode. Magnesium
 63

TABLE 66. DEPTH OF ATTACK FOR ALUMINUM ALLOYS 7,..---·------------------,70

AFTER 368 DAYS' EXPOSURE IN SEAWATER,

i
KEY WEST, FLORIDA(91) Corrosion rate - water
. CorrOSIOn rate - sediment
:.:. Pitdepth,moximum
Depth of Attack(a), mils-_ _ . P
No Cathodic With Cathodic 6 f- P Perforated -60
Alloy Protection Proteetion(h)
----
5052-H32; 5083-0 <I <1
5086-H32; H34, H 112
. 5257-H25, 5456-H321 5 50
6061-T651 ; X7005-T63
7106-T63

1100-HI4; 5050-H34; 5052-H34; 1-4 I mil except

5154-H38; Ale. X7002-T6; 1100-H14 (2 mils), and ~
E~ 4
Ale.7178-T6(c) Ale. 7178-T6 (4 mils)(c)
~
J 40 .!!!
E
IIOO-F; 2014-T6; 6061-T6; 5-10 1 mil or less except (£
I
I
X7002-T6(d) 2014-T6 (2 mils) c
o
3003-H 14; 7079-T6; 7075-T735I 11-20 .~ 3 f-
I mil or less
(;
30 ~
2024-T351; 2219-T87; 7178-T6(d) 25-40 3 mils or less; o
71 78-T6(d)
- - - - - _ . _ - - - - - _-.-_
------------------------
---
(a) Based on average of five deepest penetrations. 2f- -20
(h) Aluminum anode used.
(c) Edges cracked severely.
(d) Edges cracked.

anodes should not be used, since their higher voltage will 10

overprotect and increase the pH developed at the cathode.
Aluminum is amphoteric and will be attacked under these
alkaline conditions.
O*++~f+""+--""I+.I:O:.IIIWI-+--++--f+""'+'~O
Days 181 366 1971 402 123 403 751 1064 1402
Another method of control is to clad the susceptible alloy
with a sacrificial metal. As long as the cladding is not con- Depth I 5 FI 2500 FI 6000 FI /2poor l

sumed, the underlying metal will be protected. Note the Alloy 1l00-HI4 1180
reduced degree of pitting of Alclad 3003-H12 as compared
with that of the unclad alloy in Figure 69. FIGURE 7 0. CORROSION RATES AND MAXIMUM AND
AVERAGE PIT DEPTHS OF 1000 SERIES ALLOYS IN
High-strength alloys in the 2000 and 7000 series are PACIFIC OCEAN WEST OF PORT HUENEME(90)
Used with perrnission of U. S. Naval Civii Engineering Laboratory
generally not suitable in seawater. However, with corrosion
control, such as paint and cathodic protection, high-strength
alloys are uscd occasionally. Alloys such as X7002-T6 and
7178-T6 tend to delaminate or exfoliate in seawater,(91) This 6
Waler, INCO
is really a form of intergranular attack on these wrought Waler, INCO
materials where the grains have been enlarged in the plane of Waler, Allanlic, NRL
>. Harbor Island, N.C., Goddard
rolling. Local corrosion also is associated with weldments, C1.
Panama Canal, NRL
especially in alloys that obtain their strength by heat treat- E 4 NCEL
ment, such as the aluminum-copper and the aluminum-zinc- 0>
magnesium-copper series. C
Cl: 3
c:
o
Stress-corrosion cracking is a problem with high-strength .~ 2
alloys in marine and other environments and is discussed (;
separately. o

Highlights of the corrosion behavior of individual alloys,

frequently used in marine service, are discussed below. o L_..J.._~C:=::r:~~==::tS:u=rl=a=ce%::=:::t~=:t::=~
o 200 400 600 BOO 1000 1200 1400 1600 1800
Exposure Time. days
1000 Series. From a corrosion viewpoint, Alloy 1100 has
good resistance to seawater. However, because of its low FIGURE 71. CORROSION RATES OF 1100 ALLOY IN
strength, other, more suitable alloys usually are chosen for a SEAWATER AT DIFFERENT LOCATIONS(90)
marine application. The corrosion behavior of Alloy I 100 is Used with perm ission of U. S. Naval Civil Engineering Laboratory

summarized in Figures 70 and 71. In surface waters, both the Groover, et al,(91) compared the pitting and crevice-attack
corrosion rate (as determined by weight loss) and the depth of behavior in :;urface water at Key West, Florida, for Alloy 1100
pitting attack are relatively low. In the Pacific Ocean after 16 in the F and H14 tempers. These data are shown in Figure 72.
years, the corrosion rate was 0.97 mpy,(88) Groover, et aJ.(91) Pitting was minor for either heat treatment but the H 14
found a maximum depth of attack of 12 mils in I year on seemed to provide better resistance to crevice attack. Deeper
Alloy llOG-F in the crevice area. However, the attack on the pits are observed on some 1000 series alloys in the deep-ocean
exposed surface was less than I mil. Alloy II OG-H 14 showed a water than in the surface water. Ailor(93) compares Alloy
mean depth of pitting of less than 3 mils in I year. 1180-H14 with other aluminum alloys in surface water and in
 64

Alloy
3Or----------------,
o Average af 5 deepest penetrations 1180 - H14 {I{~~~iiiiiiiiiiiiiiii-==:J
2014 ~
• Deepest attack in crevice
6 Deepest attack on surfaces
E 2219
_20 3003
"""
<.)

E 5050
~ No
anode 5052
.....o o Deepest pit
5086 • Average of 20
J:: 10
Ci 5154 deepest pits
C1l
o
5257
5456
8A28
6061
X7002
Sheet
FIGURE 72. CORROSION AND EFFECT OF CATHODIC
PROTECTION ON II0o-F AND 11Oo-HI4 ALLOYS
AFTER 368 DAYS' SEAWATER EXPOSURE AT
KEY WEST, FLORIDA(91)

ocean water at 2,370 feet in Figure 73. Alloy 11Oo-HI4

showed a maximum depth of pitting at 5,640 feet of 39 mils o 10 20 30 40 50 60
in 123 days compared to 13 mils at a depth of 5 feet for an Pit Depth, mils
exposure of 366 days.C 90 )
FIGURE 74. MEASURED PIT DEPTHS AFTER I-YEAR
As shown in Figure 74, Alloy 118o-HI4 - compared with EXPOSURE AT 2,370 FEET IN PACIFIC OCEAN WEST
the 5000 Alloy series and with 6061 - showed higher pitting OF PORT HUENEME, CALIFORNIA(93)
attack after I year at 2,370 feet. Normally it is expected that
high alloy purity will promote pitting resistance, but this is not Since the 5000 series alloys are more corrosion resistant
the case for this exposure condition. to shallow- and deep-ocean environments and have other attrac-
tive properties, it is concluded that there is no particular
advantage in the selection of a 1000 series alloy for most
Alloy
marine applications.
1180-H14

2219 Alloy 3003. A study of Figures 68, 69, and 74 shows that
Alloy 3003-H14 has a tendency to pit in seawater. In addition,
3003
it exhibited a higher rate of general attack than did the 1100
alloy at Key West, FloridaJ91) However, the high-purity Alloy
5086 o Harbor Island
1180-H 14 shows a greater tendency to pit in surface and
• Deep Sea
5154 deep-ocean environments than does Alloy 3003.(93)

5257 Corrosion-rate data for Alloy 3003, based on weight loss,

5456 are shown in Figures 75 and 76. There is some indication that
well-aerated surface waters are less corrosive to this alloy than
6061 deep-ocean waters. Corrosion rates of less than 2 mpy seem
X7002 typical for this alloy in surface waters, whereas rates as high as
Sheet 4 mpy are observed in the deep ocean.
X7002
Plate By cladding the 3003 alloy with a suit"able layer of
Alclad unalloyed aluminum, the tendency to rapid pitting can be
X7002
alleviated (see Figures 69 and 77). Furthermore, the corrosion
Alclad
7079 rate is reduced to about half. However, once the cladding has
been removed by corrosion, the core metal (3003) will revert
0 10 20 30 40 to the higher rate. In typical cases, the life is extended several
Pit Depth, mils years by cladding, but the strength is reduced for a given total
thickness.
FIGURE 73. RELATION BETWEEN AVERAGE PIT DEPTH
(20 DEEPEST PITS) AFTER I-YEAR EXPOSURE AT THE
SURFACE AND AT 2,370 FEET AT HARBOR ISLAND, 5000 Series. Among the 5000 series alloys, those which
N. c., AND IN PACIFIC OFF PORT HUENEME, find application in seawater installations include 5052, 5083,
CALIFORNIA(93) 5086, 5154, and 5454. As with aluminum alloys in general, the
 -
65

c::::J Water
Mud
* denotes a I x 6
11
piece
II••• } /23 days-5,640 II
Welded }
197 days - 2,340 II
-h } /23 days - 5,640 It } Unwelded

3OO3-
HI4
1 * } /,064 days - 5,300 It

} /97 days -2,340 It

1II•••••• } 123 days -5,640
~*i~~~~}~I~'0~6;4JdaYs - 5,300 II
It

h } 123 days-5,640 It
~ } 197 days - 2,340 It

123 days - 5,640 II

Alclad
~}1,064 days - 5,300 II
3003-H12

1 } 197 days - 2,340 It

} 123 days - 5,640 It

1,064 days - 5,300 It
} 197 days - 2,340 It

} Welded, 123 days - 5,640 II

"
1
2219-T81 } 1,064 days - 5,300 It } Welded } 197 days - 2,340 It
} Unwelded
} 197 days - 2,340 II 123 days -2,500 II
123 days -5,640 I
7178-T6
Ix6
11
{ 1,064 days -5,300 II
} 197 days -2,340 It
• • • • } 123 days -5,640 It

. . . . . } /,064 days - 5,300 It

7039-T6
{ } 123 days -5,640 It

} /97 days - 2,340 II

• • • • } 197 days - 2,340 It

123 days - 5,640 It

} 123 days }
Na.2
5,640 II
7079-T6
{ b III d a y s } 5,600 It,
~ 1,050 days
.
} 197 days
2,340 II

Allanllc Ocean
6061-T6

l,~~~~}
} 1,064 days -5,300 It

197 days - 2,340 It

o 2 3 4 5 234 5
Corrosion Rate, mpy Corrosion Rate, mpy

FIGURE 75. CORROSION RATES OF ALUMINUM ALLOYS IN THE DEEP OCEAN (PACIFIC OCEAN UNLESS
OTHERWISE SPECIFIED)( I)

4r----""-----------------~ 4.----- ·--------------.40

o NCEL ,6000 II, waler

i
>. Corrosion rate -water
a. • NCEL,60oo II, sed,menl Corrosion rate - sediment
E~ 3 o NCEL, 2500 II, waler :.: Pit depth, max/mum
Cll • NCEL,2500 It ,sediment Pit depth, average 30 l/l

~c 2
X NCEL,surlace
6 Goddard ~
E
o .... Port Hueneme ,California
v; (£ 2
~
c
o
o
u
o0!-~2~00~~4~00~=600I::~8:t00==100::l::0=1=2I::oo==14±:00::;::=I600:l::=I::l8oo~-2JOOO
~
v;
(;
-
Ii:
u
Exposure Time, days
oLl-tW'44JUo.
Days 181 366 197 402
FIGURE 76. CORROSION RATES OF 3003 ALLOY AT
DIFFERENT DEPTHS AND SURFACE LOCATIONS IN
Deplh 5 Ft I 2500 FI

THE OCEANS(90)
Used with permission of U. S. Naval Civil Engineering Laboratory FIGURE 77. CORROSION RATES AND MAXIMUM AND
5000 series alloys tend to pit. Reinhart's data for both shallow-
and deep-ocean waters are summarized in Table 67,(90) Corro- .
AVERAGE PIT DEPTHS OF ALCLAD 3003 ALLOy(90)
Used with perm ission of U. S. Naval Civil Engineering Laboratory

sion rates of 2 mpy or less are reported at all depths, while the
average of the deepest pits may be as much as 50 mils. After attack for Alloy 3003-H 14 as compared with the 5000 alloys
I-year exposure in the surface water at Key West, Florida, all shown in Figure 78.)
5000 series alloys showed a mean pit depth of less than 3 mils
(see Figure 68). To illustrate the fact that the corrosion rate is not far
different for these alloys at the surface and at ocean depths,
Pitting and crevice-attack data are summarized for three consider Alloy 5086-H34. In well-aerated surface water the
alloys, 505Q-H34, 5052-H32, 5052-H34, and 5083-0, in Figure corrosion rak ranges from about nil to about I mpy. In
78. Usually the crevice attack was the more evident, but all deep-ocean WJter a rate as high as 2 mpy has been obtained
three alloys have excellent resistance. (Also note the higher (Figure 79).
 66
TABLE 67. AVERAGE CORROSION RATES AND AVERAGE The pit formance of Alloy 5086-H34 is quite a different
PIT DEPTHS OF AI-Mg ALLOYS (5050, 5052, matter. Pit depths of less than 5 mils are typical in surface
5454,5456,5083 AND 5086)(90) waters, but may range anywhere from 50 to 75 mils in deep-
ocean water. These facts are illustrated by the bar graph in
Average Figure 80.
Average
Exposure Corrosion Rate, Pit Depths,
Time, Depth, mpy mils
days feet Water Sediment Water Sediment
7 72
~
..,
73 75
A
70

~ eo"",," ",to - .,to,

Corrosion rote- sediment
181 5 l.l 5.0
6 .:: Pit depth, maximum 60
366 5 0.6 Pit depth, average
197 2340 0.9 0.8 17.4 22.8
5 50
402 2370 0.6 0.6 32.4 13.5 ~
E .J!!
123 5640 0.8 1.9 11.8 36.5
~ 4 40 E
403 6780 1.9 0.7 50.0 31.6 0
a: .c:.

751 5640 1.6 2.7 48.6 29.7 c a.

30 ~
0
"iii 3
1064 5300 1.0 1.4 46.2 47.8 e a::
15
u
2 I- 20

4Or-----------------------,
o Average of 5 deepest penetrations 10
No
anode
• Deepest attack in crevice
A Deepest attack on surfaces
Days
o ~ Ir . ~:~~ ImrJ 0
181 197 1t402 1'23 14031 751 1064 181 366 402
Depth 5F 2500Ft GOOOFt
II
5Ft
I 2500Ft
I

.><
U
o
Alloy 5086-H34 II ~~- I
5086-
~20 HII2
.....o
FIGURE 80. CORROSION RATES AND MAXIMUM AND
.C-
AVERAGE PIT DEPTHS OF 5086 ALLOy(90)
o. Used with permission of U. S. Naval Civil Engineering Laboratory
~ 10
The 5000 series of alloys, if they are to see deep-ocean
service, may be provided with galvanic anodes to reduce the
tendency toward pitting and crevice attack. With such pre-
cautions, they should give satisfactory service, except as noted
'---y----J '---y----J '---y----J '---y----J below.
3003-HI4 5050-H34 5052-H34 5083-0
There is some evidence that alloys with high magnesium
FIGURE 78. CORROSION AND EFFECT OF CATHODIC content, e.g., Alloy 5456 with 5.25 percent magnesium, are not
PROTECTION OF 3000 AND 5000 SERIES ALUMINUM resistant to seawater corrosion in some of the heat-treatment
ALLOYS EXPOSED FOR 368 DAYS IN SEAWATER AT conditions that develop maximum strength. For example, Alloy
KEY WEST, FLORlDM91) 5456 in the H34 heat-treatment condition is found susceptible
Used with perm ission of U. S. Naval Research Laboratories to exfoliation, craterlike pitting, and severe corrosion. Stress
corrosion, as discussed elsewhere, can take place when the heat
3.--....,.---------------------, treatment results in an intergranular precipitate of a mag-
o NCEL ,6000 ft , water nesium-aluminum compound. Alloys with less than about 4.5
• NCEL,6oo0 ft, sediment
>- o NCEL, 2500 ft , water percent magnesium seem to be relatively immune to the effects
a. • NCEL,2500 ft ,sediment
E of heat treatment on corrosion behavior.
- 2 X NCEL,surface
Q> A NRL, 5600 ft' Atlantic
o
a:
c Alloy 6061. Of all the aluminum alloys used in seawater
o
iii applications, Alloy 6061 appears to be the most frequently
e
~
selected. This alloy combines good strength with good resis-
8 tance to seawater. Corrosion rates for both deep- and shallow-
ocean environments are summarized in Figure 81,(90) In both
o0~-~~~-~400~--=:::6oo~==;8;00;::=::::;;1000;;;~-~,2oo Atlantic and Pacific surface waters, corrosion rates are of the
Exposure Time, days order of 0.3 mpy. At the lower oxygen levels in Pacific deep-
ocean exposures, the rate is higher, typically around I to 2
FIGURE 79. CORROSION RATES OF 5086-H34 ALLOY AT mpy, although rates up to 3 mpy at 6,000 feet have been
THE SURFACE AND AT VARIOUS DEPTHS IN THE observed (see Figure 81). The 16-year results for the surface-
OCEANS(90) water condition in the Pacific Ocean are shown in Figure 66.
Used with permission of U. S. Naval Civil Engineering Laboratory
Alloy 6061-T was found to corrode at 0.91 mpy.
 Corrosion
4r------------------------, 7_.....:;B
6°i---r---;:--"":;:---i---r-_;:-_-r
o NCEL ,6000 fl, Pacific
!3~~
'0
f), NCEL,2500 fl,PaClfic
'1 NCEL, surface, Pacific
X NRL ,5600 fl, Atlanlic
o Surface ,AllantlC ...... 5 X Maximum pit depths
a:: 2 f- .. NRL,surface,PCZ Pacific E o Corrosion rate
a .P • MEL,6000fl, Pacific
4
gl~ ~
c
.2
'0
<3 '/;" Q; 3
00 200 400 600 800 1000 1200 1400 1600 IBOO 2000
U
c
o
Exposure Time, days u 2
C
Ql
FIGURE 81. CORROSION RATES OF 6061-T6 ALLOY IN 0>
~,
SEAWATER IN THE OCEANS(90) o
Used with permission of U. S. Naval Civil Engineering Laboratory

As with other aluminum alloys, Alloy 6061 tends to pit in

seawater exposures. Figure 82 shows the higher pitting rates FIGURE k3. CORROSION RATES AND MAXIMUM PIT
obtained in deep water, as compared with those in surface DEPTHS OF 6061-T6 ALLOY AS RELATED TO
water. The main effect seems to be oxygen availability rather OXYGEN CONCENTRATION AFTER I YEAR OF
than depth, per se. Although weight loss is not greatly affected, EXPOSURE(90)
there is a striking increase in depth of pitting with decrease in Used with permission of U. S. Naval Civil Engineering Laboratory

oxygen concentration, as shown in Figure 83. It should be

stated that the pitting behavior of 6061-T6 tends to vary some Mud Zone
from lot to lot. At 5,640 feet, for example, some panels were
entirely free from pitting, whereas others showed severe attack. Ocean-bottom sediments vary considerably in composition,
Ailor(93) has compared the pitting tendency of Alloy 6061-T4 depending on their origin. Experiments conducted in the
with other aluminum-base alloys (Figure 74). Here, Alloy 6061 Pacific off Port Huemene( I) have provided most of the infor-
compares favorably with many of the 5000 series alloys in the mation on the performance of aluminum alloys imbedded in
same program, such as 5050-H34 and 5052-H34. the mud. The sediment in this area contains various organisms,
including sulfate-reducing bacteria. Since aluminum alloys are
resistant to sulfides, one might expect them to do well in the
mud zone. Such is not the case, however. Probably because of
9 the low oxygen content in the sediment, the depth of pitting
in the mud zone is high and of the same order as that in the
deep ocean. For example, panels of 6061-T6 both in the mud
B and just above it showed maximum pits of 78 mils after 3
years at 5,300 feet. As shown in Figure 69, the 5000 series
alloys (as well as others) all tend to pit severely in the mud
7
zone.

6 Until more experience has been developed, the corrosion

>- allowance for exposure of aluminum alloys to the mud zone
a.
E should be similar to that employed for exposure in the deep
~ 5 ocean.
0
a::
c
0
iii 4
e Stress Corrosion of
u
0 High-Strength Alloys
3

2 2000 and 7000 Series Alloys. High-strength aluminum

alloys of the 2000 and 7000 series are susceptible to stress-
corrosion cracking in marine environments. The degree of
sensitivity varies with composition and heat treatment. Heat
treatments which produce highest strength are most apt to
increase susceptibility to stress-corrosion cracking. The alloys
o "+Io"t+l~ may also suffer rapid intergranular corrosion. This is par-
Days
Depth ticularly true for alloys with heat treatments that reduce
susceptibility to stress-corrosion cracking.
FIGURE 82. CORROSION RATES AND MAXIMUM AND
The information on stress-corrosion cracking of aluminum
AVERAGE PIT DEPTHS OF 6061-T6 ALLOy(90)
Used with permission of U. S. Naval Civil Engineering Laboratory alloys is based on (I) service experience, (2) marine exposure
 68
of experimental panels, and (3) the 3.5 percent NaCI alternate- Alloy 2219 was found susceptible to stress-corrosion
immersion test in the laboratory* Not all alloys respond to cracking in chloride environments in the T37 but not in the
this laboratory environment to the same degree as they do T87 condition. Alloy 7075 is susceptible in the T6 condition
actual marine atmosphere. For example, the performance of but the T73 heat treatment produces a high resistance to
aluminum alloys 7l78-T651, 7079-T65I, and X7006-T63I is stress-corrosion cracking.( I00)
compared is Figure 84. Although the two seacoast atmospheres
give different resul ts, performance of the same order of merit is Williams, et al.,(l 0 I) studied weldments produced by
developed by the three alloys.( 96 ) A quite different order of electron-beam welding on 7039-T61. Samples under tensile
merit is developed in the 3.5 percent NaCI test. The acidified 5 stresses up to 100 percent of the .02 percent offset yield were
percent NaCl, applied by an intermittent spray, is found to exposed to alternate immersion in synthetic seawater. During
provide better correlation with marine experience for these the 500-hour test, no failures by stress-corrosion cracking were
three alloys, but not necessarily for all aluminum alloys. observed. A mild pitting attack occurred in the heat-affected
zone and this accounts for the losses for the as-welded speci-
mens (see Table 68).
~] 6Or-------------------------,
TABLE 68. EFFECTS OF STRESS-eORROSION TESTING
U1 €
:::l
50 ON THE TENSILE PROPERTIES OF 7039
c= ALUMINUM PLATE(101)
.~~ 40 (SJmples were subjected \0 500 hours of -.:ydic lInml'rsJon In synthetiC seawatn)
c
~~ 30 Pre-Strt.'sS- Post-Stre.s.s~ DeneJsl'
<n
-o:::l Stress Corrosion ('orrosion ,,,
~8 20

--
Corrosion Ultimate Ultllna1e Ultimate
'0 Yield Strength. Stress TetlSlk Tensile Tensile
<nO 10 (.02(;;: Offscl), Levels(al, Stren~th, Strength, Strength.
:::l.l::
U11- ........~:i,,;o,L--l
oL_t:...:t~Il...._I:.<1l~L___lI:...&.IIo.::lJL...____I~::I...>I-
Condition ksi kSI ksi bl pLru::n~

New Kensington Pt. Judith Pt. Comfort 5 % NoCI 3.5 % NoCI Longitudinal welds, 28,35 ,55 53.(} 39.5 26.0
Industrial Seacoast Seacoast Intermittent Alternate welded in T61 22.6
Atmosphere, Atmosphere, Atmosphere, Spray, Immersion, condition 198
791 Days 764 Days 738 Days 28 Days 84 Days
Longitudinal welds, 35 ,~ 31.7 5115 51 15
wddl'd in T4 and ,8,
FIGURE 84. RELATIVE RESISTANCE TO STRESS artificially aged 24,0
to Ttll
CORROSION CRACKING OF THREE ALUMINUM
Long-tr:.Jnswrse 22.85 20,6 471 405 14.0
ALLOYS USING 2.5-INCH-DIAMETER ROLLED welds, 18.3
ROD SPECIMENS(96) welded in To I 16.0
Used with perm ission of American society for Testing and condition
Materials
Long-lr:.Jt1SVer.sl' 41,5 41.,5 5615 5683 0
The stress levels employed corresponded to 75, 50, and welds. 37.13
25 percent of the respective transverse yield strengths. welded in To I 33.0
resolu{lon and
:.JrlifidallY:.Jged
A plot of the stress-corrosion results for commonly used
aluminum alloys is shown in Figure 85.(97) As is evident, the (al 100 percent 01 02 perlTnt offset
short-transverse samples, taken from plate 2.0 to 7.0 inch
thick, were the most susceptible. Special heat treatments have
been developed to increase the resistance of high-strength These examples demonstrate that some of the high-
aluminum alloys to stress-corrosion cracking. Several of the strength alloys can be used in marine environments at a
alloy-temper combinations shown in Figure 86 have relatively sacrifice in strength. The tensile strength of Alloy 7075 in the
high stress-corrosion-cracking thresholds in the short-transverse T7351 condition is about 10 percent less than that of the same
direction. alloy in the T6 condition. Under the circumstances, it may be
preferable to use either Alloy 6061-T6 or one of the strain-
Hunter and Fricke(99) have observed the corrosion hardened 5000 series alloys which are more resistant to stress-
behavior in chloride environments of Alloys 7079-T6 and corrosion cracking and to other forms of corrosion.
7039-T6 as compared with the same alloys under stress. Un-
stressed 7079-T6 was attacked intergranularly on both
"former" grain boundaries and fragment boundaries. For 5000 Series Alloys. Strength is imparted to the aluminum-
7039-T6, unstressed samples corroded by pitting. Stress- magnesium series of alloys by strain hardening. This is usually
corrosion cracks in 7079-T6, 7039-T6, and 7075-T6 always followed by a partial anneal, with some reduction in strength.
initiated in "former" grain boundaries perpendicular to the Cold working introduces residual stresses, but is also believed
stress. Boundaries between "grains" having considerably differ- to promote intergranular precipitation of a magnesium-
ent orientation were preferred in many cases. Pits resulting aluminum compound during aging. Alloys with higher
from dissolution of minor constituents, or in the matrices, were magnesium content, especially those with more than 4.5 per-
not related to crack initiation in 2219-T37, 7075-T6, or cent (e.g., Alloys 5356 and 5456; see Table 69), tend to form
7079-T6, but may be related to the cracking behavior of Alloy this precipitate more readily. When the intergranular precipitate
7039-T6.(99) has developed in these alloys, the combination of a susceptible
path and applied or residual tensile stress will accelerate inter-
*For all oVL'rall view of strcss-,...-orrlhlOIl lTJcking of aluminum. granular corrosion cracking of the alloy in the marine environ-
thL' [(,;ldcr is n:fcffcd to DMIC Memorandulll ~O~,(94) Recent ment. Distortion of the grain structure by the strain-hardening
Luropc:tn (bta arc n.'vil'\VeJ ill D\t1C r-.kmor:llHlulll 240.( l))) process may result in a less direct path.
 69
Environment: 3.5 percent NoCI alternate immersion, 12 weeks Tensile slrenglh (oyg)

ji
Specimen: 0.125 -inch -diameter tension bar ield slrength (Oyg)
Highesl susloined lens ion slress
Ihol did nol couse failure
2 Number of loIs

100
'iii
.><.
80
vi
II>
~
u; 60

""c
0 40
£:
0'
C ZO
~
u;
0
Longit~dinal Long - Trdnsve rse Trans~erse
0,2 to 7.0 in. Thick 0,2 to 1.0 in. Thick 0.2 to 7.0 in. Thick

FIGURE 85. COMPARISON OF THE RESISTANCE TO STRESS-eORROSION CRACKING OF ALUMINUM-ALLOY

EXTRUSIONS TO SALT WATER(97)
Used with permission of American Society for Testing and Materials
Observe height of white bars.

c::J Tensile yield strength

'iii
.><. ~ Long transverse s.c.c. threshold
vi tsS3 Short transverse s.c.c. threshold
""<5 100 I2ZI Fatigue - crack growth rate at K = 15 ksi./in.
.J:. Q)
:0 _ Critical stress intensity foetor (Kcl, I-inch-thick panel

~~S
r- . c
.!: .- 80
t··......··• Plain ·strain stress intensity foetor (K1c)
0.:1.
~
en Q).><.
- II>

-g~ - 60
....
0
.J:..J:.
O'~
co"" 40
-
u
:.::

~ t5 :5
en.><. u
"O8l11::
ZO
~u
.!!
'iii 111111111
c 0
~ 202O-T65I 7001-T7551 2024-T85I 7178-T765I 7075-T651 7079-T651 7075-T735I 2219-T851

FIGURE 86. COMPARISON OF THE EIGHT ALUMINUM ALLOY-TEMPER COMBINATIONS ON THE BASIS OF TENSILE
YIELD STRENGTH, STRESS-eORROSION-eRACKING THRESHOLDS (USING 3.5% NaCl ALTERNATE IMMERSION),
FATIGUE-CRACK GROWTH RATES, AND FRACTURE-TOUGHNESS CRITERIA, Kc AND KIc(98)

Long transverse direction except where noted, I-3/8inch plate.

 70
TABLE 69. COMMERCIAL ALLOYS OF THE 5000-SERIES In practice, aluminum hulls exposed to seawater often are
GROUPED BY MAGNESIUM CONTENT(l03) not painted. In the case of a small vessel, sufficient thickness
must be provided to allow for pitting. Some fishing boats are
Magnesium unpainted but make use of zinc anodes to control galvanic
Content, % Alloy Designation attack at critical areas such as in the vicinity of the
propelled 104) Biofouling is removed periodically by skin
Maximum divers.
<3.5 5005,5050,5052
5454 The major reason for painting aluminum which is exposed
5357,5457,5557 to seawater is to prevent biofouling. Antifouling formulations
3.5 - 4.5 5154 (3.1 to 3.9 Mg, 0.1 max Mn) based on toxic organo-tin compounds are safe and effective for
5086 (3.5 to 4.5 Mg, 0.2 to 0.7 Mn) aluminum. On the other hand, paints using copper compounds
should be avoided since copper ions released from the paint
>4.5 5083 (4.0 to 4.9 Mg, 0.3 to 1.0 Mn) may deposit on exposed aluminum and stimulate pitting. By
5155 (3.5 to 5.0 Mg, 0.2 to 0.6 Mn) interspersing a thick coating of anticorrosive primer, this
5056 (4.5 to 5.6 Mg, 0.05 to .20 Mn) problem has been mitigated to some extent, but with the
5356 (4.7 to 5.5 Mg, 0.05 to .20 Mn) advent of organo tins, the use of copper-bearing paints no
5456 (4.7 to 5.5 Mg, 0.5 to 1.0 Mn) longer can be justified. In no case should an antifouling paint
Nominal containing mercury compounds be allowed to contact
3.5 5154 aluminum. Mercury amalgamates with aluminum, and will
4 5086 promote cracking under tensile stress.
4.5 5083
5 5356-5456 Aluminum alloys serve well in the marine atmosphere if
properly selected and applied; however, poor workmanship can
lead to failures. Welds often are the source of failure.
The effect of nine different tempers on Alloy 5456 with
and without sensitization (to simulate welding) was investigated Where aluminum sheet or plate is to be joined to another
by Niederberger, et al.(l02) Failures occurred with the H12, metal, the aluminum should be on the weather side so as to act
H16, H32, and H36 tempers. No failures occurred in sensitized as a flashing, as illustrated in Figure 87. A fitting of another
or unsensitized samples in 0, H22, H24, and H321 tempers. metal should be electrically insulated from the aluminum (see
Alloy 5456-H32, as well as a series of other magnesIUm-bearing Figure 88). Stainiess steel (e.g., Types 304 or 316) fasteners
alloys, showed no signs of stress-corrosion failure after expo- have been used with success on aluminum. Here the area ratio
sure for about 400 days in the deep ocean.(90) is favorable, i.e., small cathode and large anode. Steel fastenings
clad with zinc (galvanized), aluminum (aluminized), or
In practice, the use of alloys with the higher magnesium cadmium (electroplated) also have given satisfactory service
content has been restricted to deckhouses and nonsensitive with aluminum, especially when the entire system is painted.
structural applications. This resulted from experiences with Whether paint is used or not, it is essential that the fasteners
stress-corrosion cracking. It would appear that by the use of be coated, as this will reduce the attack on the adjacent
suitable strain-hardening and temper combinations and by aluminum.
avoiding fit-up welds, or other sources of residual tensile
stresses, the alloys containing higher amounts of magnesium
can be used in marine service. Weather Side

Alloy 6061. Alloy 6061 is one of the aluminum- Aluminum deck house
magnesium silicide types and it may be susceptible to stress-
Stainless steel
corrosion cracking in the T4 heat-treatment condition if a high huck bolt
heat-treating temperature is employed, followed by a slow To suit framing
quench. In the fully aged condition, T6 temper, the precipitate requirements
is present as small discrete particles and the alloy is immune to
stress-corrosion cracking. I
For marine service, this alloy has a combination of
strength and corrosion properties that make it a preferred
choice over most of the 2000 or 7000 series of alloys.

Marine Applications FIGURE 87. ALUMINUM DECKHOUSE JOINT DETAIL(103)

Used with permission of Society of Naval Architects and Marine
Engineers
The application of aluminum to ocean-going vessels has
taken years. On ships, for example, there has been a step-by- Beryllium
step introduction of aluminum-alloy components, first in
pleasure boats, then for larger vessels. The Navy is now gaining
experience with aluminum-hulled vessels, including some Although beryllium is resistant to humid air, pitting is apt
hydrofoil ships.c I03) to occur in the marine atmosphere.
 71
stress, certain pits become more active and penetrate the metal
rapidly.

TABLE 70. PITTING OF PICKLED BERYLLIUM

Base of [CONTINUOUS TOTAL IMMERSION
fitting
IN IS C (59 F) NATURAL
C"8~:ZXZ:~lJ~X:8'.:gJ:Q~~~~~rAluminum
,... insert
plate or doubler
SEAWATERj(l06)

bushing
Metal washer Exposure Percent
Time, Pit Depth, mils of Surface
Self -locking nut
days Avg Max Pitted

FIGURE 88. TYPICAL INSTALLATION DETAIL OF

o Negligible 0.2(a) Negligible
2 Negligible 1.5 Negligible
DISSIMILAR-METAL FITTINGS( I 03)
Used with permission of Society of Naval Architects and Marine 3 1.3 1.9 Negligible
Engineers 5 I. 1.6 I
Pitting also occurs in seawater. As shown in Figure 89, the
10 1.2 1.8 2
pitting is most intense in synthetic seawater during the first 2
14 1.4 2.0 3
months. Pitting becomes more widespread with time, and pits
20 1.4 3.0 5
up to 4 mils deep have been observed. As presented in Table
30 1.2 3.0 12
70, pitting of the same order was obtained in natural seawater
40 1.0 2.5 15
at 59 F. Seawater at warmer temperatures than this would
60 1.2 3.0 20
normally be expected to have more fouling activity. Beryllium
in tropical waters, for example, would typically be covered
(a) Resulted from pickling.
with marine organisms and this would induce a rate of pitting
higher than those reported in Table 70.
Some method of controlling the corrosion is required if
beryllium is to be used in marine environments. Anodized
~o
coatings sealed with sodium silicate have shown improved
0 stability in saline solutions. A ceramically bonded aluminum
36 0 coating (Serme Tel W) is also employed on beryllium. The best
0 results are obtained by applying a double coat to a grit-blasted
Maximum pit depth
32 surface, drying at 175 F, and curing at 650 F.(l07) In marine
0 atmospheres, this coating can be used above 400 F, but the
2.8 anodized coatings cannot because they become unstable.
0 0 0
~ 0 Since information on behavior of beryllium in marine
2<4 0
'E environments is very scanty and the composition of commercial
.c
beryllium vanes considerably, any consideration of its use
0. 50 should be preceded by an intensive study of the corrosion
Q)
't:l
behavior in the actual environment involved.
-
0
~
(l.
40 ~
• Average pit Q)

30
() Magnesium
~:::>
en
20
'0 Higllly purified distilled magnesium corrodes in seawater

10 -c
Q)
()
a;
at a rate of about 10 mpy. or roughly double the rate of iron.
However, commercial magnesium often corrodes at several
(l. hundred times that rate, largely because of the presence of
0 impurities such as iron, and the corrosion is accompanied by
20 40 60 80 100 120 140 160
Exposure Time, days
visible hydrogen evolution. In view of this poor behavior,
magnesium and its alloys are not used in seawater. For
FIGURE 89. PITTING ATTACK OF UNSTRESSED example, after only I year in the Pacific Ocean at Panama a
PICKLED BERYLLIUM SHEET MATERIAL EXPOSED controlled-purity magnesium alloy (AZ31 X) 250 mils thick had
TO SYNTHETIC SEAWATER AT 77 F(l05) a pit 153 mils deep at mean tide.< I 09) The deep pits were
associated with a mollusk infestation. As a sacrificial anode
Continuous total immersion testing. however, magnesium has had considerable use in seawater a~
discussed earlier. '

The stress-corrosion-cracking behavior of beryllium in salt Judging from magnesium's poor behavior in seawater, one
solutions has been studied by several investigators.(l 05-1 08) might not expect good resistance to marine atmospheres. In the
The results to date have not indicated any susceptibility to marine atmosphere, however, magnesium is more resistant than
stress-corrosion cracking in salt solution or seawater for iron. The corrosion rate depends on (I) the amount of
commercial-purity beryllium. On the other hand, severe pitting chlorides reaching the surface and (2) the degree of rainfall,
that drastically lowered the load-carrying ability of the material dew, or moisture. Corrosion rates vary. but I mpy is fairly
has been encountered. There is some evidence to suggest that typical. For Alloy AZ31. the rate was 0.94 mpy after 16 years
while no greater incidence of pit density is observed with at Cristobal; about 0.9 mpy after 32 months at Daytona
 72
Beach; and 0.57 and 0.5 mpy, respectively, after 4 years at the magnesium in the presence of moisture develops a strong
SD- and SOD-foot lots at Kure Beach, N. C. Part of the varia- alkaline reaction at defects in a protective coating.
tion in rate at these four marine sites may be attributed to the
aggressiveness of the climate and part probably results from Zinc chromate pigmented primer often is used in pro-
different levels of impurities, such as iron, in the specimens, tective systems; this is followed by a top coating of a vinyl,
since they were taken from different heats. The relation epoxy, acrylic, or a urethane resin type of formulation.
between corrosion and exposure time for AZ61 X and AZ31 X
alloys at Cristobal is shown in Figure 90. Note that the higher Since magnesium is the most anodic metal in the galvanic
purity AZ61X alloy has slightly greater resistancdSS) Figure series, galvanic coupling to another metal will cause accelerated
91 shows the straight-line relation for the corrosion with time attack on the magnesium. The other metal in the couple also
for Alloy AZ3l A at Battelle's marine site south of Daytona, may deteriorate. For example, when a couple between
Florida. magnesium and aluminum was exposed at the 80-foot lot, Kure
Beach, N. c., anodic attack took place on the magnesium and
alkali attack, from the cathodic reaction, developed on the
-;; 20
If) aluminum; both metals corroded more rapidly than when
!!!. 0
·E -.J AZ31X uncoupled.

C
0
-
.s::
0>
Q)
15
AZ61X

:;: 3: Special-Purpose Metals

~
a; E 10
0
c
Q)
0..
Lt
5 The refractory metals are used in electronic and instru-
Q)
0> " Q)
ment applications, which may involve a marine environment.
~ ~
Q) ::J
~
The noble metals, likewise, have electrical, electronic, and other
>
<l:
U
0
2 4 8 16 special applications. Zinc is used as a sacrificial anode and as a
Exposure Time, years protective (galvanic) coating. Lead is used as an impressed-
current anode. Cadmium is used as a metallic coating over
steel, and is very protective. Tin, which is quite resistant to
FIGURE 90. CORROSION RATES OF MAGNESIUM AZ6IX
marine environments, is not extensively used as a metal, but is
AFTER 16 YEARS' EXPOSURE IN MARINE ATMOSPHERE
used in alloys.
ON CARIBBEAN COAST, CANAL ZONE(SS)

Refractory Metals
-;;
If)
8
If) 0 X Mg -8.8Li -7AI-1 Sn The refractory metals covered here include tantalum,
--.J
·E _ 0 Mg -8.8 Li -7AI - 0.05 Sn -I Mn
zirconiu m, niobium, molybdenum, tungsten, vanadium,
.s:: t;,. Mg-8.7Li -5AI-8ln
6f-
~O> 2611 hafnium, and chromium. Comparatively few data are available
5 .a; 0 Mg -3AI -Iln -0.3Mn
for these metals in marine environments. As a group, however,

~--
:;:3:
~ E 4- 2613 these metals show an outstanding degree of resistance to attack
OJe

'-g
by a variety of corrosive environments. The chemical properties
~LL
0.. of these metals have several points in common. Foremost

-"
-~
o 0
o
I-~
0
-::J
0 1
2615

Al31A
among these is the fact that they all form a tight, thin, passive
oxide film on their surface. This feature is related to their
good-to-excellent corrosion behavior in saline environments. All
~ 0 4 8 12 16 20 24 28 32 of these metals are fouled by marine organisms in ocean
Exposure Time, months waters. However, most of them are sufficiently passive to
perform well even in the presence of deposits and fouling.
FIGURE 91. MAGNESIUM-ALLOY CORROSION IN
MARINE EXPOSURE AT THE 300-FOOT RACKS AT
THE BATTELLE EXPOSURE SITE SOUTH OF
Tantalum. Of the refractory metals, tantalum is the most
DAYTONA BEACH, FLORIDA(lI 0)
corrosion resistant to a wide spectrum of corrosive solutions.
This inertness is caused by the presence of a self-healing film of
These examples indicate that unprotected AZ3l of com-
Ta205. As shown in Table 71, the corrosion rate for tantalum
mercial quality has moderately good resistance to marine atmo-
was only 0.0 II mpy after exposure to a 3 percent salt solution
spheres. Some roughening of the surface by pitting is apt to
at room temperature for 84 days. In seawater, with a pH of 8,
occur, especially with alloys of lesser purity.
tantalum rivals titanium in inertness. After 181 days' exposure
in shallow seawater, no measurable change was observedJ92)
Magnesium is not widely used for equipment in marine
An alloy of 90Ta-IOW also has been found to be completely
services. However, aircraft and military gear have used
resistant to ambient seawater.
magnesium components. A tremendous effort has gone into the
development of protective treatments and coatings for TABLE 71. CORROSION RATES OF REFRACTORY METALS
magnesium. DMIC Memorandum 205 discusses surface treat- IN 3 PERCENT NaCI(l12)
ments for magnesium in great detail.( Ill) Test Corrosion Rate, mpy
Temperature, Period, (Calculated From Weight Loss)
F days T, Zr HI V Nb Ta Cr Mo W
A recommended method of providing protection is as
follows: first apply a conversion coating, such as Dow-17 68 7(a) a 007 a 0013 0015

anodize, to the metal surface; then apply an alkali-resistant 68 84 a 0011 057 00069 00017 a 0011 00031

coating system such as an unpigmented epoxy resin base, and ~I~ a 0.067 0.022 07 005 003 a 004 028

cure by baking. Alkali resistance is important because Lll Alkrn<1ft>immcrsion: the other two tt'sts <.ITe for continuous·immersion
 73
As shown in Table 71, the corrosion rate of tantalum in a contains 30 percent tungsten. These two alloys were compared
salt solution is an order of magnitude higher at 212 F than at with molybdenum in substitute ocean water as a liquid and as
68 F. Presumably in hot seawater, there also would be an a spray. In the substitute ocean-water test at 140 F. the
acceleration in the attack. It is also possible that crevice attack corrosion rates for molybdenum. TZM, and M030W were 2.1,
in tantalum may become a factor in hot seawater. 1.7, and 1.4 mpy, respectively. In the spray test. the rates, in
the same order. were 0.4. 1.1, and 0.5 mpy. All specimens
Tantalum is also inert as an impressed-current anode in developed a thin black deposit with very slight corrosion.( II 5)
ambient seawater. The tantalum surface, in this application, is These results would suggest that the two alloys have marine
normally platinized. resistance of the same order as that for unalloyed molyb-
denum.
When coupled to such structural metals as steel or
aluminum, tantalum may develop nascent hydrogen on its
cathodic surface. In acid solutions, this leads to embrittlement Tungsten. Tungsten. like molybdenum, resists attack in
of the tantalum.(l12) However, in alkaline sea~ater there marine atmospheres (see Table 71). In synthetic seawater,
appears to be less danger of this action taking place. The same corrosion rates of 0.2 mpy (95 F), 0.3 (140 Flo and 0.7 mpy
rules apply for coupling tantalum as for coupling other metals, (212 F) are reported.(l14) In live seawater. a corrosion rate of
such as titanium, to common structural metals. 0.3 mpy after 181 days was obtained. These results are similar
to those for molybdenum.

Zirconium. Zirconium is resistant to a wide spectrum of

saline solutions. For example, it resists CaCl2 solutions up to Vanadium. Vanadium shows good resistance to sodium
boiling temperatures and, as shown in Table 71, its corrosion chloride (see Table 71) and to synthetic seawater. In air-
rate in 3 percent NaCI is 0.01 I mpy at 68 F and 0.067 mpy at saturated NaCl solutions at 95 F. corrosion rates of 0.4 mpy
the boiling point. In synthetic ocean water, zirconium is fully were obtained. In live seawater. vanadium corrodes at 3
resistant up to the boiling point. The Navy has reported the sea- mpy.(46) From this evidence, one would expect vanadium to
water behavior of zirconium to resemble that of titanium.(l13) be less resistant to marine environment than are titanium and
Seawater with free chlorine present attacks zirconium, and in tantalum, but to have a resistance similar to that of molyb-
this respect, zirconium is different from titanium. denum.

Zirconium, from the evidence at hand, can be expected to

be completely resistant in marine environments, including the Hafnium. Hafnium, for which no marine data were found,
atmosphere, at ambient temperatures. would be expected to resemble zirconium in resistance to
marine corrosion. In stagnant 20 percent NaCI solution at 95
F, hafnium corrodes at 0.08 mpy .(116) (See also Table 71.)
Niobium. Niobium is similar to tantalum and zirconium in
its corrosion properties, in that it will resist acids and salt
solutions. There are some exceptions. Niobium, as indicated in Chromium. Chromium, as a metal sheet, is not attacked
Table 71, showed the same order of corrosion resistance in 3 by NaCI solution (see Table 71) at temperatures up to the
percent NaCI as did zirconium. Niobium should be resistant to boiling point. In this environment it was as resistant as
all marine environments. Niobium showed no measurable attack titanium. In seawater, the strong passive film should be
after 181 days of exposure in seawated92) resistant, 'and local attack should be less likely than in the case
of the stainless steels.
Molybdenum. Pure molybdenum oxidizes slowly in the
marine atmosphere, thus developing a series of interference Chromium. as an electroplate over a nickel coating confers
colors. ASTM tests have shown corrosion rates of 0.1 mpy good resistance to the basic metal, e.g.. steel, brass. or zinc-base
after 7 years for specimens at the 80- and 800-foot lots at die castings, in marine atmospheres.(46)
Kure Beach, N. c.(l2) The maximum pitting was 2.4 mils.

There is some attack under submerged conditions, par- Noble' Metals

ticularly when the solutions are aerated. In the German work
reported in Table 71, the corrosion rate obtained for molyb- I>latinum is the most resistant of the precious metals in
denum in aerated 3 percent NaCI was only 0.011,(113) as the ~roup consisting of platinum, palladium, gold. and silver.
compared with a rate of 0.4 mpy obtained by the Bureau of
Mined 115) Evidently, the aeration of the salt solution was Platinum is completely resistant to marine atmospheres
more effective in the Bureau of Mines' experiment. At 95 F, and to seawater. In the latter, its main application is as
corrosion rates of 0.4 mpy in 3 percent NaCl and 0.3 mpy in impressed-current anodes. Platinum is more often used with
synthetic ocean water have been obtained.(l14) At still higher another metal as a backing. such as platinized titanium or
temperatures, the rate of attack increases, e.g., up to 2.1 mpy tantalum. It also is an essential part of the lead-platinum anode
at 140 F and 3.5 mpy at 212 F for synthetic ocean water. system. All types of platinum impressed-current anodes have
been hi,ghly successful. On titanium or tantalum, for example, a
In seawater at Port Hueneme, California, molybdenum platinum coatll1g 100 microinches thick will provide for
showed uniform corrosion, with a rate of only 0.1 mpy after impressed cutrents as high as 100 amp/ft 2 . The oxidation loss
181 days.(92) Thus, molybdenum is very resistant in ambient of platinum' in seawater anode applications is taken as 6
seawater, but at elevated temperatures, some attack may be mg/amp-yr.(l17)
expected.
Palladium resembles platinum in marine resistance. In sea-
TZM is a dilute molybdenum-base alloy containing about water as an anode, palladium also is resistant, but less so than
0.45 percent titanium and 0.10 percent zirconium. M030W platinum.
 74
Gold is completely resistant to the marine atmosphere and 10
to seawater. It has been used to protect electrical contacts
from tarnishing and corrosion in a marine atmosphere. Gold t;. Monel
also has been used as a coating to protect a magnetic
diaphragm exposed directly to seawater. •
X
Zinc
Si bronze
0 Lead
Silver has good corrosion resistance to marine environ- B .... Low brass
ments, but will tarnish in a marine atmosphere, especially if 0 Cu-Ni
sulfur compounds are present. After 2.6 years at Kure Beach,
N. c., the corrosion rate of silver in seawater was 0.5 mpy.(46)
• Aluminum

Silver's main use in the marine field is in electrical and ~

electronic equipment such as radar waveguides'(26) On electri- 'E
cal contacts, a thin coating of palladium or gold is sometimes 6
used to retard tarnishing. Lead-silver alloys are used for 0
c
impressed-current anodes.(118)
-
~
Cl>
C
Cl>
a..
Cl>
C' 4
0
Lead, Zinc, Cadmium and Tin Q;
>
oCt

Lead. Lead is resistant to the marine atmosphere. At

Cristobal, Canal Zone, corrosion rates of 0.1 mpy were
recorded for an 8-year exposure.(119) The corrosion was uni-
form, and as shown in Figure 92 is proportional with time. 2
Even lower rates were found at La Jolla, California, namely,
0.016 mpy after 10 years. Although lead is cathodic to steel, it
does confer protection as a metal coating. For thicker coatings Rc ~ 0.02 mpy
of say I mil or more, lead corrosion products tend to plug
damaged areas such as at a scratch. Protection is improved if
the marine atmosphere is polluted.
2 4 B 16
Exposure Time, years

o Cristobal marine atmospheric exposure FIGURE 93. COMPARISON OF AVERAGE PENETRATION

OF WROUGHT NONFERROUS METALS AFTER 16 YEARS'
CONTINUOUS IMMERSION IN SEAWATER(1 09)
Used with permission of National Association of Corrosion
Engineers

TABLE 72. CORROSION OF LEAD IN SEAWATER(121)

Exposure
Time, Corrosion Rate
Specimen Form years Mdd Mpy Location
99.96% Pb Bar 4 4.0 0.5 Weston super Mare
1.6% SbjPb Bar 4 3.0 0.4 Weston super Mare

2 3 4 5 6 7 B Chemical lead Sheet 0.5 3.1 0.4 San Francisco HIlrbour

Exposure Time, years Lead Plate 1.7 4.7 0.6 Kure Beach

FIGURE 92. RELATION BETWEEN CORROSION AND

EXPOSURE TIME FOR LEAD EXPOSED TO MARINE Information from a variety of exposures indicates that the
ATMOSPHERE IN PANAMA CANAL ZONE(l20) rate of attack for lead and lead alloys in seawater is about 0.5
mpy.(121) However, recent tests in shallow- and deep-ocean
The corrosion of lead is 0.3 mpy after 16 years in the environments showed rates ranging as high as 1.2 mpy for
Pacific Ocean.(120) A comparison of lead with other metals several types of lead (see Table 73). The attack was uniform
(Figure 93) indicates that its corrosion rate stabilizes at about for exposures of up to about 6 months. After longer periods of
the same rate as that for Monel, and is somewhat less than that time, the attack would be expected to diminish. It is of
of zinc'< I09) Pitting was observed in this exposure and was interest to note that the 67Pb-33Sn solder reported in Table 73
ascribed to local cell attack under marine fouling. It may be showed rates similar to that of lead in the deep ocean, but 3.7
that H2S generation from decaying organisms, in the lowest mpy in shallow seawater,(92)
layer of marine fouling, modifies the corrosion of lead.
The main use of lead in seawater has been as a protective
There seems to be little variation in the corrosion behavior sheath for submerged communications cables. The excellent
of lead in the seawater at different geographical sites. Typical resistance of the sheath is an indication that lead will endure in
rates for lead and lead alloys are presented in Table 72. both seawater and the bottom sediments.
 75
TABLE 73. CORROSION OF LEAD, SOLDER, TIN, AND ZINC TABLE 74. ASTM DATA ON ZINc( 122)
IN SEAWATER(92)
Penetration. mpy
weight loss Pit Depth,
Remarks Location 10 Yr 20 Yr
Metal Days Depth, ft mpy mils
Key West 0.019 0.022
Chemical 0.073
lead(a) 181 1.2 Uniform attack Sandy Hook 0.059
La Jolla 0.068 0.069
Ditto State College 0.040 0.044
\97 2340 0.3

123 5640 0.8

Tellurium TABLE 75. KURE BEACH TESTS ON IRON-CONTAINING

lead(b) 181 1.0 ROLLED ZINc( 122)
197 2340 0.3
Penetration, mpy
8o-Foot Rack 80o-Foot Rack
123 5640 1.1 6 I 6' I
Iron,
'il Months Year Months Year
Antimonial
lead(e) 181 1.2
0.0003 0.4 0.4 0.3 0.2
0.0008 0.45 03 0.3 0.2
197 2340 0.3
0.0014 0.5 0.4 03 0.2
0.0021 0.5 0.4 0.3 0.2
123 5640 0.8
0.006 0.45 0.4 0.3 0.2
0.011 0.45 0.6(a) 0.3 0.2
Solder<d) 181 3.7
=~-------- ---_..~-======-..,,=====
(a) 0.2 and I mil/year on duplicate panels.
197 2340 0.5

123 5640 0.5

environment are being conducted. Galvanized 22-gauge steel
Tin(e) 181 8.3 panels (with zinc coatings ranging from 1.5 to 2.6 oz/ft 2 )
coated on both sides have gone more than 32 years without
197 2340 1.8 any rust appearing. At the present rate of attack, it is
estimated that the 2-ounce coating* will last 79 years,( 122)
123 5640 0.5
However, higher corrosion rates would be expected where
ZinC<O 181 4.5 actual seawater splash strikes the galvanized surface.

197 2340 2.3 In seawater,-the corrosion rate of sheet zinc is usually I to

2 mpy(122), although some recent data indicate higher rates.
123 5640 6.7 After 3 years' exposure at Eastport, Maine, a rate of 1.0 mpy
(a) 99.9 Pb. was obtained. Similar rates are reported for zinc exposure in
(b) 99+ Pb, 0.04 Te. the Pacific Ocean off the Panama Canal Zone. Corrosion rates
(c) 94.0 Pb, 6.0 Sb. in flowing seawater at Kure Beach for special high-grade zinc
(d) 67 Pb -33 Sn. are given below,(122)
(e) 99.9Sn.
(0 0.01 Fe, 0.09 Pb. Exposure Corrosion
Time, yr Rate, mpy
0.5 1.9
4 0.8
Zinc. Although zinc is used mainly as a galvanic coating to
protect steel in the marine atmosphere, it is of interest to Corrosion rates ranging from 2.3 to 6.7 mpy were
examine the corrosion rates of zinc itself. During the first few obtained for zinc specimens containing 0.01 percent iron and
years, zinc corrosion tends to diminish and stabilize at a steady 0.09 percent lead in Pacific waters,(92) These data are
rate. By way of illustration, after 10 and 20 years at the presented in Table 73. Pits as deep as 13 mils were reported.
marine-atmospheric-exposure site at La Jolla, California, rolled On the other hand, in experiments conducted at Harbor Island,
zinc had reached a steady rate of 0.069 mpy.(122) At Key North Carolina, zinc with as much as 0.011 percent iron
West, Florida, an even lower rate 0.022 mpy was obtained. showed a rate of only 1.4 mpy. These data are listed in Table
Comparative data from four sites are presented in Table 74. In 76 along with tidal and low-velocity data. Note the good
the rural, mildly corrosive atmosphere at State College, behavior of zinc in the tide zone and the increase in attack
Pennsylvania, for example, the rate is double that of Kev West with a velocity of only 2 fps.
and two-thirds that at La Jolla.
Even though zinc usually corrodes at a rate lower than
The corrosion of zinc varies some with time of year first that of iron, it is not recommended as a metal for service in
exposed. Other corrosion experience with zinc suggested that seawater. There has been little actual use of metallic zinc in
purity might be a factor in the marine environment. However, seawater, partly because of poor physical properties and partly
as shown in Table 75, in I-year tests, iron contamination up to because of its susceptibility to localized attack.(46) Zinc's
0.011 percent did not adversely affect the corrosion behavior. major contribution is as a sacrificial anode in seawater, as
discussed elsewhere. Zinc is also used as a galvanic coating on
The excellent corrosion resistance of zinc in the marine
atmosphere helps explain its usefulness as a coating to protect *A l-ounce coating is about 1.8 mils thick and, therefore, a
iron. At Key West, exposure tests in an aggressive marine 2-ounce coating would be 3.6 mils thick.
 76
steel. Galvanized-steel piping is used on board ship to handle this out. The tendency of tin to pit as well as its susceptibility
seawater lines used for fire fighting. The limited oxygen present to crevice attack and to local corrosion under biofouling and
in the stagnant seawater inside the pipe no doubt is a factor in deposits would predicate against using tin in seawater. Tin is
the low rate of corrosion observed. about 0.25 volt cathodic to iron and, therefore, will not serve
as a practical coating system for the protection of steel alloys
TABLE 76. SEAWATER CORROSION OF IRON- in seawa ter.
CONTAINING ZINC(l22)

Corrosion Rate(a), mpy Cathodic Protection

Iron, Total Tidal 2 FPS
% Immersion Zone Flow
The corrosion of many metallic structures immersed in
0.0003 1.4 0.8 3.0 seawater can be reduced to a low value by the application of
0.0008 0.8 0.8 2.0 cathodic protection. Protection is achieved when the potential
0.0014 0.8 0.9 2.0 of the steel, for example, is brought to about -0.80 volt with
reference to the saturated calomel half cell. For submerged
0.0021 0.8 0.9 2.0
structures, cathodic protection is widely used, together with
0.006 0.8 0.8 2.0 coatings, to restrict corrosion.
0.01 I 1.4 0.9 2.0
Mechanism
(a) Average of two I x 4 x 1/2-inch specimens There are a number of ways of explaining the mechanism
exposed I year. of cathodic projection. Simply stated, a metal tends to develop
local anodes and cathodes when first immersed in an electro-
lyte like seawater. These arise because of compositional or
other variations on the surface. When an external cathodic
Cadmium. Cadmium is used as a metal coating over steel current is applied, the local cathodes tend to polarize to the
in marine applications. In the marine atmosphere, zinc is potential of the local anodes. Once this potential is achieved,
usually preferred, but if the local conditions are very corrosive, corrosion currents no longer flow. The quantity of electricity
cadmium may be better by a substantial margin, as illustrated to be supplied to achieve this condition will vary, depending on
by Figure 94. the metal and the depolarizing characteristics of the
environment.

100
Major Parameters
u
~
<J) 80
::J In seawater, the major parameters that affect cathodic
0::
polarization are resistivity, oxygen content. and velocity of the
OJ 60
u seawater, and the deposition of a calcareous scale. If the metal
.g is coated, the integrity of paint film will affect the current
::J
en 40 required for polarization.
-c:
OJ
~ 20 Resistivity decreases with increase in salinity; for seawater
OJ
D.- of constant salinity, the resistivity decreases as the temperature
O
is raised. In ordinary seawater, the resistivity may vary from 35
0 180 ohm-em in arctic waters to 16 ohm-em in tropic waters.( 124)
Resistivity will tend to increase considerably in harbors and
estuaries where there is freshwater dilution. Thus, for main-
FIGURE 94. COMPARISON OF PROGRESSIVE DEVELOP- taining polarization on a ship moving in and out of waters of
MENT OF RUST ON ZINC- AND CADMIUM-PLATED varying resistivity, a cathodic protective system responsive to
STEEL PANELS AT 80 FOOT LOT, KURE BEACH, N.C the changes in environment is required.
N.cJI23)
Oxygen is the principal depolarizer in seawater. An
Coating thicknesses 0.0002 and 0.0005 inch. increase in the oxygen content will promote greater depolari-
zation of the cathodic reaction and a corresponding increase in
Tin. Tin is resistant to marine atmospheres and could be current will be required to maintain polarization.
used in some special applications. After 10 years at a marine
location, tin showed a weight gain of 0.11 mdd'< 4) When the An increase in the velocity of the seawater causes the
deposit was removed, the penetration (calculated from the products of the cathodic reaction to be removed more rapidly.
weight loss) was found to be 0.089 mpy. The amount of oxygen arriving at the cathode surface per unit
of time also will increase. These combined actions will increase
Recent results for tin in seawater are given in Table 73. the current demand for polarization. For example, as shown in
Weight-loss penetrations of 1.8 and 0.5 mpy were obtained for Figure 95, increasing the velocity from stagnant to 13 fps
two deep-ocean exposures. The 3D-mil-thick sample in the would increase tenfold the current density required to maintain
surface exposure perforated in 181 days, and the corres- polarization on bare steel in seawater. For offshore platforms,
pondingly high penetration figure based on weight loss is only the movement or vibration of the structure may have to be
approximateJ(2) Although the older results suggested that tin added to the velocity effect of the ocean currents sweeping by
was resistant to seawater. the new informaton does not bear to arriving at some estimate of the increased cathodic-current
demand for polarization.
 77
~ consumed more rapidly than would be expected if the
"0 experiment were conducted at the surface. Since the pH is
>
lower at great depths, and the calcium carbonate concentration
E is below saturation, higher currents apparently are required to
U achieve polarization.
u
en
VI
> TABLE 77 . POLARIZATION OF BARE STEEL
0
600 IN SEAWATER(l25)
:;:
c
20
a.. 400 Current
0 5 10 35 40
Density
Applied
Required
FIGURE 95. CATHODIC POLARIZATION OF MILD Initial for
STEEL IN SEAWATER FLOWING AT DIFFERENT Current Continued
VELOCITIES AT 26 C(l24) Density, Exposure Protection,
Used with permission of National Association of Corrosion ma/ft 2 Time Film ma/ft 2
Engineers
Temperature also may affect the degree of polarization.
200 I day Soft, with high mag- 2-3
An increase in temperature decreases the solubility of oxygen
nesium content
but increases the rate of diffusion. In a particular situation,
these factors may tend to balance out. 100 2-3 days Fairly hard 2-3
50 5-6 days Hard, mainly calcareous 2-3
20 20-30 days Medium thickness, 3-4
Calcareous Coating
hard
The application of cathodic current promotes the forma- 10 2-3 months Medium thickness, 4
tion of hydroxyl ions at cathodic areas. Also, the concentration hard
of calcium and magnesium ions tends to increase in the film of 6 Up to 6 months Light, hard 4-5
seawater over the cathode. As a result of these changes, the if at all
solubility of calcium carbonate and magnesium hydroxide is
exceeded and a calcareous coating is deposited. The
development of this coating can be accelerated by using some-
what higher current density than that normally employed for
90
polarization in practice. For electrocoating, 50 to 350 ma/ft 2
gives satisfactory coatings'< 125) The most dense deposits tend Potential
80
Weight loss
to form at 100 to 200 ma/ft 2 and are found to contain equal
parts of calcium carbonate and magnesium hydroxide. (I 25) At
high current densities, above 200 ma/ft 2 , the deposit is quite ,-
N
70

60
-- -- -- -- --
1.2

, --
soft. The current density-time req'uirements for the formation I.I
0' "0
>
of calcareous films that result in low current requirements for 50 ",'
iii 1.0
protection are summarized in Table 77. It will be seen that at VI
W-
0
-.J 40 I

-
high current densities, films can be formed in a few days, after U
0.9 en
which a much lower current density is required for continued ..c 30 VI
0' >
protection. This fact is further illustrated by an experiment 'iii 0.8
conducted on prefilmed steel panels by the Dow Chemical 3: 20 0
Company. As shown in Figure 96, their work suggests that 07 C
once a calcareous deposit has been formed, only 3 ma/ft 2 is 10 -----"" 0'"
06 a..
required for protection. For these conditions, higher current 0
densities do not offer any additional protection. Current o 1 2 3 4 5 6 7 8 9 10
densities below 3 ma/ft 2 were not sufficient to maintain Applied Current Density, ma/ft 2
complete protection.
FIGURE 96. STEEL PANELS, FIRST COATED WITH
In practice, steel structures are polarized initially at higher CALCAREOUS SCALE (COX COATING) THEN
current densities than are required for continued protection, in CATHODICALLY PROTECTED FOR I YEAR IN
order to take advantage of the calcareous coa ting. Such a SEAWATER, SHOWING WEIGHT LOSS AND
technique can result in a considerable saving in current POTENTIAL AS RELATED TO CURRENT
requirements. For example, if a current of 50 ma/ft 2 is applied DENSITY( 125)
Used with perm ission of National Association of Corrosion
to a structure for the first 5 days or so, polarization can then Engineers
be maintained with a current of about 3 ma/ft 2 , as mentioned
above. Ampere-hour savings of as much as 40 percent can be Current Requirements
achieved during the first year of protection by this rapid
polarization procedure.( 125) It is pointed out that the discussion on the amount of
current required to prevent corrosion of steel is based primarily
There appears to be less tendency for the carcareous scale on relatively quiet seawater conditions. At some geographical
to form in the deep ocean. In an experiment conducted by the locations, the current requirements are often higher, for
Navy, galvanic anodes were found effective in providing example,S to 10 ma/ft 2 , depending on the velocity and other
cathodic protection to bare steel in the ocean at 5,600 factors. In Cook Inlet, Alaska, where ocean currents are
feet.(75) However, the anodes were found to have been particularly strong, a current density of as much as 15 ma/ft 2
may be required to achieve complete protection
 78
For steel in seawater, it is more typical to apply a protec- Selection of Anodes
tive alkali-resistant paint over the surface. This, in combination
with cathodic protection, results in an effective method of Two types of anode systems are employed in cathodic
corrosion control. Current requirements are much lower than protection. The anodes may be (I) the sacrificial type or (2)
for bare steel since it is necessary to provide protection only at the impressed-current "insoluble" type.
the damaged areas in the paint coating. These, in tum, will be
polarized more rapidly by the calcareous scale. The net effect
is to promote more uniform polarization of the entire struc- Sacrificial Type. Use of sacrificial anodes dates back to
ture, since damaged areas closest to the anode will be Faraday. Their major advantage is simplicity and little need for
"repaired" first, forcing the current to travel to more distant supervision.
coating defects (holidays). Cathodic protection does not inter-
fere with the performance of anitfouling coatings. The sacrificial-type anodes being used for seawater applica-
tions include zinc, aluminum, and magnesium. The charac-
teristics of these are given in Table 78.
Overprotection Effects

In seawater, steel structures can be protected at a poten- Zinc. Cathodic protection systems employing zinc anodes
tial of about -0.80 volt or higher versus the saturated calomel have been very successful. The design is simple, anodes of high
reference cell. At higher cathodic voltages, for example, -1.10 current efficiency are available, and the inherent self-regulating
volt or greater, there is danger of damaging effects from the characteristic is a distinct advantage. Zinc anodes need to
excessive hydrc,xyl-ion formation and from the large volumes employ a low resistance circuit so that the anode can develop
of hydrogen gas generated. Amphoteric metals and some pro- the necessary current needed to maintain the facility at polar-
tective organic coatings are sensitive to alkali. Blistering of ization. Zinc anodes have a high ampere-hour capability per
paint films may result from endosmosis effects or from hydro- unit volume. The protective coating or paint system on the
gen developed under the film. These effects frequently are marine structure is not subjected to local high potential, as
observed on that portion of the metal structure nearest the may occur with magnesium anodes in some installations.
anode. Nascent hydrogen can damage steel, especially the high-
strength low-alloy steels. On carbon steels, hydrogen damage in When zinc is employed in the cathodic protection of a
seawater usually is not observed under cathodic protection. steel ship's hull, the lesser volume of the zinc anodes compared
With excessive cathodic protection, the hydrogen liberated can with that of magnesium or aluminum can be an advantage from
promote catastrophic cracking with high-yield-strength steels the hydrodynamics involved. A general rule of thumb for a
(e.g., above 150,000 psi) when under tensile stress (hydrogen- steel hull is to employ one 22-lb anode, 6 x 12 x I. 25 inches
stress cracking). (or equivalent), for each 100 square feet of painted surface. In
addition, one such anode is provided for each 5 square feet of
One of the "poisons" that tend to promote hydrogen cathodic metal, such as the bronze propeller, bearings, shafts,
penetration into the metal is sulfide. Sulfides are present in etc. These extra anodes are installed close to the sites where
seawater that is polluted and also in waters at the bottom the cathodic metals are located. Anode life is only I to 2 years
where the mud may have sulfate-reducing bacteria. following this rule. Extra anodes can be installed if it is desired

TABLE 78. CHARACTERISTICS OF COMMERCIALLY AVAILABLE SACRIFICIAL ANODES IN

SEAWATER SERVICE(75,124,126-129)

Max
Structure Solution Current Ampere-hours Pounds
Potential, Potential, Efficiency, per per
Anode Description volt volt percent Pound I Amp-Year Notes
Magnesium 0.03 Cu (max), -U5 -1.50(a) 50 500 17.5
0.003 Fe (max),
and 0.10 Mn (min)
Zinc -0.90 -1.05(a) 95 354 24.7
-1.10(c)
Al-Zn-Hg 99.9% purity Al + -1.00 -1.05(b) 95 1280 6.1 No heat treatment
0.045 Hg + 0.45 Zn -l.I(c) req uired - good
efficiency
Al-Zn-Sn See Table 80 85(d) 1150 7.6 Requires precise
control of heat
treatment

(a) Closed-eircuit potential referred to Ag/AgCl electrode.

(b) Closed-eircuit potential referred to saturated calomel electrode.
(c) Closed-eircuit potential referred to Cu-CuS04 electrode.
(d) Efficiencies as low as 32 percent have been reported with improper heat treatment.
 79
to extend the time between replacement. When anodes are stable potential. The current efficiency is high for a wide range
mounted directly on the hull or structure, an anode shield, of current demand, as illustrated by the results in Figure 98.
usually of plastic, is employed to insure proper current
distribution.

The performance of zinc anodes depends upon the control

of impurities in the zinc. The presence of very small amounts Zinc anode
of certain impurities promotes the formation of a dense ad- MIL-A-1800IG
herent skin of corrosion product which polarizes the anodes.
The major harmful impurity is iron which, in amounts as little
as IS ppm, seriously impairs anode efficiency. This adverse
effect of iron can be counteracted by additions of silicon,
aluminum, and cadmium. Zinc anodes which meet Military 'E
Specification MIL-18001 G, presented in Table 79, are con- t Aluminum Zinc anode Aluminum
sidered entirely dependable and generate current at close to <3 0.2 anode 35 MIL-A-18001 G anode 36
100 percent efficiency.

TABLE 79. COMPOSITION OF ANODE

ZINC (MIL-1800IG)(127)

Composition, percent FIGURE 97. COMPARISON OF CURRENT OUTPUT IN SEA-

WATER OF ALUMINUM-ZINC-MERCURY TYPE ANODES
Al 0.10 -0.50 AND ZINC ANODES(91)
Cd 0.025-0.15
Pb 0.006 max Current was controlled by (a) 0.01 ohm shunt and (b) 0.5 ohm
Si 0.125 max shunts, respectively, to a steel cathode which was unpolarized.
Cu 0.005 max
Fe 0.005 max
Zn (balance) .0
~ 1350 100 'E
.s::
I
~ 0
0 0 ~
90 ~
a.
E 1215 ,,::;
0
<>
c
Aluminum. Although aluminum anodes have been avail- .~ 1080 80 Q)
'0
<>
able for many years, it is only during the last decade that they 0
a. 945 70 :::
have found extensive application in the marine field. The first 0
Seawater electrolyte w
u
anode developed for marine service was the Al3Zn (3% Zn)
alloy. The newer anode types are tertiary alloys of aluminum-
-
c
~::J
810

675
60 'E
~
50 u::J
zinc-tin and aluminum-zinc-mercury. Their characteristics are u 100 1000
given in Table 80. Applied Current Density I ma/tt!

TABLE 80. NOMINAL CHEMICAL COMPOSITIONS AND FIGURE 98. CURRENT CAPACITY AND EFFICIENCY AS
EFFICIENCIES OF SEVERAL PROPRIETARY RELATED TO CURRENT DENSITY FOR A NOMINAL
ALUMINUM-ALLOY ANODES(9 I) Al;0.04SHg-0.4SZn ALLOY( 130)
Galvanic
Chemical Composition, percent Efficiency,
If the aluminum-zinc-tin alloy is carefully controlled as to
Zn Sn Hg B Fe AI(b) percent composition and heat treatment, it too will provide high cur-
A 4.66 0.22 Not 0.08 Balance 84-87 rent and stable potential. Aluminum anodes can be used
detected(a) wherever protection with the magnesium type would be a
B 6.85 0.14 Ditto 0.02 0.05 Balance 45-80 problem.
C 4.36 0.13 0.07 Balance 60-85
D 1.65 0.08 0.07 Balance 31-69
E 0.60 0.04 0.07 Balance ·95 Magnesium. With the advent of the high-purity zinc anode
and, more recently, the ternary-alloy aluminum anodes, the use
(a) Spectrographically. of magnesium anodes for service in seawater has declined
(b) Minus the common impurities such as Si. markedly. However, magnesium is still used for some special
applications. The alloy preferred for marine service is
As in the case with zinc anodes, control of impurities for Mg-6AI-3Zn, with careful control of iron and nickel to less
aluminum anodes is essential for best performance. In addition, than 0.003 percent each and copper to less than 0.10 percent.
however, the AI-Zn-Sn alloy anode also requires a closely con- Its higher driving potential and lower density can be an advan-
trolled heat treatment to develop the desired electrochemical tage, even at 50 percent current efficiency, in some special
properties. Because of the reactive nature of mercury, special applications. For example, a 20o-pound anode has been
processing is also involved in obtaining the desired electro- developed to provide 6 amperes' output for a life of 2 years. It
chemical characteristics in the AI-Zn-Hg alloy anode. As shown is suspended from, and grounded to, the marine structure to be
in Figure 97, the current output of the AI-Zn-Hg anodes protected by a wire cable,( 127)
compares favorably with zinc in a 2SS-day test. According to
Schreiber and Reding( 130) the AI-Zn-Hg alloy not only has In one anode of recent development, 20 pounds of mag-
high current capacity, but reproducibility of performance, and nesium is cast over a 37S-pound anode of zind 127) This type
 80
of anode should provide higher polarizing currents during the Impressed-current anodes normally are secured to the hull,
initial period when the calcareous scale is being formed. After in the case of a ship, and may be fastened directly to a
that, the zinc takes over and maintains polarization. structure. Fewer anodes are used than would be the case with
the galvanic type. Since greater distances are involved to insure
coverage, these anodes must be driven at a higher voltage.
Impressed-Current Type. For many installations involving Thus, a shield (usually plastic), about 3 or 4 feet square, must
seawater, an impressed-current system, which requires a local be applied to the surface around the anode to avoid damage to
power source, is now preferred. In this system, direct current the paint and structure immediately adjacent to the anode.
from a low-voltage source is introduced into the seawater at a Alternatively, the anode can be mounted several yards from the
suitable distance from the object to be protected using insoluble nearest metal in the structure.
anodes of the type indicated in Table 81. An advantage of the
impressed-current anode system is that the amount of current
supplied can be adjusted to meet changing demands resulting
from such factors as velocity, resistivity, oxygen level, and
damage to protective paints.

TABLE 81. IMPRESSED CURRENT ANODES USED IN SEAWATER APPLICATIONS(l17,127,131)

Anode Description Characteristics Notes

Platinum Used as thin sheets with support, No restrictions on anode

e.g., O.OOS-inch-thick disk with current density.
a cast polyester plaster, plus
glass-fiber backing

Platinized titanium Very thin film of platinum on A current density of 100

titanium; a.aaaal-inch film, amp/ft 2 , can be em-
for example, on rod or disk ployed. Some pitting
copper core for electrical con- may occur at higher
ductivity; anode to cathode current densities
voltage about 12 volts

Platinized tantalum (Similar to above) Higher voltage can be. used

(or niobium) than with platinized titanium

Lead/Silver Dark-brown coating is formed Once coating is developed, Electrical lead attachment
to make anode "insoluble" anode must be handled can be a problem
Alloys: 93Pb-6Sb-IAg or with care. Breakage is
98Pb-2Ag a problem

Graphite Double-boiled linseed oil Chlorine and oxygen Leads are factory installed
used to impregnate graphite generated in seawater following design plans of
seems to attack installation
impregnant. Poor
mechanical properties

Silicon/Iron Brittle alloys with 14%Si, Performance variable in Ditto

3%Mo, rest Fe or 14% Si, seawater. Does better in
SCr, IMn, rest Fe brackish water than in
seawater. Poor mechan-
ical properties. Local
failure by pitting in
seawater
 81
UPDATE 1977 TABLE 82. GALVANIC SERIES FOR HIGH-PURITY
METALS(J35) (69 DAYS IN SEAWATER
AT KEY WEST, FLORIDA)
The Ocean Environment

Median Potential,
Metal Purity, SCE Reference
Factors Affecting the
Metal percent, volts
Corrosivity of Seawater
Palladium 99.99+ +0.308
The effect of oxygen concentration in seawater 011 the corro- Platinum 99.99+ +0.295
sion of 181 metals and alloys has been evaluated at the Naval
Civil Engineering Laboratory.(l32) Linear regression analyses were Titanium Iodide +0.200
performed on the results of deep-ocean tests conducted for I year (zone re fined)
at 1.5, 760, and 1830 meters depth (5.75, 0.4, and 1.35 ml 02/1 Tantalum 99.9 +0.195
seawater, respectively). The corrosion rates of the following alloys Gold 99.97+ +0.175
increased linearly with oxygen concentration in the seawater: car-
bon and low alloy steels, cast iron, copper alloys (except Muntz Columbium 99.9 +0.110
metal and Manganese Bronze A), Type 410 stainless steel, Ni-200,
Zirconium 99.9 +0.010
Monel 400, Inconel 600 and X-750, Ni-30Mo-2Fe, and lead. The
Silver 99.95 -0.025
corrosion rates of many other alloys increased with temperature but 99.99+ -0.038
Nickel
not linearly or uniformly. Many of the alloys were not corroded at (zone refined)
any of the 3 oxygen levels after I year's exposure. This group in-
cluded silicon cast irons, several 18 Cr-8 Ni stainless steels, several Silver 99.999 -0.115
Ni-Cr-Fe and Ni-Cr-Mo alloys, titanium alloys, columbium, and Copper 99.99+ -0.141
tantalum. (zone refined)
Nickel 99.99+ -0.172
The effect of aerobic marine bacteria on the corrosion of (zone refined)
metals has been studied by the University of Miami and the Office Tantalum 99.99+ -0.172
of Saline Water. (133) Specimens were exposed to untreated (zone refined)
aerated seawater from a tidal channel and to the same water passed Molybdenum 99.9 -0.173
through a Millipore filter to remove living microbiota. Corrosion
Vanadium 99.99+ -0.209
rates obtained by polarization resistance methods in these studies (zone refined)
are summarized below: Tungsten 99.9 -0.240
Bismuth 99.9 -0.248

Corrosion Rate, mils/yr Indium 99.999 -0.368

Bacteria Water Bacteria-Free Water (spectrographic
grade)
Steel 6.7 7.4 Rerun -0.525
5052 Aluminum 0.2 to 0.48 0.12toO.35 Tin 99.999 -0.671
Type 316 Stainless Steel 0.1 0.01 (spectrographic
grade)

A chemical engineer's guide to seawater has been prepared by Iron 99.9+ -0.749
the Dow Chemical Company.(134) Information in the papers on (electrolytic
seawater covers average monthly temperature and salinity at various grade)
locations off the U.S. coast, chemical composition, physical proper-
ties at concentrations varying from that of fresh water to four times Aluminum 99.99+ -1.472
normal seawater, foaming and turbidity characteristics, deposition (zone refined)
99.99+ -1.455
of solids, and marine life.
(ingot)

Forms of Corrosion

The electrochemical potentials of high-purity metals have

been determined in quiescent seawater by the Naval Research Corrosion of Carbon and Low Alloy Steels
Laboratory J 13 5) The electrochemical potentials of many metals
varied with time. Those of tin and bismuth were relatively stable in
full-strength seawater, but were less stable in dilute seawater. The Splash, Tide, and Submerged
potential for high-purity aluminum was quite negative, suggesting
that it might find application as a galvanic anode. A galvanic series, Much of the current knowledge involving the corrosion of steel
prepared based on the median of the values obtained over 69 days' piling in seawater has been presented in a literature survey prepared
exposure, is presented in Table 82. by the Army Coastal Engineering Research CenterJl37) Included
in the report are the causes of corrosion, effects of environmental
Some cavitation-erosion experiments were described on steels conditions, corrosion rates of bare steel, test results on protective
(HY 80, HY 120, and SAE 1020), aluminum alloys, and copper in coatings, the use of cathodic protection, and the use of concrete
synthetic seawater as well as distilled water. (136) Various intensi- jackets for protection. The survey indicated that flame-sprayed
ties of erosion were applied using the standard ASTM vibratory zinc sealed with Saran or vinyl is possibly the best coating system
apparatus. In general, the corrosive seawater environment increased tested; properly designed and constructed concrete jackets are very
the maximum erosion rates, decreased the exposure period needed effective; cathodic protection is also effective; and combinations of
to attain the maximum rates, and decreased the erosion strength of cathodic protection with coatings or concrete jackets may be
these materials. advantageous.
 82
The effect of alloying additions on the corrosion behavior of AISI 4340 (220 ksi yield strength) steel was selected for the above-
steel in seawater at velocities to 2 m/sec and temperatures to 20 to Klscc study while HY-80 was selected for the below-Klscc study.
55 C has been studied by Sumitomo in Japan,(138) Chromium, The former is known to be highly susceptible to stress-corrosion
molybdenum, manganese, copper, and aluminum additions were cracking, while the latter is known to have high resistance to stress-
beneficial in reducing corrosion rates. A more seawater-resistant corrosion cracking. The vacuum fatigue crack-propagation rate was
steel alloy was developed that contains 2 percent chromium and only slightly lower for the HY-80 steel than for the 4340 steel.
0.2 percent molybdenum. Compared with mild steel, this new The fatigue crack-propagation rate for 4340 steel in 3.5 percent
alloy is two times better in flowing aerated seawater and ten times NaCl was constant at frequencies lower than 0.5 Hz indicating that
bctter in flowing deaerated seawater. the environmental attack controls the crack-growth rate. On the
other hand, the cyclic crack-propagation rate of HY-80 in 3.5 per-
The use of a Monel weld inlay to extend the fatigue life of cent NaCl solution increased with decrease in loading frequency
nickel-steel propellor shafts in seawater has been studied at the from 10 to 0.1 Hz indicating an increase in environmental attack
Naval Ship Research and Development Center.(139) A Monel that was due to attack of fresh surface areas generated by the
inlaid six-foot-Iong shaft was rotated at 600 rpm at 10 ksi stress fatigue loading. Applying cathodic protection to both materials
level in Severn River water. The test facility was shut down over- increased the cracking rates above those of the freely corroding
night and on weekends, at which time there was no load on the rates, thus indicating that hydrogen embrittlement was the
shaft. but the inlaid area was covered with seawater. Fatigue mechanism of environmental attack.
failure occurred after IS ,500,000 cycles which was about normal
for a regular nickel-steel shaft and the Monel inlay, as installed, Additional fat,igue crack-propagation studies have been con-
evidently did not prolong the fatigue life of the propellor shaft. ducted by the Naval Research Laboratory in support of the devel-
opment of advanced surface ships such as hydrofoils and surfacc-
effect ships. (146) Single-edge-notch cantilever specimens of
Stress Corrosion Cracking HY-130 steel, 17-4PH steel, Ti-6AI-2Cb- ITa-0.8Mo. and 5456-
H 116 aluminum were fatigue tested in air and in seawater with and
U.S. Steel has studied the effects of prior uniform plastic without applied potentials. Both seawater and negative potential
strain (to 5 percent) on the mechanical and environmental proper- accelerated crack-growth rates in the ferrous alloys. l\either sea-
ties of HY-80, HY-130, l2Ni-5Cr-3Mo maraging steel, and 10Ni- water nor negative potential affected crack-growth rates in the
Cr-Mo-Co quenched and tempered steel. (140) Preeracked canti- titanium alloy. Seawater caused a moderate increase in crack-
lever beam specimens were used to determine KIx and KIscc growth rates in the aluminum alloy, but both negative and posi-
values in air and synthetic seawater, respectively. The results tive potentials were beneficial.
showed that prior plastic strain improved the mechanical properties
and that K Ix decreased in a consistent manner depending on the Additional corrosion-fatigue crack-propagation studies on the
yield strength and the level of strain. However, the apparent HY-130 alloy have been reported elsewhere (147) Also, the effect
KIscc value did not follow a consistent behavior pattern. The of load shedding (partial or full removal of load) on the SCC of
KIscc value of HY-80 (immune to SCC) was not affected by plastic D6 ac steel has been described.(148)
strain, while that of 12Ni-5Cr-3Mo maraging steel was increased
and those for HY-130 and 10Ni-Cr-Mo-Co Q & T were decreased
a moderate amount. Corrosion of Stainless Steels

The susceptibility of gun steel (4337 modified) to stress-

corrosion cracking has been studied at Watervliet Arsenal, using Splasll, Tide, and Submerged
precracked cantilever-beam specimens, in air at 100 percent relative
humidity. distilled water, and 3 percent NaCl solution,(141) The Additional data from the extensive Naval test program at
susceptibility to cracking increased in the order of environments Port Hueneme, California, have been reported.(149) In all. a total
given. Increasing the yield strength of the gun steel from 142 to of 1,750 specimens of 57 different stainless steels were exposed in
200 ksi increased the susceptibility to cracking. seawater at the surface and at depths of 2500 and 6000 feet in the
Pacific Ocean for times from 123 to 1064 days. Corrosion rates,
The stress-corrosion cracking behavior of cold worked A-286 type of corrosion, pit depths, and stress corrosion cracking resist-
has bcen investigated at the George C. Marshall Space Flight ance were among the parameters evaluated. Representative clata
Center. (142) No stress-corrosion cracks were detected in specimens for a selected group of these alloys are given in Table 83.
cold worked to 53 percent reduction and exposed 180 days to a
3.5 percent NaCI solution in alternate immersion testing. In general, corrosion at the surface was more severe than at
depths of 2500 or 6000 feet or in the sediments at these depths. A
The stress corrosion cracking behavior of 200 ksi yield cast Fe-23Ni-2ICr-5Mo-1Si alloy was uncorroded. Types 317 and
strength 4340 steel has been explored in a 3.5 NaCI solution under 319 were attacked only by incipient «I mil deep) crevice corro-
conditions of anodic and cathodic polarization .(143) Both sion; 20 Cb-3 was attacked by both incipient crevice and incipient
anodically and cathodically charged specimens exhibited cracking. pitting; Type 325 exhibited general surface attack; all other stain-
Time to cracking increased as t!lC specimens were made cathodic less steels investigated in the AISI 200, 300, 400, and 600 series
and decreased as the potential was made more negative. These were attacked by pitting, tunneling. and crevice corrosion ranging
results were rationalized in tenns of hydrogen liberation. from I mil in depth to complete penetration (greater than 100 mils).
Sensitization of Types 304 and 316 decreased their corrosion
In studies at U.S. Steel, precracked weld specimens of the resistance. Precipitation hardening stainless steels which failed by
HY-80 and HY-130 steels were found to be susceptible to both stress corrosion cracking included 630-H925, 631-TH 1050.
stress corrosion cracking and hydrogen embrittlement in a 3 per- 631-RHI050, 632-RHI100, 15-7AMV-Annealed, -RH950, and
cent NaCl solution whereas in the absence of a fatigue crack, -RHII50, and PHI4-8Mo-SRH950. Stainless steel wire ropes of
neither alloy was susceptible'c 144) the Type 304, 316, 18Cr-14Mn, and the Cr-Ni-Mo-Cu. Cr-Ni-Mo-
Si-N, Cr-Ni-V-N, and Cr-Ni-Si compositions were also attacked by
The corrosion-fatiguc crack-growth behavior of steels above the pitting and crevice types of corrosion.
and below KIscc has been studied at the University of Illinois.( 45 )
 83
TABLE 83. DEEP OCEAN BEHAVIOR OF water. The alloy demonstrated satisfactory stress-corrosion re-
STAINLESS STEELS(49) sistance and excellent fatigue resistance in seawater - Kri/YS was
1.38 VTr1. after 1300 hours in seawater which was a reduction of
only IS percent when compared with air values,
Exposure, Depth. Corrosion Max. Pit
Alloy Environment(a) days feet Rate, mpy Depth, mils(b)
The mechanical, corrosion, and fatigue properties of 15-5PH
201 W 366 5 0.6 0 stainless steel, Ineonel 718, and Rene 4J have been studied at the
W 402 2370 <1J.I 0
S 402 2370 <1J.1 0 Naval Ship Research and Development Center as candidates for
W 1064 5300 <1J.I 0 hydrofoil applications'c 154) Fatigue tests were conducted in
S 1064 5300 0.5 50P Severn River water on smooth specimens at 1450 cpm in fully
310 W 366 5 0.1 0
402 2370 <1J.I 0
reversed bending. General corrosion, crevice corrosion, and bent
W
S 402 2370 <1J.1 0 beam and WOL loaded stress-corrosion tests were conducted in
W 1064 5300 <1J.1 0 seawater at Wrightsville Beach, North Carolina, The 15-5PH and
S 1064 5300 <1J.1 0
347 366 5 0.7 50P
Incone! 718 exhibited crevice attack (more severe on the 15-5PH)
W
W 402 2370 <1J.1 0 and stress corrosion tests were invalidated because of specimen
S 402 2370 <1J.1 0 relaxation due to crevice corrosion. The Rene 41 did not exhibit
W 1064 5300 <1J.1 I
<1J1
any corrosion attack. No stress-corrosion failures were observed,
S 1064 5300 0
446 W 366 5 0.6 50P and two WOL specimens loaded to 59.5 and 77.6 ksi yill. showed
W 402 2370 <1J.1 0 no crack extension after a I-year exposure, Because of the diffi-
S 402 2370 <1J.I 0
<1J. )
culty in machining and welding thick sections of Rene 41 and
W 1064 5300 0
S 1064 5300 <1J.1 0 Inconel 718, the 15-5PH steel was considered the best overall
PHI4-8Mo. W 181 5 1.7,3.1 120P, 120P candidate for the hydrofoil applications.
SRH950 W 402 2370 <1J.I,0.5 1,1
S 402 2370 <1J.I. 0.3 l. 120P
W 403 6780 <1J.I, 0.4 1,1
S 403 6780 <1J.1. 0.2 1,120P Crevice Corrosion
15-7 AMY. Ann. W 402 2370 0.5 48P
S 402 2370 0.5 48P
W 1064 5300 3.0 48P The crfvice corrosion of selected stainless steels in seawater
S 1064 5300 0.9 48P has been studied by the Naval Research Laboratory.(l55) Speci-
18Cr-14Mn-0.5N W 366 5 2.6 SOP
2370
ments were tested unprotected or bolted to zinc or steel for up to
W 402 0.8,1.1 II SP, 0
S 402 2370 <1J.I. I 0, liSP 550 days in Florida tidal and pumped natural seawater. None of
W 1064 5300 <D.I.0.2 0,0 the stainless steels tested (24Ni-20Cr-6.5Mo, 26Cr-IMo. nCr-
S 1064 5300 0.3.0.4 115P,62P 13Ni-5Mn, and Type 216) was completely immune to crevice
(a) Wand S represent specimens exposed in water and partially in bottom sediment, corrosion except for several specimens of the 24Ni-20Cr-6,5Mo
respectively. alloy. Cathodic protection from mild steel or zinc protected the
(b) P designates perforated and I designates int:ipicnt. stainless steels against crevice corrosion, but edge attack and general
corrosion were observed on some of these specimens.
In another program, specimens from a 1250-foot length of
Type 304 stainless steel wire rope were examined after 34 months' Studies of the crevice corrosion of Type 304 stainless steel
continuous immersion in the Gulf of Mexico,(l50) The absence of in 3,5 percent NaCI solution indicated that intermittent applica-
corrosion on the top 1000 feet of the stainless steel wire rope was tions of cal hodic protection were sufficient to prevent crevice
attributed to the beneficial effects of a retained lubricant, to corrosion.( 156)
cathodic protection from a steel anode located above the rope,
and to probable inadvertent cathodic protection from the 6062-T6 The factors contributing to crevice corrosion of 13Cr stain-
aluminum surface buoy. Relatively severe corrosion was observed less steel in seawater have been reviewed by Soviet investiga-
on the bottom 250 feet of the rope where it was shielded from tors. (5 7) In agreement with earlier studies in the Western World,
cathodic protection because it had been jacketed with Neoprene these workers observed that no passive film fonned. and crevice
to prevent abrasion of the synthetic rope used for the lower section corrosion occurred when the dissolved oxygen content in the sea-
of the mooring system, water was 0,07 ppm or less,

The corrosion behavior of 18 Ni (180) and 18 Ni (200) In Japanese have developed a new duplex stainless steel
maraging steels in seawater has been studied by International (26Cr-6Ni-0.4Cu-3Mo plus Wand N) with improved resistance to
Nickel. (151) General corrosion rates were about half those of crevice attack in seawater'c 158) In their studies, they also have
4340 and HY-80 steels, The KIscc values in seawater were 130 developed a new laboratory crevice-corrosion test method which
and 94 ksivm. for the Ni 18 (180) and Ni 18 (200) alloys, consists of immersing the alloy in a solution of 3 percent NaC!-
respectively. 0.05M Na2S04-activated charcoal. The accelerated laboratory test
results correlated well with field experience.
The corrosion behavior in seawater of 190 ksi yield strength
I ONi-2Cr-l Mo-8Co steel has been evaluated by the Naval Ship
Research and Development Laboratory.(l52) The alloy corroded Stress Corrosion Cracking
uniformly at a rate of 6 mils/yr in a one-year test and exhibited
moderate crevice corrosion at the edge of a crevice with a maximum Stress-corrosion-cracking test results have been included in
depth of 9 mils after one years' exposure, Precracked cantilever the Battelle-Columbus evaluation of newly developed materials of
beam tests indicated a threshold stress intensity Krscc of 135 interest to the Air Force for potential weapons system
ksivrn. in seawater. usage.(l59,160) Four-point loaded beams stressed to 80 percent
of yield strength were exposed 1000 hours to 3,5 percent NaCI
In other seawater studies, the corrosion behavior of Nitronic solution under alternate immersion conditions (10 minutes in,
50 (Fe-22Cr-I3Ni-5Mn-2Mo) has been investigated at the Naval 50 minutes out). No stress-corrosion cracks were observed in 7
Ship Research and Development Center.(l53) One-inch base plate replicate specimens of each of the following materials: 15-5PH
and gas-metal-arc weldments were exposed to air and Severn River (HI025) forged bar; HP9Ni-4Co-0.20C forged bar; PHl3-8Mo
 84
(HIOOO) forged bar; 7049-T76 extrusion; Ti-6AI-2Sn-4Zr-6Mo Corrosion of Nickel-Base Alloys
sheet; Inconel 702 sheet (aged); Inconel 706 forged bar (creep-
rupture heat treatment); 17-4PH (H900) ESR bar; Udimet 710
forged bar; X7050-T7E56 hand forging; 2214-T351 (Alcoa 417 The corrosion of 22 commercially available nickel alloys in
Process) plate; and Ti-6AI-4V (DBHT) diffusion bonded quiet and low velocity (2 fps) seawater have been studied by the
component. Naval Ship Research and Development Laboratory .(172) General,
crevice, and stress corrosion were investigated in exposures of two
Additional KIscc data for high-strength steels are summarized years' duration. No stress-corrosion cracking was observed in any
in a report issued by the Naval Research Laboratory. (161) Most of the alloys (U-bend specimens). Alloys containing:> 54 nickel
data were obtained in 3.5 percent NaCI solution for I-inch plate :> 16 chromium:> 9 molybdenum were resistant to general, pitting,
with a through-the-thickness direction of crack propagation (WT and crevice attack. Other nickel-chromium-molybdenum alloys
and RT). KIscc' yield strength, and KIc or KIx data are plotted exhibited no general corrosion, little or no pitting on boldly ex-
for AISI 4340, 9Ni-4Co, 12Ni Maraging, 18Ni Maraging, and posed surfaces, and varying degrees of crevice attack. Nickel-
PH 13-8Mo steels. A limited study of specimen orientation revealed chromium-iron alloys, as well as 60Ni-19Cr-17Co and 97Ni-2Be,
little or no effect of the direction of crack propagation on KIscc, as exhibited no general corrosion, but experienced moderate to
shown in Table 84. severe pitting on boldly exposed surfaces and in crevices. General
corrosion plus moderate localized corrosion was found on 65Ni-
TABLE 84. EFFECTS OF SPECIMEN ORIENTATION WITH 27Mo, 65Ni-35Cu, 60Ni-40Cu, 45Ni-55Cu, and 65Ni-30Cu-3AI
RESPECT TO WROUGHT TEXTURE ON KIscc specimens.
OBTAINED ON PRECRACKED CANTILEVER
BEAM SPECIMENS IN 3.5 PERCENT NaCI The corrosion behavior of Multiphase Alloy MP35N (35Ni-
SOLUTION( 161) 35Co-20Cr-IOMo) has been investigated by Standard Pressed
Steel. (I 73) The alloy is an extremely noble metal with a potential
of +0.056 (versus Ag-AgCI) in seawater. It is cathodic to most
KIscc, ksi v'ii1. materials and caused galvanic corrosion of K-Monel, Type 316
RT(a) WT(a) WR(a) RW(a) stainless steel, and carbon steel in couple tests conducted in sea-
Alloy
water. No galvanic corrosion was noted in similar tests conducted
115 104 with titanium-MP35N couples. Wire-rope samples made of MP35N
9Ni-4Co-O.2C
alloy have shown no evidence of attack after 2.5 years' exposure in
18Ni-180 125 145
the mud, seawater, tidal zone, splash zone, or marine atmosphere.
12Ni-5Cr-3Mo 19 19 25
12Ni-5Cr-3Mo 70 60
The excellent resistance of Inconel 702 and 706 and Udimet
12Ni-5Cr-3Mo 105 103
710 to stress corrosion cracking in tests at Battelle-Columbus has
4340 (200 YS) II 10
been sited previously .(159,160)
(a) Convention is that of ASTM Committee E-24.
The effect of impurity additions of sulfur, phosphorus, Corrosion of Copper and Copper-Base Alloys
carbon, chromium, and silicon + manganese on the fracture tough-
ness and stress-corrosion cracking (SCC) of 18Ni (300 grade)
maraging steels have been studied in 3.5 weight percent NaCl A 5-year study on fouling and corrosion in seawater has been
solution with the following results:(l62) conducted at the Inco Laboratory at Wrightsville Beach, North
Carolina.(l74) Highly corrodible materials such as steel fouled
Fracture Resistance to readily, but the fouling could be removed easily and sloughed off
Variable Toughness SCC periodically with the corrosion product. Passive alloys such as
aluminum fouled readily, and the fouling was tightly adherent.
High-purity heat Increase None Crevice corrosion beneath the fouling caused pitting on these
«0.005C) alloys. Toxic alloys such as beryllium and lead were not completely
0.01 to 0.06 carbon Decrease Slight increase resistant to fouling. The copper alloys possessed fouling resistance
Up to 0.03 phos- None Slight increase because they formed cuprous oxide corrosion products that are
phorus additions toxic to the organisms. An overlayer of cupric hydroxychloride
0.24 chromium addition None Decrease often forms on these alloys which is not toxic and leads to fouling,
Up to 0.03 sulfur additions None None but the fouling can be easily removed. Pure copper, 90-10 Cu-Ni
Silicon + manganese Decrease None and 70-30 Cu-Ni were equally resistant to fouling. Copper alloys
additions did not provide fouling protection to adjacent materials, thus
indicating that the toxicity does not result from the release of
Five other stress corrosion cracking studies have been con- poisonous ions to the seawater.
ducted which have involved the determination of KIscc values for
stainless steels in a 3.5 percent NaCI solution. The materials in- The influence of chromium on the corrosion behavior of
volved and the respective references to these investigations are given copper-nickel alloys in flowing seawater has also been explored by
as follows: 17-4PH(163), Type 420SS(l64), AFC77 (I 65), and this same Inco Laboratory.(l75) This work showed that chromium
18Ni maraging steel'c 166, 167) Similarly, corrosion fatigue studies additions of 0.5 to 3 percent were effective for both strengthening
in seawater have been reported for 17-4PH(l68,169), 15-5PH(169), and increasing seawater velocity limitations (up to 40 m/s) limita-
and 18 Ni'c 170) tions for turbulent flow conditions without adversely affecting
other properties of this alloy system. Selected corrosion data il-
Finally, research results on the pH and analysis of the corro- lustrating this effect are given in Table 85.
dents in stress corrosion cracks of the following steels (after ex-
posure in a 3.5 percent NaCl solution) have also been re- Copper-nickel alloys for use at even greater seawater velocities
ported(l71): 0.45C, 4340, 9Ni-4Co-0.2C, 17-4PH, and the have also been evaluated by the Navy.(l76) Efforts to include
12Ni-5Cr-3Mo, 18Ni, 13Cr-9Ni-Mo maraging steels. velocities up to 120 FPS (36 m/s) resulted in new approaches and
 85
TABLE 85. SUMMARY OF PARALLEL FLOW SEA WATER crevice attack was observed. The improved perfonnance was at-
CORROSION TESTS(l75) tributed to lower temperature and lower dissolved oxygen at
depth. Carbon steel exhibited a minimum in attack at 27 meters
(0.039 g/m 2.hr) that was attributed to heavier marine growth at
Localized Atlack(a) ~ mm
this level. The corrosion of copper alloys increased with depth
Avg. Sea 3 mls 6 mls II mls IS mls
Alloy Water Temp., C (10 FPS) (20 FPS) (35 FPS) (50 FPS) (0.042 g/m 2-Ju at 80 meters) and this was attributed to the forma-
tion of nonprotective corrosion films in the absence of light.
CA-706 10 .10 .10 .08 .08
CA-715 10 .03 .03 .08 .13 A modest amount of effort in the past 7 years has been de-
IN-838 20 <.03 .03 .10 .13 voted to laboratory studies of the stress corrosion cracking of
Cu-70Ni-3Cr 10 <.03 <'03 <.03 <.03 various titanium alloys in the presence of either seawater or a 3.5
percent NaCl solution. The Ti-6AI-4V alloy has received most of
(a) 30 day exposures. the attention with individual studies being reported on the effects
of specimen thickness(l78), sample orientation(l79), and heat
treatment( 180) on stress-corrosion cracking behavior. Similar
a reassessment of available test techniques. Four different test
stress-corrosion cracking studies have also been reported for the
techniques were employed, including two rotating specimen tests,
Ti-6A1-6V-2Sn(l79), Ti-3Cu(l80), Ti-7AI-2Ib-ITa(l81)_ and
one impingement, and one multivelocity jet tests. Some of the
Ti-8AI-8Mo-2Fe-3AI( 182) alloys.
results are summarized in Figure 99 which illustrates the benefit
of iron and chromium additions to copper-nickel in increasing their
The fatigue crack growth of Ti-6AI-2Cb-1 Ta-0.8Mo alloy in
resistance to corrosion-erosion and impingement damage.
air and natural seawater has been investigated at the Naval Research
Laboratory .(183) Single-edge-notched (SEN), side-grooved speci-
mens were tested in zero-to-tension loading. The alloy showed no
evidence of environmental sensitivity on fatigue cracking in sea-
water at its free corrosion potential or at cathodic-protection
potentials of -800 or -1050 m V versus Ag/ AgCI reference cell.
The fatigue crack growth rate of this alloy was later compared with
110 that for several other high strength alloys in follow-on work by this
same laboratory.(l84) Environments were seawater at the free
100
corrosion potential and several hundred millivolts more negative
90 than the free corrosion potential. Compared with results in air:

~ 80 • Seawater or negative potential had no effect

~
on Ti-6AI-2Cb-ITa-0.8Mo (114.5 ksi YS)
OJ 70
a
a: 60 • Deleterious effect of seawater and no effect
c
.2 of negative potential on 17-4PH VM steel
<f> 50 (153.6 ksi YS)
~
~

<340
• Deleterious effect of seawater and negative
30 potential on 17-4PH OAM steel (135 and
163 ksi YS)
20

10 • Deleterious effect of seawater and negative

potential on HY-130 steel (147.2 ksi YS)
oL:=e§~~~J:::::CL:ZJ
o 10 20 30 40 50 60 70 80 90 • Deleterious effect of seawater and beneficial
Seawater Velocity, fps effect of negative potential on 5456-H 116
aluminum (31.1 ksi YS).
FIGURE 99. RESULTS OF MULTIVELOCITY AND
HIGH VELOCITY JET TESTS ON The excellent resistance to SCC of the Ti-6AI-4V and
COPPER AND COPPER ALLOYS(176) Ti-6AI-2Sn-4Zr-6Mo alloys has been cited previously.(159, 160)

CA706: Cu-IO.6Ni-1.5Fe-0.44Mn
CA715: Cu-31.4Ni-0.6Fe-0.72Mn Corrosion of Aluminum Alloys
CA716: Cu-29.6Ni-5.4Fe-0.08Mn
CA717: Cu-32.6Ni-0.75Fe-0.55Mn-0.58Be
CA719: Cu-29.7Ni-0.2IFe-0.58Mn-3.ICr Atmosphere, Splash, Tide,
and Submerged

Corrosion of Titanium and Titanium-Base Alloys Seven aluminum alloys and panels of high-purity aluminum
were evaluated after exposure for ten years in seawater at Wrights-
ville Beach, N.C. in half-tide immersion and full immersion.(l85)
The corrosion of several alloys at various depths (7, 27, 42, All panels were heavily fouled with barnacles and other marine
and 80 meters) in the Black Sea has been reported by Russian growth for all exposure periods. The fouling had little apparent
scientists. (177) Titanium was resistant at all depths with a cor- effect on the pitting depth of the aluminum in tidal immersion, but
rosion rate of <0.00Igjm 2-hr. 18Cr-9Ni stainless steel pitted generated heavy etching on some alloys during the 5 to 10 year
(2.8 mm deep after 21 months of exposure), but corrosion per- exposure interval.
fonnance improved with depth, and at 80 meters, only slight
 86
Little change in tensile properties after ten years' exposure was when the alloy was coupled to 90-10 copper nickel, yellow brass.
noted for any of the test alloys. Tensile losses reported for several Type 304 stainless steel, or mild steel. The galvanic corrosion
alloys after full immersion include: 5086-0 (3'.7 percent), 5154- could not be completely prevented by cathodic protection. The
H38 (5. I percent), and 5457-H34 (5.2 percent). The high-purity 6061-T6 aluminum was severely corroded when immersed in
1199 and alloys 5154-H38, 5456-0, and 5456-H321 showed losses quiescent seawater or Potomac River water. The best overall pro-
of 16 to 27 percent in elongation while the change in elongation for tection to both aluminum alloys was a vinyl anti,'u!Tosive harrier
the 5086-0 was a decrease of about 6 percent. with a tributyl tin toxicant (for antifouling.) and cathodic
protection.
Confirming otlJer work, the corrosion rates were found to be
greater for the full seawater immersion than for the tidal immer- Corrosion, stress-corrosion. and corrosion fatigue have been
sion. The lowest ten-year corrosion rate in the half-tide location determined by Alcoa for fifty-one lots of 7050-T76 sheet, 7050-
was 0.014 mpy (mils per year) and the 5456-0, and the highest rate T73651 plate, 7050-T73652 hand forgings. 7050-T736 die forgings.
for the aluminum-magnesium 5000 series was 0.051 mpy for the and 7050-T76511 extruded shapes.(i89) All products showed a
5456-H321 alloy. In full-immersion tests, the lowest rate was high order of resistance to exfoliation in accc'lcratcd corrosion
0.064. For comparison, the rates for the 1199 alloy were 0.036 tests. No stress-corrosion cracking (sec) failures occurred in
mpy in tidal and 0.061 mpy in full immersion. Corrosion weight tensile specimens of sheet, plate, and hand forgings in tests to
losses and depth of pitting had reduced rates of growth over the 60S days in a seacoast atmosphere and to 763 days in an industrial
interval between five years and ten years. Maximum depth of atmosphere. SCC failures have occurred in four of ten 7053-T736
pitting for an alloy was generally at least four times the magnitude die forgings stressed at 35 ksi and two of four 7050-T76511 ex-
of average of the twenty deepest pits. Maximum pitting depths truded shapes stressed at 25 ksi. In the industrial atmosphere, only
for each of the materials tested in half-tide and full immersion are one specimen of a die forging failed at 45 ksi. Fatigue crack propa-
given in Table 86. gation in humid air and salt fog tended to be two or three times
that in dry air. The fatigue strengths of the 7050 plate, hand
TABLE 86. PITTING BEHAVIOR OF ALUMINUM ALLOYS forgings, and extruded shapes were about the same in salt fog, but
AFTER 10 YEARS EXPOSURE(l85) were somewhat lower than values reported for 7475-T761 sheet,
2124-T851 plate, and 7049-T73 and 7175-T736 hand forgings.

Half-Tide Exposure Full Immersion

Max. Pit Max. Pit Galvanic Attack and Velocity Effects
Alloy Rating(a) Depth, mils Rating(a) Depth, mils
Galvanic couples of Alodine 600 coated 7075. 6061. or
5154-H38 5 19.5 2-1/2 15.2 2024 aluminum to Ti-6AI-4V or Type 304 stainless steel have been
1199 4 39.0 2-1/2 12.7 studied at Rockwell International Science Centcr( 190) Calvanic
5457-H34 I 22.0 2-1/2 12.0 corrosion current and weight-loss data were obtained in 3.5 percent
5086-0 2 27.0 2-1/2 18.1 NaCI solution at room temperature. The Adoline 600 coating
5083-0 6 38.0 5 24.0 greatly reduced the dissolution rates of the aluminum alloys.
5454-H34 3 19.9 6 20.0 Damage to bare or coated aluminum alloys was greater when
5456-H321 8 72.0 7 45.3 coupled to the Type 304 stainless steel. Dissolution rates obtained
5456-0 7 68.5 8 131.0 from galvanic current data were lower than those calculated from
weight-loss data. However, with appropriate correction factors.
(a) Based on average of 20 deepest pits; number I is best. the continuous recording of galvanic current data could be used
to obtain instantaneous corrosion rates which could be used to
Additional marine corrosion behavior on three of these same extrapolate to long-term rates.
alloys (5086,5083, and 5456) in the Hl16 and Hll7 tempers
have also been reported.(l86) Panels were exposed for 2 years to In later work by the same laboratory the galvanic corrosion
the marine atmosphere, at the splash and spray zone, and fully behavior of 1100, 2024, 2219, 6061. and 7075 aluminum alloys
submerged in seawater at Wrightsville Beach, North Carolina. No coupled to copper. Type 304L stainless steel. Ti-6AI-4 V. 4130
exfoliation attack occurred on any specimen, although some slight steel, or zinc were studied.c 191) Electrochemical- and weight-loss
pitting and edge attack were observed. Aging the H-I16 and H-117 data were obtained in several environments. In 3.5 percent NaC!.
tempers I week at 100 C prior to exposure caused increased pitting the dissolution rates of aluminum alloys in couples decreased in
and edge attack but did not appear to pose a long-term corrosion the order of copper> 4130 steel> 304L > Ti-6AI-4V.
problem.
The effect of velocity on the seawater corrosion behavior
The effect of exposure conditions on the corrosion of 6061-T6 of high-performance ship materials has been studied by Bell Aero-
aluminum in seawater has been studied by the Naval Research Lab- space and Ocean City Research.O n ) A water wheel was used to
oratory.(87) Specimens exposed 730 days under a pier at Key obtain velocities to 90 knots in ambient seawater. General corro-
West, Florida, exhibited random shallow pitting not associated with sion rates of aluminum alloys 5086-HI17 and 5456-H117 were
intentional crevice areas. In laboratory static corrosion cells and in less than 0.1 mpy at zero velocity and increased to about .12 mpy
a flume at 3/4 fps velocity, corrosion in the intentional crevice was at 90 knots. The general corrosion rates for Inconel 625, 17-4PH
far more severe than on the exposed surfaces. Attack in the crevice stainless steel, and Ti-6AI-4V were less than 0.1 mpy at zero
was severe for the flume specimens which were found to be com- velocity and increased to 0.5 to 1.5 mpy at 90 knots. The galvanic
pletely penetrated (0.16 cm) after 730 days of exposure. corrosion rates of the aluminum alloys were less than 0.6 rr.py at
zero velocity and increased to as high as 59 mpy at 90 knots.
The results of corrosion studies with 5086-H32 and 6061-T6 Coupling to Ti-6AI-4V had less effect on the galvanic corrosion
aluminum alloys in seawater and in the Potomac River have been of the aluminum than did coupling to 17-4PH or Inconel 625.
reported.(l88) Exposures ranged to 3.5 years. The 5086-H32
alloy was corrosion-resistant to both waters. Severe galvanic In an extension of this work, the relationship between elec-
corrosion occurred in both waters (Potomac River was most severe) trode potential and the velocity of seawater on the pitting behavior
 87
of aluminum alloys has been reported in a paper jointly prepared hardenability than the 7175 control and exhibited equivalent or
by Bell Aerospace Textron and Ocean City Research Corpora- better resistance to stress-corrosion cracking. The alloys with the
tion.(l93) Aluminum alloys 1100 and 5456-H117 were exposed optimum combination of properties contained
to seawater velocities ranging from 0 to 60 knots. Potentiostatic
techniques were used to obtain critical pitting potentials, protec- Element Percent
tion potentials, and corrosion potentials. The results indicated that
all three of these potentials became more active (negative) as velo- Zinc 5.75 to 6.25
city increased except for a discontinuous shift in the noble (posi- Magnesium 2.0 to 2.5
tive) direction between 15 and 30 knots. The extent of pitting Copper 2.lt02.6
decreased with increasing seawater velocity. Zirconium 0.09toO.15
Silicon 0.10 max
Iron 0.12 max
Stress Corrosion
The culmination of this effort was the development of Alcoa's
A modest effort has been exerted over the past 7 years in MA 15 alloy. (199) This material has longitudinal yield strength of
obtaining a better understanding of stress corrosion cracking of 61 ksi and good resistance to stress-corrosion cracking at 25 ksi
the 2014(194,195), 2024(194,196), and 6061(194) alloys in sea- stress in the short transverse direction, based on 30 days' exposure
water and saline solutions. A Navy study on forgings of all three in the 3.5 percent NaCl alternate immersion test. The alloy with
of these alloy plus 7075 is representative of these programs.(l94) optimum strength and stress-corrosion resistance contains 5.5 to
In this work, smooth and precracked cantilever beam specimens 6.5 zinc, 1.9 to 2.4 magnesium, 2.25 to 2.75 copper, 0.08 to 0.14
were exposed to natural sea water. The KIscc values for the short- zirconium, 0.12 maximum iron, 0.10 maximum silicon, and 0.04
transverse orientation of these specimens were: maximum titanium. However, long-term tests (84 days) in 3.5
percent NaCI produced erratic results, and caution was recom-
Alloy Forging Size, inches KIscc ksi vm: mended in evaluating this alloy until the results are obtained for
long-time atmospheric tests. The corrosion and mechanical proper-
6061-T652 9 x 24 x 24 24 ties of three tempers of commercially fabricated 1- to 6-inch plate
6061-T652 6 x 12 x 24 26 of this alummum alloy (MA 15) have been evaluated by Alcoa in
2024-T352 6 x 12 x 24 23 later property comparisons of this alloy with 7075-T651, 7075-
2024-T852 6 x 12 x 24 14 T7351, 7079-T651. and 2024-T351,(200) Compared at equal
7075-T7352 6 x 12 x 24 18 strengths, the MAI5 alloy developed higher resistance to exfolia-
2014-T6 8xl6xl9 16 tion corrosion and stress-corrosion cracking, higher toughness, and
better fatigu(' performance than the established commercial alloys.
In general, the alloys with low KIscc values failed early in the Compared at equal resistance to stress-corrosion cracking, MAI5
smooth-specimen tests. Notable exceptions were the smooth speci- developed higher strength than the established commercial alloys.
mens of 2024-T852 which appeared to outlast 2024-T352. even
though the latter had a higher KIscc value. Earlier, the mechanical, fracture, fatigue, and stress-corrosion
properties of a Boeing-recommended aluminum alloy (Alloy 21)
However, most of the emphasis in recent studies on SCC in had been evaluated by Boeing,(201) The alloy contains 6.4 zinc.
aluminum alloys has been centered on the high strength 7000 series 2.5 magnesium, 1.1 copper, 0.13 iron, 0.10 manganese. and 0.13
alloys, particularly of the 7075 type. In 1972, for example, Alcoa zirconium. A T6 + 35 hour at 325 F heat treatment achieved a
published the results of studying the effects of alloying additions 25-ksi short-transverse stress-corrosion threshold for smooth speci-
or substitutions on the SCC behavior of this prominent AI-Zn-Mg- mens. The mechanical properties of the Alloy 21 were comparable
Mn alloy's composition.(l97) to those of 7049-T73. The fracture toughness was as good, or
better than, that of other high-strength aluminum alloys. The
Short-transverse constant-strain tensile specimens were ex- smooth and notched-axial (tension-tension) fatigue properties were
posed to the alternate immersion 3.5 percent NaCI test and to the comparable to those of 7075-T6 and 7075-T73.
industrial atmosphere at New Kensington, Pennsylvania. The
effects of the various additions are summarized below: Two other extensive evaluation programs have been reported
which included exposure of high strength aluminum alloys in
Stress-Corrosion marine atmospheres. One of these included studies of exfoliation
Element Resistance Strength corrosion and SCC of the 7075-T6, -T73, 7078-T7, and 7178-T6
compositions.(202) The other was concerned with determinations
Silver Marginal Increase No Increase of the SCC of 7075,7475,7050, and 7049 alloy plates in several
tempers. (203)
Zirconium or man- Decrease Increase
ganese substitu-
Corrosion fatigue and fatigue crack growth in aluminum
ted for chromium
alloys in seawater and saline solutions have also been the object of
Increased zinc Increase study in four other programs. Two of these were devoted to the
5456-H117(204) and 7075(205) alloys exclusively. Another
Increased copper Increase Increase
program(206) covered the 2024 and 7075 alloys in several tempers
in chromium free alloys
while the fourth program(207) embraced the 2014, 7075, 7079,
X7080, and CH70 compositions.
In another program, aimed at the development of a high-
strength aluminum alloy with improved resistance to SCC in short Finally, Alcoa has reported the results of a 4-year study on
transverse direction, the alloys studied included a 7175 control and comparing stress-corrosion cracking behavior using fracture me-
variations of 5.8 to 7.4 percent zinc, 2.0 to 2.5 percent magnesium, chanics techniques and conventional smooth specimen proced-
and 2.1 to 2.7 percent copper, with either separate or combined ures.(208) Commercial plate and rolled or forged bars 2 to 2.5
additions of zirconium, manganese, and chromium.(l98) All the inches thick of 13 aluminum alloys, 13 precipitation hardening
alloys developed more attractive combinations of strength and stainless steels, and 2 titanium alloys were studied. Bolt loaded
 88
precracked compact tension specimens and axially loaded smooth water line for attaching each of the following materials to itself or
tensile specimens were exposed to 3.5 percent NaCI (alternate to any of the other materials: wood, fiberglass, rubber, plastic
immersion), a seacoast atmosphere, and an inland industrial atmos- (Nylon), aluminum, steel, galvanized steel, copper, brass, nickel,
phere. Aluminum specimens with a low threshold stress for smooth stainless steel, and Monel.
specimens also exhibited a low threshold stress-intensity factor
KIscc for precracked specimens. Similar correlation was found
for high threshold stress levels and high KIscc' However, most of Corrosion of Composites and Miscellaneous Materials
the precipitation hardening steels and the titanium alloys exhibited
a low KIscc and high SCC growth rate even though the threshold
stress level for smooth specimens was high. The saltwater corrosion behavior of aluminum graphite com-
posites has been studied by the Aerospace Corporation. (213)
Exposed to 3.5 percent NaCI were aluminum/graphite and
Corrosion of Fasteners aluminum/boron composites, AZ31B magnesium, A356 aluminum,
and these two alloys coupled to block graphite or 4340 steel. Based
on test results, the corrosion performance of the alloys was rated
In studying hydrofoil craft, the Naval Ship Research and as follows (l is most resistant, 4 is least resistant):
Development Center has investigated the seawater corrosion of
fasteners installed in various structural materials.(209) Seven bolt (l) A356 aluminum alloy
materials were inserted in five panel materials with and without a Aluminum/boron composite
sealant (Coast Pro-Seal 800-B-2). The bolt materials were 2024
aluminum, ASTM Grade 5 steel, Types 304, 316, and A-286 (2) Aluminum/graphite composite
stainless steels, MP35N Multiphase, and Ti-6AI-4V. The panel (3) A356/4340 couple
materials were fiberglass, 5456-H117 aluminum, HY-130 steel, A356/graphite couple
Ti-6AI-4V, and 17-4PH stainless steel. Specimens were completely
immersed in natural seawater at Wrightsville Beach, North Carolina, (4) AZ31B magnesium alloy
commencing in June, 1974. The MP35N and Ti-6AI-4V bolts did AZ31 B/4340 couple
not corrode in any structure tested. Unpainted steel fasteners AZ31 B/graphite couple.
corroded, bare aluminum fasteners pitted, and bare stainless steel
fasteners exhibited crevice corrosion. Sealant was required in the The aluminum/graphite couple exhibited a slightly greater corrosion
fiberglass panels to minimize crevice corrosion and on the rate than the A356 aluminum presumably because of the galvanic
aluminum and steel panels to minimize galvanic corrosion. Sealant coupling effect. Boron is nonconductive and, thus, produced no
was not necessary to minimize corrosion in the titanium panels. galvanic effects in the aluminum/boron composite.
Sealant was detrimental in 17-4PH stainless steel panels, apparently
because it produced a tighter crevice and increased the severity of The galvanic corrosion of aluminum coupled to graphite-
crevice attack. epoxy composite materials has also been studied at the Naval Air
Development Center.c 214 ) Electrochemical measurements in 3.5
The results of the third and fourth years' program to develop percent NaCI solution revealed a I-volt potential difference between
a full temperature range (-65 to 325 F) protective system for the graphite-epoxy and 7075-T6 or 7075-T651 aluminum and
fastener areas of carrier-based Navy aircraft have been reported by 0.3 volt difference between the composite the Ti-6AI-4V. Cor-
Lockheed-Georgia. (210) Screening tests on coating systems in- rosion current measurements showed that aluminum alloys,
cluded thermal stability at 350 F, tensile and elongation properties cadmium plate, and cadmium plate plus chromate conversion coat-
at -65 F, bend and impact tests on coated panels at -65 F, and sea- ing are much more reactive than Ti-6AI-4V when coupled to the
coast exposure of coated panels. Final evaluations were based on graphite-epoxy composite. Posttest tensile results after 2 weeks of
fatigue tests that simulated five cycles of simulated flight spectrum exposure to salt spray and synthetic seawater +S02 spray indicated
on coated titanium and aluminum specimens which had a typical significant strength losses in graphite-epoxy-aluminum honeycomb
aircraft joint with eight fasteners. The most effective coating com- structures, but little or no loss if the composite were made without
binations were three-layer systems composed of MIL-P-23377 the aluminum. Galvanic coupling the graphite-epoxy composite
epoxy-polyamide primer, an aliphatic linear polyurethane topcoat to 7075-T65I aluminum had no effect on the stress-corrosion
and intermediate coats of elastomeric polyurethane or inhibited cracking of the alloy but did increase its general corrosion rate.
polysulfides. These systems were applied to A-7 carrier-based Navy
aircraft in 1975 and will be inspected periodically for 3 years. Information on the deterioration of materials and undersea-
system components in seawater is compiled in a report issued by
The corrosion behavior of high-strength fastener materials the Naval Research Laboratory.c 215 ) Materials included are metals,
has been evaluated by Standard Pressed Steel. (211) The behavior plastics and composites, ceramics, paper, and natural fibers. Com-
in crevices, stress-corrosion cracking, hydrogen embrittiement, and ponents included photographic materials, magnetic tape, electronic
the simulated service environment was compared for some but not components, propellants, and explosives.
all material combinations. The materials (and minimum tensile
strengths) were: Custom 455 (220 ksi), PH13-SMo (220 ksi),
PHI2-9Mo (220 ksi), Incone! 718 (220 ksi), Hli (220 and 260 Corrosion of Coated Structural Metals
ksi), Multiphase MP35N (260 ksi), and Marage-300 (260 ksi). In
general, the results showed that the ferrous alloys were susceptible
to crevice corrosion, the alloys were not very susceptible to stress- Coatings for Steel
corrosion (bolts torqued to 75 percent of yield and exposed to
3.5 NaCl alternate immersion), and hydrogen embrittlement could Coated, unscored steel panels prepared by the Wisconsin
be a problem. Protective Coating Corporation were exposed 2 and 7 years in the
atmosphere, splash zone, half submerged and fully submerged in
Corrosion-resistant fastener selection for marine applications a partially shielded area south of Long Island, New York9 16 ) Of
has been described in an article prepared by ITT Harper.(212) the primers studied, inorganic and organic zinc primers were ef-
Tabular data are presented for fasteners to be used above or below fective at 2-1/2 to 3-1/2 mils thickness; the optimum thickness
 89
of organic epoxy-type primers was 8 mils; and vinyl primers were 302,303, and 304 stainless steel.
suitable only for vinyl systems. The projected film thickness
needed for ten-year life in this area was 2-1/2 to 3-1/2 mils of in- The maintenance painting of steel structures for underwater
organic zinc primer without topcoat for atmospheric exposure and splash zones has also been reviewed by Oriska and
100 and 1000 feet from the shore. In other systems the recom- Brouillette. (220)
mended thicknesses were:
Electroplated chromium-over-nickel coatings on steel have
been tested at and near the coast and in a rain forest in the Panama
Thickness. mils Canal lone.! 221) After 9 months' exposure at the tropical marine
System Atmospheric Splash lone Immersed site, coatings 40 microns thick provided effective protection while
those 20 microns thick did not. After 35 months' exposure only
Epoxy (chalking) 10 12 10 40 micron-thick coatings protected against severe attack of the base
Vinyl and vinyl 7 9 7 metal.
acrylics
Diffusion coatings for improving the seawater erosion resist-
2-1/2 to 3 mils ance of steel and other metals have also been studied.(l22) The
zinc-rich primer 7 7 7
diffusion coatings were applied by the molten salt electrolytic
plus topcoat (topcoat) (topcoat) (topcoat)
process as indicated below:

Beryllium into: Monel, nickel, 10 18 steel, copper,

Grit blasting to near white metal was sufficient surface preparation cupronickels. Cu-6AI
for these systems.
Boron into: Nickel, 4340 steel, 10 18 steel. and
line coatings on steel have also been evaluated in the marine 1018 coated with nickel electro-
atmosphere at the NASA Kennedy Space Center and by Metco. deposit or molybdenum spray
The NASA program compared the results of an 18-month exposure
of fifty-nine commercially available zinc-rich coatings and forty- Chromium into: 4340 steel, 1018 steel.
seven topcoat materials as applied to carbon steel. (217) The in-
organic (Type I) classes of zinc-rich coatings were far superior to The erosion tests were carried out in synthetic seawater using an
the organic (Type II) classes in the seacoast atmosphere. The inor- ultrasonic horn at 20 kc and I mil displacement to produce cavita-
ganic coatings were effective at 3-mil film thickness whereas 4 to tion. Only the beryllium coatings on the copper-base alloys showed
6 mils was required for the organic coatings to survive 12 months' good resistance to erosion. Their performance was comparable
exposure. Topcoat systems adversely affected the performance of with that of Alloy 718 and superior to that of Type 316 stainless
the zinc-rich systems. Panels sheltered from the environments steel,
deteriorated at about the same rate as unsheltered panels.

The Metco work covered 18 years of testing of flame-sprayed Coatings for Aluminum Alloys
zinc and aluminum (sealed and unsealed) on low carbon steel
panels exposed to sea water at mean tide and below low tide Six different experimental claddings for corrosion protec-
levels at two different locations'(218) Panels were also exposed tion of 7075-T6 aluminum have been studied bv the Air Force
to atmospheric conditions at six different locations including rural, Materials Laboratory.(223) Claddings tested we're 1199. 5457,
industrial, salt air and salt spray environments. 7004,7039,7072, and 7472 aluminum. Exposures were conducted
for periods of up to 24 months in tropical, semitropical, and inland
The results were consistent with the above described exper- industrial sit"s at Panama, Cape Kennedy. Florida, and McCook.
iences and indicated that low carbon steel can be protected from Illinois, respectively. Cladding alloys 1199 (99.99 AI). 5457 (0.9
the corrosive effects of these environments for eighteen years or Mg), 7004 (4.4 In. 1.7 Mg. 0.3 Mn. 0.14 Cr). and 7472 (1.6 In.
more by the application of flame sprayed zinc or aluminum 1.2 Mg) were superior from a corrosion standpoint to the 7072
coatings. alloy now in use. Alloy 1199 had the best overall corrosion per-
formance and alloy 5457 was a close second.
Seven different paint coating systems were tested on structural
steels, high-strength stainless steels, and aluminum alloys in the Sea atmosphere corrosion experiences have also been described
deep Pacific and Atlantic Oceans.(219) The Pacific specimens were for the Alclad 2024-T8l (224) and Alclad 7050-T76(225) alloys.
placed on the bottom in 5900 ft of water for six months while the
Atlantic specimens were on the bottom at 4050 ft for more than Lockheed-Georgia also has investigated a variety of organic
four years. coatings for improving the resistance of aluminum to stress-
corrosion cracking.(226) Alternate immersion tests were conducted
The epoxy paint system provided good to excellent corrosion in 3.5 percent Nael on tensile specimens coated with acrylic and
protection at both test locations. butyl rubber. polysulfides, aluminum foil, polyester film, and
polyurethanes. A three-layer system composed of an inhibited
The inorganic zinc coating provided adequate protection to polysulfide primer, aluminum foil or Mylar intermediate coat,
the steel specimens for six months in the Pacific Ocean, but would and an aliphCltic linear polyurethane topcoat prevented SCC for
have to be at least 0.0 I 0 to 0.020 in. thick to be effective for up 24 months in the test media but was considered impractical because
to one year. of difficulties associated with applying the intermediate films of
aluminum or Mylar. Substitution of an elastomeric polyurethane
The two stainless steels Almar 362 and Carpenter 455 were for the intermediate coat resulted in a more practical system that
highly susceptible to crevice corrosion when not coated. Uncoated provided protection for more than 10 months in the 3.5 percent
specimens suffered from crevice attack in the same manner as types NaCI solution
 90
Desalination Experiences most effective method of preventing corrosion. This procedure
greatly lowered the magnitude of the attack, but did not com-
pletely eliminate corrosion. Conventional inhibitors were not en-
As noted earlier, this section on Desalination Experiences was tirely effective in eliminating attack on the aluminum when coupled
a new feature of Update 1977. This is not meant to imply that to Monel 400.
DMIC Report 245, "Corrosion of Medals in Marine Environments",
omitted mention of desalination applications for metals. Rather,
in the earlier report these experiences were presented separately Carbon and Low Alloy Steels
in the various sections dealing with the individual metals and
alloys, e.g., seawater distillation experiences with copper alloys The Dow Chemical Company has issued a summary report
were described in the "Submerged, Heat-Exchanger-Corrosion" on corrosion studies conducted for the OSW that were related to
section under "Copper and Copper-Base Alloys". the desalination of seawater.(230) Among the results of the study
are: the pitting tendency for stainless steels is suppressed at sea-
One important event since the issuance of DMIC Report 245 water pH greater than 6.7; aluminum alloys pit in 220 F high salin-
was the publication of a very extensive bibliography covering de- ity seawater at pH 6.1 but not at pH 7.0; 15 to 20 ppm bicarbonate
salination experiences over this earlier time period. Thus, from seawater alkalinity increases the pitting and corrosion resistance of
December, 1968, through June, 1972, the Oak Ridge National aluminum alloys, but an 8-ppm bicarbonate level gives only partial
Laboratory prepared and issued a 15 volume set of an indexed pitting resistance; mild steel, COR-TEN, and Copper Alloy 122
bibliography on the corrosion and performance of materials in show acceptable rates in aerated softened seawater at pH 9 to 9.5
saline water conversion processes. Each volume carries an identical and 290 to 320 F. The report also describes techniques and appar-
title, differing only by the volume number927) The volumes atus to study pitting, determine bimetallic corrosion rates, deter-
contain abstracts for 870 publications taken from the computerized mine critical velocity, determine heat-transfer coefficients, analyze
storage and retrieval system for the Materials Information Center of dissolved oxygen and carbon dioxide, and determine total alkalinity
the Office of Saline Water. The abstracts are grouped in 33 cate- in seawater.
gories relating to the various stages and aspects of saline water
conversion. Because of their vintage, no effort was made to incor- An earlier Dow report described similar evaluations on a var-
porate information from any of these 870 references into this iety of other types of steel and some aluminum alloys. (231) It was
review. Rather, Update 1977 has concentrated on desalination shown that the corrosion performance of copper-bearing steel
experiences since June, 1972, which are summarized in the para- (ASTM A-242) was about 30 percent better than that of mild steel.
graphs which follow. Both of these steels performed well with 5 ppb oxygen in the sea-
water, but had high corrosion rates with greater than 100 ppb
oxygen in the water. Steels containing 4 to 8 percent nickel and
Galvanic Attack 3.5 percent chromium also exhibited high corrosion rates in hot
water containing 125 ppb oxygen, but were not tested at the
The potentials of sixteen metals in aerated seawater at 30 to lower oxygen levels. The pitting and crevice corrosion behavior of
200 C (86 to 392 F) have been determined at the Rosenstiel School wrought stainless steels were not consistent; preliminary ratings of
of Marine and Applied Science'(228) In general, all metals became stainless steel types in descending order of merit were: 316, 304,
more electronegative as the temperature was increased. The most 409, and 430. Cast stainless steels CF-8, CF-8M, and CA-15 showed
active metals at 30 C were carbon steel, aluminum alloys, and zinc. highly localized attack with 125 ppb oxygen in the water, but had
At 200 C, carbon steel shifted to more noble potentials leaving only greatly improved performance with 5 ppb oxygen in the water.
aluminum and zinc in the most active group. The galvanic series
for these metals in aerated seawater at 200 C was in the order Additional studies at Dow compared the performance of
(positive to negative): carbon, low alloy, Alloy 20, Type 304 and Type 311 steels, alum-
inum alloys, and copper alloys'(232) Oxygen was the primary
(I) Inconel625 cause of attack in all alloys studied. Low-alloy steels were better
(2) Titanium-6AI-4V than mild steels, particularly at high velocities. Attack rates on the
(3) Hastelloy C steels doubled between 82 and 120 C (180 and 250 F). Aluminum
(4) 316 stainless steel alloys were unaffected by oxygen under I ppm and temperatures to
(5) Monel K-500 120 C had no effect, but they were sensitive to galvanic, velocity.
(6) 70-30 Cu-Ni and scavenging effects (plating out of heavy metal ions).
(7) CDA 194
(8) 90-10 Cu-Ni
(9) Aluminum Brass Stainless Steel
(10) Arsenical Admiralty Brass
(II) Yellow Brass Electrochemical and in-plant corrosion studies have been made
(12) Nickel 270 by Westinghouse on ferritic stainless steels for use in desalination
(13) 1016 Steel plants,(233) The results revealed that many high-purity stainless
(14) 1100 Aluminum steels are resistant to deaerated seawater at 250 F (120 C). How-
(15) 5086 Aluminum ever, as the dissolved oxygen content of the water was increased.
(16) Zinc. the chromium-plus-molybdenum concentration of the steels had to
be increased to maintain adequate corrosion resistance. Ferritic
The corrosion in closed seawater systems of aluminum-base stainless steels containing 21 to 23 weight percent chromium and
alloys coupled to Monel 400, brass, titanium, and stainless steel 3 to 5 weight percent molybdenum were resistant to 250 F sea-
has also been investigated by scientists from Battelle-Columbus, water containing 200 to 500 ppb dissolved oxygen.
Pennsylvania State University, and the Environmental Protection
Agency.(229) Galvanic corrosion of aluminum in aerated seawater The corrosion behavior of austenitic stainless steels in Baltic
was severe when coupled to Monel 400, less severe when coupled seawater (3200 to 3900 ppm chloride) has been studied in
to hard anodized aluminum, and least severe when coupled to Sweden'(234) Tests were conducted for times up to two years
titaniurTIorstainless steel. The removal of dissolved oxygen was the on tubes in heat exchangers in a test loop at 50 C (122 F) and
 91
0.1 and 10 meters/sec (0.33 and 33 feet/sec) velocity. Pitting was • Silicon bronze bolts are susceptible to corrosion/erosion
observed wherever there were crevices. All unwelded, fully exposed where falling water droplets impinge, and the attack is
specimens were resistant at both water velocities. A study devoted aggravated by sulfides in the water
specifically to the effect of seawater on the corrosion behavior of
Type 304 stainless steel at elevated temperatures has also been • Sulfides from polluted water or process leakage cause
reported.(235) severe corrosion of copper-base alloys

Designing with stainless steels for service in a variety of sea- • Sulfides can be countered by use of oxidizing biocides
water environments has been discussed in a paper by Moller of the such as chlorine or hypochlorite which oxidize the sulfides
International Nickel Company.(236) Conditions conducive to the to less corrosive sulfates.
stress corrosion cracking of the various kinds of stainless steels
are described. Nineteen case histories of SCC failures are described • Pitting of Type 316 stainless steel in crevice areas where
in applications that include boilers, steam lines, salt-water conden- poor cleanliness or microbiological control is maintained
sers, sour-water heated reboiler, bolts in a distillation column, and excellent perfonnance in well-aerated portions.
MEA reboilers, and a seawater desalination plant.

Sandvik Corporation in Sweden has developed a stainless Titanium and Titanium-Base Alloys
steel that resists stress-corrosion cracking in low-chloride environ-
ments,(237) Designated 3RE60, the alloy contains 0.03C-18.5Cr- Seventeen different heat-exchanger tubing alloys have been
4.7Ni-2.7Mo-1.7Si-1.5Mn and has a minimum yield strength of evaluated after 15,000 hours of exposure to Baltic seawater
45 Kp/mm 2 (about twice that of the usual 18Cr-8Ni stainless (0.4 percent chloride) at 50 C and 2 to 5 m/sec in tests conducted
steels). The general corrosion resistance of the alloy compares in Sweden.(240) In the clean seawater employed. titanium, Alloy
favorably with that of Type 316L stainless steel. Although 3RE60 825, and molybdenum-containing austenitic stainless steels were
cracks readily in boiling 42 percent MgCI2 solution, it has not completely resistant to attack even at rolled-in crevices. Intergran-
cracked in a number of low-chloride environments that produced ular attack occurred adjacent to welds in ferritic-molybdenum
cracking in 18Cr-8Ni alloys. These included water at 295 C (565 F) stainless steels, but these were found to have been accidentally
containing 100 ppm chloride and 8 ppm oxygen, refinery heat carburized prior to welding. Aluminum alloys and a number of
exchangers handling 190 C (375 F) water containing 900 ppm copper alloys exhibited erosion-corrosion at the velocities studied.
chloride, and cooling coils with partial evaporation of Baltic The 70-30 Cu-Ni-Fe resisted attack at the 4 to 5 m/sec velocity.
seawater (about 3000 ppm chloride) at 270 C (520 F).
Letvin and Smith have observed that because of its excellent
record of performance in salt water, titanium has become a serious
Copper-Base Alloys candidate for the entire shipboard seawater piping systems. (241)
Land-based titanium seawater piping in the form of heat exchangers
The incipient corrosion of copper alloys, arising from the use is becoming increasingly used; twenty-one condensers representing
of polluted water in the seawater cooling systems of new construc- a 12,424-megawatt generating capacity in coastal power plants are
tion ships, may proceed in subsequent service leading to early already installed or on order.(242)
failures,(238) To investigate these effects, the Danish Ship Re-
search Laboratory undertook a study to determine how far a pre- The Oak Ridge Natiqnal Laboratory has issued a compilation
treatment of copper alloys with a suitable inhibitor solution, of its research efforts on reactions and transport phenomena at
accomplished before assembling of the seawater carrying compo- surfaces as related to desalination.(243) Included are separate
nents on board the ship, could prevent initiation of corrosion attack articles on the following subjects:
from polluted water.
• Kinetics and Pitting Attack of Titanium in Chloride
After a pretreatment in a sodium-dimethyldithiocarbamate Solutions
solution, heat exchanger tubes from AI-brass, CuNi 90/ I0 and
CuNi 70/30 were simultaneously exposed for a 5 week fitting-out • Pitting of Titanium in Saline Waters
period at selected harbors in more parallels with different surface
preparations ("as received" and inhibitor pretreated). It was found • Kinetics of Initiation of Crevice Corrosion of Titanium
that the shop pretreatment of copper alloy components, carried
out before mounting of the pipe system, as in these tests, does not
provide safe protection of copper alloys during and after the fit- Aluminum-Base Alloys
ting out period. On the contrary, the pretreatment in more
instances increased the corrosion in the subsequent operation Verink and George reported the results of an inspection of
period. It was also concluded that: aluminum components in the Aluminum Association experimental
desalination plant at Freeport, Texas, after approximately 36
• CuNi 90/10 was the least resistant material toward sulfide months of service,(244) Five tubing alloys (1200, 3003, 5050,
polluted seawater in these tests and the intensity of attack 5052, and 6063), two plate alloys (5454 and 6061), and one pipe
increased with the flow velocity. alloy (6061) are being evaluated under conditions likely to be
encountered in desalination plants. No significant corrosion has
• AI-brass suffered in general less corrosion than CuNi been found on any of the process equipment, including piping,
90/1 O. tube sheets, flanges, flash tanks, heat exchanger heads, or support
structures. N,) special corrosive attack under barnacles has been
• CuNi 70/30 was least affected by polluted seawater with observed and overall plant appearance remains excellent. The
a slight tendency to some recognizable corrosion at the minor amount of pitting apparent in several of the heat exchanger
lower flow velocities. tubes after six months service appeared no more severe during the
present inspection. This initial pitting was attributed to heavy
Materials problems in salt-water cooling towers have been re- metal ion scavanging. With the passage of time, the alloy surface
viewed by Exxon Research and Engineering Company.( 239 ) Speci- apparently became immune to further damage. The relative be-
fic problems include: havior of the tube alloys in a heat exchanger operating at a water
 92
TABLE 87. EVALUATION OF TUBES FROM THE HEAT RECOVERY UNIT E_22(244)

First Pass
Max. Pit Avg. Pit
Months Temp., Depth, Depth, No. of
Alloy Tested F Inches Inches Pits/In 2 Remarks

3003 32 125 0.010 0.002 1 Pitted areas

5052 32 125 0 0 0 Slight etch (one small depression)
6063 32 125 0.008 0.002 1
5050 20 125 0.018 0.005 0.01 Very few pits, but few deep pits
1200 6 125 0 0 0 Slight etched area, no real pits

Last Pass

3003 32 210 0 0 0 Excellent appearance, very slight

etch
5052 32 210 0 0 0 Excellent appearance, very slight
etch
6063 32 210 0 0 0 Excellent appearance, very slight
etch
5050 20 210 0.003 0.002 0.1 Few shallow pits, very slight etch
1200 6 210 0 0 0 Excellent appearance, very slight
etch

velocity of 5 fps and water temperatures from 125 to 210 F is In view of their excellent corrosion resistance, low cost, and ease of
shown in Table 87. fabrication, aluminum alloys are prime candidates for the construc-
tion of desalination equipment.
Alcoa investigators have also reported on an electrochemical
study of the corrosion behavior in seawater of 1100-F, 6063-T6,
and 5052-H34 aluminum alloys. (245) One conclusion was that Cathodic Protection
after a short break-in period, the general corrosion rates of these
alloys would be less than 1 mil per year at operating temperatures
to 300 F. The 6063 alloy was judged slightly more susceptible to Two reports have been published which describe experiences
pitting than the 5052 alloy within the 75 to 125 F temperature with the use of sacrificial Al-ln-Hg anodes in the cathodic protec-
range if corrosion products were allowed to accumulate. Although tion of offshore structures(248,249) and another which compares
the 1100 alloy showed a somwhat lower capability to repassivate the electrochemical characteristics of commercial Al-ln-Hg, AI-ln-
pits than the magnesium-containing alloys, it was considered In, and AI-ln-Sn alloys in seawater at Key West, FloridaJ250) The
satisfactory for service to 260 F. AI-ln-Hg anode consistently produced the highest efficiency with
a minimum of 1250 amp hr/lb. The current capacity of AI-Zn-In
Additional corrosion experience with aluminum in three de- anodes was 757 to 900 amp hr/lb at nominal in-service current
salting plants has been described by the Resources Conservation densities while that of AI-Zn-Sn anodes was 630 to 1000 amp hr/
Company.(246) The plants were a desalination plant in the Virgin Ib with the lowest value being obtained at low current densities.
Islands, a brine concentrator in EI Paso, Texas, and a small OSW The heat treatable AI-ln-Sn anodes were not considered to be
test plant at Roswell, New Mexico. Aluminum 3003, 6061, and suitable for galvanic anodes in seawater based on their current
6063, and titanium comprised most of the equipment in these outputs and current capacities.
plants which operated with acidified water containing 10 to 50 ppb
oxygen near atmospheric boiling. In general, the aluminum per- The electrochemical properties of magnesium and zinc anodes,
formed well. Notable exceptions were (I) severe attack with in addition to aluminum alloys, were also reviewed and compared in
oxygen-saturated intake water at 5 to 6 pH and 21 to 100 C, and a comprehensive study by the Navy .(251) The principal con-
(2) severe pitting where copper was present in one feed. The clusions from the review are:
former problem was solved by replacement with fiberglass piping
while the latter was solved by raising the pH to 7.5 and allowing 1. By using magnesium anodes confonning to MIL-A-2 1412A,
the oxygen to rise to 50 ppb. zinc anodes conforming to MIL-A-1800 1H or aluminum
anodes of the proper identity, one can readily obtain
Finally, Taylor has summarized over seventy publications dependable electrochemical properties from galvanic
describing either corrosion studies of aluminum alloys in seawater anodes for seawater service. Aluminum alloy anodes
or actual experience with aluminum components in desalination containing small percentages of zinc and mercury have
equipment. (24 7) Experience in a number of areas suggests that consistently given satisfactory electrochemical character-
alloys containing 1 to 3 percent magnesium (5052, for example) istics, but the current capacity may be lowered consid-
exhibit superior corrosion resistance in a seawater environment. erably if the anodes are used in anaerobic muds covered
Avoidance of galvanic contact with steel or copper-base alloys is by seawater.
important. Pitting also can be troublesome, especially in water
entry areas, when high heavy-metal ion concentrations are present 2. The aluminum-zinc-mercury alloy anodes have the lowest
in the water. Methods for reducing pitting problems in such cases relative metal cost per ampere year compared to mag-
through the use of entry screens or heavy-metal traps are described. nesium, zinc, or other aluminum alloy anodes studied.
 93
Five studies were noted where the major emphasis was on The corrosion behavior and response to cathodic protection
techniques for the cathodic protection of stainless steels. Sacri- of wire ropes have been studied by the Naval Research Labora-
ficial zinc anodes were favored in two of these(252,253) while tory,(258) Wire ropes with and without zinc anodes were exposed
zinc, aluminum, iron and magnesium anodes were evaluated in partially or completely submerged in seawater at Key West, Florida.
another,(254) One study was confined to the use of impressed Based on 790 days of exposure, Ti-13V-IICr-3AI, aluminized steel,
currents,(255) In another, broad program it was shown that and a nickel alloy (Ni-22Cr-9Mo-2Fe-3.75Cb+Ta) were suitable for
carbon steel was a very effective anode material, protecting stain- 2 years of exposure without cathodic protection. Phosphor bronze,
less steel in excess of 8 years in seawater and through 16 years at galvanized steel, and 90/10 copper-nickel clad Type 304L stainless
mean tide,(256) steel were suitable if cathodically protected. Unclad Type 304 and
90/10 coppn-nickel clad Type 205 stainless steel exhibited local-
Researchers at the Shell Development Company have reported ized corrosion even when cathodically protected.
on the corrosion of pipeline steels in and near the bottom sedi-
ments of the Gulf of Mexico at depths of 50 to 500 feet.(257) Six articles on cathodic protection are included in the Novem-
It was shown that the corrosion of separate, buried steel panels ber, 1973, issue of Materials Protection and Performance,(259)
and the cathodic protection current densities required to control The articles discuss protection of ship hulls, Mississippi River
this corrosion are less than in the ocean immediately above the docks, buried coaxial cable, and water-tank interiors as well as
mudline. The corrosion rate of unprotected steel panels exposed direct-current concepts and the effect of anode length on anode
to seawater above the mud is as high as II mpy depending on the output.
time and location of exposure. Unprotected panels below the mud-
line, however, corrode at rates of I to 3 mpy. Pitting corrosion of Experiences with the cathodic protection of marine heat ex-
these panels is also more intense in the water above the mud than changers(260) and desalting plants(26I ,262) have also been des-
buried in the mud. The current density required to reduce the cribed. In general, techniques involving impressed currents for
corrosion rate of these panels to < I mpy is in excess of 3.2 mAl cathodic protection are favored.
ft2 above the mudline and from 0.6 to 2.5 mA/ft 2 below the mud-
line. The current density required to control corrosion decreases
with increasing depth of burial in the mud.
 94
REFERENCES

(I) Reinhart, F. M., "Corrosion of Materials in Hydrospace", (19) Southwell, C. R. and Alexander, A. L., "Corrosion of
U. S. Naval Civil Eng. Lab., Port Hueneme, Calif., Tech- Structural Ferrous Metals in Tropical Environments -
nical Report R504 (December, 1966). Sixteen Year's Exposure to Sea and Fresh Water". Paper
No. 14. Preprint, 1968 NACE Conference, Cleveland,
(2) "Hydrographic Aspects of TOTO Waters", U. S. Naval Ohio.
Oceanographic Office (March, 1962).
(20) Lattin, B. c., "Steel Piling in Seawater", Consulting
(3) Park, K. "Deep-Sea pH", Science, 154 (3756), Engineer, 10 (6), 78-83 (1958).
1540-1542 (1966).
(21) Reinhart, F. M., "Corrosion of Materials in Hydrospace
(4) The Corrosion Handbook, Edited by H. H. Uhlig, John - Part I. Irons, Steels, Cast Irons and Steel Products",
Wiley & Sons, New York (1948). U. S. Naval Civil Engineering Lab., Port Hueneme, Calif.,
Technical Note N-900 (July, 1967).
(5) Chemical Oceanography, Vol. I, Edited by Riley, J. P.,
and Skirrow, G., Academic Press, N.Y.C. and London (22) Montgomery, H.A.C., Thorn, N.S., and Cockburn, A.,
(1965), "The Physical Properties of Seawater" (R. A. "Determination of Dissolved Oxygen by the Winkler
Cox), Chapter 3. Method and the Solubility of Oxygen in Pure Water and
Sea Water", J. App!. Chern., 1:L No.7, pp 280-296
(1964).
(6) Lyman, J., Abel, R. B., "Chemical Aspects of Physical
Oceanography", J. Chemical Education, 35 (3),113-115 (23) Larrabee, C. P., "Steel Has Low Corrosion Rate During
( 1958). Long Seawater Exposure", Materials Protection, 1 (12),
95-96 (1962).
(7) Temperley, T. G., "Corrosion Phenomena in the Coastal
Areas of the Persian Gulf', Corrosion Science,S, (24) Larrabee, C. P., "Corrosion of Steels in Marine Atmo-
581-589 (1965). spheres and in Seawater", Trans. Electrochem. Soc., 87,
161-182 (1945).

(8) Fink, F. W., "Corrosion of Metals in Seawater", U. S. (25) Peterson, M. H., and Waldron, L. J., "An Investigation
Dept. of the Interior, PB 171344, OSW R&D Report No. of the Corrosion Rate of Mild Steel in San Diego
46 (1960). Harbor", Preprint, NACE 16th Annual Conference,
Dallas, Texas (March, 1960).
(9) La Que, F. L., "Corrosion Testing", Proc. of American
Society for Testing Materials, a, 495-582 (1951). (26) Rogers, T. H., The Marine Corrosion Handbook, McGraw
Hill Co. of Canada, New York and Toronto (1960).
(10) Brown, B. F., "Metals and Corrosion", Machine Design,
40 (2),165-173 (1968). (27) Copson, H. R., and Larrabee, C. P., "Extra Durability of
Paint on Low Alloy Steels", ASTM Bulletin, No. 242,
(II) Ellis, O. B., and LaQue, F. L., "Area Effects in Crevice 68-74 (December, 1959).
Corrosion", Corrosion, 2. (II), 362-364 (1951).
(28) Larrabee, C. P., "Corrosion Resistance of High-Strength
(12) Copson, H. R., "Long-Time Atmospheric Corrosion Tests Low-Alloy Steels as Influenced by Composition and
on Low Alloy Steels", ASTM Proceedings, 60, 650-665 Environment", Corrosion,2- (8), 259-271 (1953).
( 1960).
(29) Coburn, K., "A Low Cost Maintenance-Free Structural
(13) Southwell, C. R., Forgeson, B. W., and Alexander, A. L., Steel for Highway Applications", Reprint from Highway
"Corrosion of Metals in Tropical Environments, Part 4 - Research Record 110 (1966), Highway Research Board,
Wrought Iron", Corrosion, !&. (11), 512t-518t (1960). Washington, D. C.

(14) Ambler, H. R., and Bain, A.A.J., "Corrosion of Metals in (30) Larrabee, C. P., "Corrosion-Resistant Experimental Steels
the Tropics", J. App!. Chern., 2., 437-467 (1955). for Marine Applications", Corrosion, .!i (II), 50lt-504t
( 1958).
(IS) Hadfield, R. A., and Main, S. A., "Corrosion of Iron &
Steel", Journal of The Institution of Civil Engineers" (31) Alexander, A. L., Southwell, C. R., and Forgeson, B. W.,
(London),], 3-126, Disc. 613-651 (1935-6). "Corrosion of Metals in Tropical Environments, Part 5 -
Stainless Steel", Corrosion, 12 (7), 345t-352t (1961).
(16) Evans, U. R., The Corrosion and Oxidation of Metals,
Edward Arnold, London, England, 506 (1960). (32) Tuthill, A. H., and Schillmoller, C. M., "Guidelines for
Selection of Marine Materials", paper presented at The
(17) Southwell, C. R., Forgeson, B. W., and Alexander, A. L., Ocean Science and Ocean Engineering Conference
"Corrosion of Metals in Tropical Environments, Part 2 - Marine Technology Society (June 14-17, 1965).
Atmospheric Corrosion of Ten Structural Steels", Cor-
rosion, 14 (9), 435t-439t (1958). (33) Peterson, M. H., and Lennox, T. J., "The Corrosion
Behavior of Stainless Steels in Sea Water", Naval
(18) Humble, A. A., "The Cathodic Protection of Steel Piling Research Lab., Washington, D. c., Memorandum Report
in Seawater", Corrosion,S (9), 292-302 (1949). NRL 1795 (June, 1963).
 95
(34) Wheatfall, W. L., "Metal Corrosion in Deep-Ocean (49) Aziz, P. M., and Goddard, H. P., "Mechanism which
Environments", Naval Engineers Journal, 79 (4), Non-Ferrous Metals Corrode", Corrosion, 15 (10),
611-618 (1967). 429t-533t (1959).

(35) Lennox, T. J., Groover, R. E., and Peterson, M. H., (50) "Identification of Corrosion Products on Copper and
"How Effective is Cathodic Protection of Stainless Steels Copper Alloys", Report of NACE Technical Committee
in Quiescent Seawater", Materials Protection, ~ (5), T-3B, Corrosion, 11 (4), 199t-20lt (1958).
41-48 (1969).
(51) Osborn, D. H., "The Truth About Miss Liberty"
(36) Denhard, E. E., "Stress-Corrosion Cracking of High (Analysis of Patina on Statue of Liberty), Materials
Strength Stainless Steels", Armco Steel Corporation, Design Engineering, 57, 80-82 (June, 1963).
paper presented at Twenty-Fourth Meeting of the
AGARD Structures and Materials Panel, Turin, Italy (52) Hummer, C. W., Southwell, C. R., Alexander, A. L.,
(April 17-20, 1967). "Corrosion of Metals in Tropical Environments-Copper
and Wrought Copper Alloys", Materials Protection, 1
(37) Phelps, E. H., "Stress Corrosion Behavior of High Yield- (1),41-47 (1968).
Strength Steels", Seventh World Petroleum Congress, 2.,
201-209 (1967). (53) Bulow, C. L., "Use of Copper Base Alloys in Marine
Services", Naval Engineers Jrn!., 77 (3), 470-482 (1965).
(38) Slunder, C. J., "Stress-Corrosion Cracking of High-
Strength Stainless Steels in Atmospheric Environments", (54) Reinhart, F. M., "Corrosion of Materials in Hydrospace,
DMIC Report 158 (September 15, 1961). Part IV, Copper and Copper Alloys", Naval Civil Eng.
Lab., Technicfll Note N-961 (April, 1968).
(39) Copson, H. R., "Atmospheric Corrosion Behavior of
Some Nickel Alloys", ASTM STP No. 175, 141-158 (54A) Schreiber, C. F., Osborn, 0., and Coley, F. H., "Corro-
( 1956). sion of Metals in Desalination Environments", Materials
Protection,1, No: 10, 20-25 (October, 1968).
(40) Southwell, C. R., and Alexander, A. L., "Corrosion of (55) Stewart, W. C. and LaQue, F. L., "Corrosion Resisting
Metals in Tropical Environments ~ Part VIII. Nickel and Characteristics 'of Iron Modified 90: 10 Cupro Nickel
Nickel-Copper Alloys", Materials Protection,..§.. (3), 39-44 Alloy", Corrosion,..§.. (8), 259-277 (1952).
( 1969).
(56) Borge Lunn, U. S. Patent 3,214,269 (October 25,1965).
(41) Copson, H. R. (Chairman), "Atmospheric Exposure of
Nonferrous Metals and Alloys", ASTM Subcommittee (57) North, R. F., "The Protection of Copper by Ferrous
VI, 1957 Test Program, Reprint from American Society Sulfate Additions", MRL-67-PR-22, Olin Mathieson
for Testing Materials Proceedings 59, 61, 62, and 66 Chemical Corporation, New Haven, Connecticut (July,
(1959, '61, '62, and '66). 1967).

(42) The Metals Handbook, Eighth Edition, Vo!. I, American (58) White, R. A., "Selection of Materials for Multistage
Society for Metals, Novelty, Ohio (1961), "The Resis- Flash Sea Water Conversion Plants", Materials Protec-
tance of Nickel and Nickel Alloys to Corrosion" (W. Z. tion, 1. (3), 48-52 (1965).
Friend), 1115-1130.
(59) Fink, Frederick W., "Alloys for Seawater Corrosion",
(43) Reinhart, F. M., "Corrosion of Materials in Hydrospace, Materials Protection, Q. (5), 40-43 (1967).
Part II, Nickel and Nickel Alloys", Naval Civil Eng. Lab.,
Port Hueneme, Calif., Technical Note N-915 (August, (60) Rowlands, J. c., "Corrosion of Tube and Pipe Due to
1967). Polluted Seawater", J. App!. Chern., 11, 57-63 (1965).

(61) Todd, B., "The Corrosion of Materials in Desalination

(44) Reinhart, F. M., "Corrosion of Nickel and Nickel Alloys
Plants", Desalination,1, 106-117 (1967).
in Deep Ocean Environments", National Association of
Corrosion Engineers, Preprint No. 17 (1968). (62) Mattson, M. E., and Fuller, R. M., "A Study of Materials
of Construction in Distillation Plants", Joint Report by
(45) LaQue, F. L., "Deterioration of Metals in Ocean Envi- Office of Saline Water and the International Nickel Co.,
ronment", Ocean Engineering, 1 (3), 299-312 (1969). Inc., R&D Progress Report No. 163 (October, 1965).
(46) Corrosion Resistance of Metals and Alloys, Edited by F. (63) Tuthill, A. H., and Sudrabin, D. A., "Why Copper-Nickel
L. LaQue and H. R. Copson, Second Edition, Reinhold Alloys for Desalination", Paper C6-20.3 presented at the
Publishing Co., New York (1963). AS M National Metals Congress, Chicago, Illinois
(October 31 - November 3, 1966).
(47) Modern Electroplating, Edited by F. A. Lowenheim,
Second Edition, John Wiley, New York (1963) (W. H. (64) Todhunter, H. A., "Condenser Tubes in Seawater Ser-
Safranek), Chapter 6. vice", Power, ill (3),57-59 (1967).

(48) Rodgers, T. H., "The Corrosive Behavior of Non-Ferrous (65) May, T. P., Holmberg, E. G., and Hinde, J., "Sea Water
Metals in Sea Water", Jour. Amer. Soc. Naval Engrs., 73 Corrosion and Elevated Temperatures", Deckema-
(2), 387-393 (1961). Monographian Bank 47, 253-274 (1962) (inco Reprint).
 96
(66) May, T. P., and Weldon, B. A., "Copper-Nickel Alloys (80) Lane, I. R., Jr., Cavallero, J. L., and Morton, A.G.S.,
for Service in Sea Water", Congres International de la "Fracture Behavior of Titanium in the Marine Environ-
Corrosion Marine et des Salissures, Cannes, France, ment", U. S. Navy Marine Engineering Laboratory, MEL
141-156 (June, 1964). R&D Phase Report 231/65 (July, 1965); AD 467088.

(67) Newton, E. H., and Birkett, J. D., "Survey of Materials (81) Posey, F. A., and Bohlmann, E. G., "Pitting of Titanium
Behavior in Multi-Stage Flash Distillation Plants", Report Alloys in Saline Waters", Desalination, 1, 269-279
C68373 on Contract No. 14-01-0001-956 from A. D. ( 1967).
Little, Inc., to the Office of Saline Water (August,
1968). (82) Griess, J. c., "Crevice Corrosion of Titanium in Aqueous
Salt Solutions", Corrosion, 24 (4), 96-109 (1968).
(68) Feige, Norman G., and Murphy, T. J., "Environmental
Effects on Titanium Alloys", Corrosion, 22 (I I), (83) "Titanium for Industrial Brine and Sea Water Service",
32{}-324 (1966). Titanium Metals Corporation of America, Trade Litera-
ture (May, 1968).
(69) Bomberger, H. B., Cambourelis, P. J., and Hutchinson,
G. E., "Corrosion Properties of Titanium in Marine Envi- (84) Takamura, A., "Corrosion Resistance of Ti, and a Ti-Pd
ronments", Journal of the Electrochemical Society, ill Alloy in Hot Concentrated Sodium Chloride Solutions",
(9), 442-447 (1954). Corrosion, 23 (10), 306-313 (1967).

(70) Reinhart, F. M., "Corrosion of Materials in Hydrospace, (85) Logan, H. L., "Studies of Hot Salt Cracking of the
Part III, Titanium and Titanium Alloys", U. S. Naval Titanium - 8AI-IMo-IV Alloy", Proceedings of Con-
Civil Eng. Lab., Port Hueneme, Calif., Technical Note ference on Fundamental Aspects of Stress Corrosion
N-921 (September, 1967). Cracking, National Association of Corrosion Engineers,
Houston, Texas, 662-672 (1969)
(71) Danek, G. J., Jr., "The Effect of Sea-Water Velocity on
the Corrosion Behavior of Metals", Naval Engineers (86) Godard, Hugh P., "The Atmospheric Corrosion of Archi-
Journal, 78 (5), 763-769 (1966). tectural Metals", The Engineering Journal, 36 (7),
844-855 (1953).
(72) Hohman, A. E., and Kennedy, W. L., "Corrosion and
Materials Selection Problems on Hydrofoil Craft", (87) Ailor, W. H., "Five-Year Corrosion of Aluminum Alloys
Material Protection, 1 (9), 56-68 (1963). at Several Marine Sites", British Corrosion Journal, I,
327-343 (1966). -
(73) Cotton, J. B., and Downing, B. P., "Corrosion Resistance
of Titanium to Seawater", Inst. Marine Engineers Trans., (88) Southwell, C. R., Alexander, A. L., and Hummer, C. W.,
69 (8),311-319 (1957). "Corrosion of Metals in Tropical Environments, Part 6 ~
Aluminum and Magnesium", Materials Protection, 4
(74) The Encyclopedia of Electrochemistry, Edited by C. A. (12), 30-35 (1965).
Hampel, Reinhold Publishing Corp., New York (1964),
"Galvanic Corrosion" (F. L. La Que), 661-666. (89) Godard, H. P., and Booth, F. F., "Corrosion Behavior of
Aluminum Alloys in Seawater", Congres International de
(75) Lennox, T. J., Jr., Peterson, M. H., Brown, B. F., la Corrosion Marine et des Salissures, Cannes, France,
Groover, R. E., Newbegin, R. L., Smith, J. A., and 37-52 (1964).
Waldron, L. J., "Marine Corrosion Studies", NRL Memo-
randum Report 171 I (May, 1966). (90) Reinhart, F. M., "Corrosion of Materials in Hydrospace,
Part V Aluminum Alloys", U. S. Naval Civil Eng. Lab.,
(76) Brown, B. F., "A New Stress-Corrosion Cracking Test Port Hueneme, Calif., Technical Note N-I008 (January,
for High-Strength Alloys", Materials Research and 1969).
Standards, 2. (3), 129-133 (1966).
(91) Groover, R. E., Lennox, T. J., Jr., and Peterson, M. H.,
(77) Judy, R. W., and Goode, R. J., "Stress Corrosion Crack- "Characterization of the Corrosion Behavior and
ing Characteristics of Alloys of Titanium in Salt Water", Response to Cathodic Protection of Nineteen Aluminum
Naval Research Laboratory Report 6564 (July 21, Alloys in Seawater", Naval Research Lab., Washington,
1967). D. c., NRL Memorandum Report 1961 (January, 1969).

(78) "Titanium for the Chemical Engineer - Lectures Given (92) Reinhart, F. M., "Corrosion of Materials in Surface Sea-
at the A.l.Ch.E. Materials Conference, Philadelphia, water After 6 Months Exposure", Naval Civil Eng. Lab.,
Pennsylvania, April I, 1968", DMIC Memorandum 234, Port Hueneme, Calif., Technical Note N-I023 (March,
April 1, 1968, "Stress Corrosion Cracking of Titanium 1969).
and Its Alloys" (W. K. Boyd), 35-44.
(93) Ailor, W. H., "Evaluation of Aluminum After One-Year
(79) Lane, l. R., Jr., Cavallero, J. L., and Morton, A.G.S., Deep Sea Exposure", J. Hydronautics, 2 (1), 26-33
"Sea Water Embrittlement of Titanium" paper contained (1968). -
in ASTM Special Technical Publication No. 397, Sum-
mary of Fifth Pacific Area National Meeting at Seattle, (94) Jackson, J. D., and Boyd, W. K., "Stress-Corrosion
Washington (November 1-2, 1965). Cracking of Aluminum Alloys", DMIC Memorandum
202 (February 15, 1965).
 97
(95) Ogier mann, Gunter, "Stress Cracking of Aluminum (109) Southwell, C. R., and Alexander, A. L., "Marine Cor-
Alloys", (A Review of European Literature), DMIC rosion of Cast and Wrought Non-Ferrous Metals -
Memorandum 240 (December, 1968). Results of Sixteen Years Exposure in the Tropics", pre-
print of Paper No. 63 presented at the National Associa-
(96) Lifka, B. W., and Sprowls, D.O., "Stress-Corrosion Test- tion of Corrosion Engineers, Houston, Texas (1969).
ing of 7079-T6 Aluminum in Various Environments",
Stress-Corrosion Testing, ASTM STP No. 425, 342-362 (110) Frost, P. D., Fink, F. W., Pray, H. A., and Jackson, J.
(1967). H., "Results of Some Marine-Atmosphere Corrosion
Tests on Magnesium-Lithium Alloys", Journal of the
(97) Sprowls, D.O., "Reporting and Evaluating Stress Corro- Electrochemical Society, 102 (5), 215-28 (1955).
sion Data", Stress Corrosion Testing, ASTM STP No.
425, 292-316 (1967). (III) White, E. L., and Fink, F. W., "Corrosion Protection of
Magnesium and Magnesium Alloys", DMIC Memorandum
(98) Lifka, B. W., Sprowls, D.O., and Kaufman, J. G., 205 (June I, 1965).
"Exfoliation and Stress-Corrosion Characteristics of High
Strength Heat Treatable Aluminum Alloy Plate", Corro- (112) Kiefer, R., Bach, H., Binder, F., and Kurka, F., "Con-
sion, 23 (1 I), 335-342 (1967). tribution to the Corrosion Behavior of the IVA, VA, and
VI A Metals" (In German), Werkstoffe und Korrosion,
(99) Hunter, M. S., and Fricke, W. G., "Study of Crack- 19 (4) 312-316 (1968).
Initiation Phenomena Associated with Stress Corrosion
of Aluminum Alloys", Second Annual Report from (113) The Metallurgy of Zirconium, Edited by B. Lustman and
Alcoa Research Laboratories, to Marshall Space Flight F. Kerfe, First Edition, McGraw Hill, New York (1955)
Center (July 15, 1968). p.647.

(100) Jacobs, A. J., "The Mechanism of Stress Corrosion (114) Acherman, W. L., Carter, J. P., Kenahan, C. B., and
Cracking in 7075 Aluminum", Proceedings of Con- Schlain. D., "Corrosion Properties of Molybdenum,
ference on Fundamental Aspects of Stress Corrosion Tungsten, Vanadium, and Some Vanadium Alloys",
Cracking, National Association of Corrosion Engineers, Bureau of Mines, Boulder, Colo., Report of Investiga-
Houston, Texas, 530-560 (1969). tions 6"15 (1966).

(101) Williams, L., Bleecker E., Greenberg, S., "Stress Corro- (115) Acherman, W. L., Carter, J. P., and Schalin, D., "Corro-
sion Evaluation of Electron Beam Welded Aluminum sion Pmperties of the TZM and Molybdenum-3D Tung-
Alloy 7039", Northrop Corp., Ventura Division, New- sten Alloys", Bureau of Mines, Boulder, Colo., Report of
bury Park, Calif., Research Report NVR-6217, Vol. II Investigations 7169 (August, 1968).
(June 15, 1968).
(116) Rare Metals Handbook, Edited by C. A. Hampel, Rein-
(102) Niederberger, R. 8., Basil, J. L., dnd Bedford, G. T., hold Publishing Co., New York (1961).
"Corrosion and Stress Corrosion of 5000 Series AL
Alloys in Marine Environments", Corrosion, 22 (3), (117) "Platiniled Titanium Anodes for Cathodic Protection",
68-73 (1966). Englehard Industries Publication EI 6425 (May 16,
1966).
(103) Holtyn, C. H., 'The Age of Ships", Society of Naval
Architects and Marine Engineers, Preprint No. 9 (I 18) Morgan, J. H., Cathodic Protection, Leonard Hill,
(November, 1966). London (1959).

(104) Leveau, C. W., "Aluminum and Its Use in Fishing (119) Southwell, C. R., Forgeson, B. W., and Alexander, A. L.,
Boats", reprint from Fishing Boats of the World: 3, "Corrosion of Metals in Tropical Environments, Part 3 -
Fishing News (Books), Publisher, London, 1967 (Avail- Underwater Corrosion of Ten Structural Steels",
able from The Aluminum Association, New York, New Corrosion, !Q (3), 105t-118t (1960).
York 10017).
(120) Southwell, C. R., Forgeson, 8. W., and Alexander, A. L.,
(105) Miller, R. A., Myers, 1. R., and Saces, R. K., "Stress- "CorrosIOn of Metals in Tropical Environments, Part I -
Corrosion of Beryllium in Synthetic Seawater", Corro- Five Non-Ferrous Metals and a Structural Steel",
sion, 23 (I), 11-14 (1967). Corrosion, l± (2) 73t-81t (1958).

(106) Prochko, R. J., Myers, J. R., and Saxes, R. K., "Corro- (121) Von Franhofer, J. A., "Lead Corrosion 1I1 Seawater",
sion of Beryllium by Salt Water(s)", Materials Protec- Anti-Corrosion, lQ (5), 21-26 (1969).
tion, 2. (12), 39-42 (1966).
(122) Anderson, E. A., "Zinc in Marine Environments",
(107) Gilpin, C. B., and Mackay, T. L., "Corrosion Research Corrosion, 12. (8), 409t-412t (1958).
Studies on Forged Beryllium", AFML-TR-66-294, Con-
tract AF 33(615)-2242 (January, 1967); AD-646508. (123) Protective Coatings for Metals, Edited by R. M. Burns,
and W. W. Bradley, Second Edition, Reinhold Publishing
(108) Miller, P. D., and Boyd, W. K., "Corrosion of Beryl- Co., New York (1955).
lium", DMIC Report 242 (December II, 1967).
 98
(124) La Que, F. L., and May, T. P., "Experiments Relating to (139) Harbage, A. B., "Fatigue Study of a Monel Inlaid Shaft
the Mechanism of Cathodic Protection of Steel in Sea- Exposed to Seawater", Report 7-353 (AD 869198). Naval
water", The 2nd International Congress on Metallic Ship Research and Development Center. Annapolis. Md.
Corrosion, NACE, 789-794 (1966). (April 1970).

(125) Doremus, E. P., and Doremus, G. L., "Cathodic Protec- (140) Novak, s. R., "Effect of Prior Uniform Plastic Strain on the
tion of Fourteen Offshore Drilling Platforms", Corrosion, K (sub Iscc) of High-Strength Steels in Sea Water". U. S.
6 (7), 216-224 (1950). Steel Corporation, Monroeville, Pa .. paper presented at the
Symposium on Fracture and Fatigue, George Washington
(126) Potosnak, C. S., Wilson, A. J., Talbot, C.J.H., "Cathodic University, Washington, D.C., (May 3-5, 1972).
Protection of Offshore Structures", Corrosion Prevention
and Control, 15 (2), 12-14 (1968). (141) Colangelo, V. J., and Ferguson, M. S., "Susceptibility of
Gun Steels to Stress Corrosion Cracking". Report WVT-
(127) Doremus, G. L., and Davis, J. G., "Marine Anodes: The 7012, Watervliet Arsenal, Watervliet, N.Y. (November.
Old and The New", Materials Protection, 6 (I), 30-39 1970).
( 1967).
(142) Montano, J. W., "An Evaluation of the Mechanical and
(128) Hine, R. A., and Wei, M. W., "How Effective are Alumi- Stress-Corrosion Properties of Cold Worked A-286 Alloy",
num Anodes in Seawater", Materials Protection, 3 (II), Report NASA TM X-64569 (N71-18864). George C.
49-55 (1964). Marshall Space Flight Center, Ala., (February 12. 1971).

(129) Sansonetti, S. J., "To Prevent Corrosion at Sea Think (143) Smith, J. A., Peterson, M. H., and Brown, B. F.. "Elec-
Aluminum Anodes", First Offshore Technology Confer- trochemical Conditions at the Tip of an Advancing Stress
ence AIME, Houston, Texas, Preprint No. OTC 1039 Corrosion Crack in AISI 4340 Steel", Corrosion, 26 (12).
(May 18-21, 1969). 539-542 (December, 1970). -

(130) Schrieber, C. F., and Reding, J. T., "Field Testing a New (144) Smith, J. H., and Davis, J. A., "Stress-Corrosion and
Aluminum Anode". Materials Protection, 6 (5), 33-36 Hydrogen-Embrittlement Cracking Behavior of HY-80 and
(1967). HY-130 Weld Metals", Report 89.021-024(4), Applied
Research Laboratory, United States Sted, Monroeville,
(131) Cotton, J. B., and Moore, D. c., First International Pa., Contract NObs-94535 (FBM) (January 22. 1971).
Congress on Marine Corrosion and Fouling, Cannes,
France, 183-189 (June 8-13, 1964), published by Centre (145) McHenry, H. I., "A Compliance Method for Crack Growth
de Recherches e du Etudes Occanographiques, Paris. Studies at Elevated Temperatures". Journal of Materials.
§..(4), 862-873 (December, 1971).
(132) Reinhart, F. M., and Jenkins, J. F., "The Relationship
Between the Concentration of Oxygen in Seawater and the (146) Crooker, T. W., et aI., "Effects of Flowing Natural Seawater
Corrosion of Metals", Summary Report Naval Civil Engi- and Electrochemical Potential on Fatigue-Crack Growth in
neering Laboratory, Port Hueneme, California. (1961- Several High-Strength Marine Alloys", Final Report NRL-
1971). 8042 (AD A030903), Naval Research Laboratory. Washing-
ton, D.C., (August 30, 1976).
(133) Compton, K. G., et aI., "The Effect of Aerobic Marine
Bacteria on the Corrosion of Metals in Sea Water", Report (147) Ryder, J. T., and Gallagher, J. P., "Temperature Charact-
662, U. S. Department of the Interior, Office of Saline erization of the Below K (sub Iscc) Corrosion Fatigue
Water, Washington, D.C., Department of the Interior Grant Behavior of HY-130 Steel". Report UI LU-ENG-72-6003.
14-01-0001-1735 (May 1971). T. & A. M. 355, Department of Theoretical and Applied
Mechanics, University of Illinois, Urbana, Ill., National
(134) McIlhenny, W. F., and Zeitoun, M. A., "A Chemical En- Science Foundation.
gineer's Guide-Part I ", Chemical Engineering, 1SL (25),
81-86 (November 3,1969). (148) Noronka, P. J., "Kinetic Studies of the Stress Corrosion
Cracking of D6ac Steel", Report TM X-64923 (N75-21434),
(135) Groover, R. E., Smith, J. A., and Lennox, Jr., T. J., George C. Marshall Space Flight Center, Marshall Space
"Electrochemical Potentials of High Purity Metals in Sea Flight Center, Ala. (March 25, 1975).
Water", Corrosion, ~ (3),101-104 (March 1972).
(149) Reinhart, F. M., "Corrosion of Materials in Hydrospaee-
(136) Thiruvengadam, A., "Handbook of Cavitation Erosion", Part VI, Stainless Steels", Report N-II72 (AD 732365),
Final Report TR-7301-1 (AD 787073), Hydronautics, Naval Civil Engineering Laboratory, Port Hueneme.
Incorporated, Laurel, Md., Contract NOOOI4-73-C-0017 Calif. (September, 1971).
(January 1974).
(150) Lennox, Jr., T. J., "Corrosion Analysis of 304 Stainless
(137) Watkins, L. L., "Corrosion and Protection of Steel Piling Steel Wire Rope and Fittings From a NOMAD Buoy
in Seawater", Technical Memorandum 27, Army Coastal Mooring System After 34-Months Continuous Service in
Engineering Research Center, Washington, D.C. (May 1969). the Gulf of Mexico", Report 2045, Naval Research Lab-
oratory, Washington, D.C., (September, 1969).
(138) Kowaka, M., et aI., "Sea Water Resistant 2Cr-0.2Mo Steel",
The Sumitomo Search, (10), 15-27 (November 1973).
 99
(151) Kenyon, N., Kirk, W. W., and VanRooyen, D., "Corrosion (166) Humphries, T. S., and Nelson, E. E.. "Stress Corrosion
of 18Ni 180 and 18Ni200 Maraging Steels in Chloride En- Cracking Susceptibility of 18Ni Maraging Steel". Report
vironments", Corrosion, II (9), 290-400 (September, TM X-64837 (N74-21136), Marshall Space Flight Center,
1971). Ala. I April, 1974).

(152) Holsberg, P. W., "Corrosion Studies of IONi-2Cr-IMo-8Co (167) Floreen, S., Hayden, H. W., and Kenyon, N.. "Stress-Cor-
Steel", Report 8-438 (AD 867332), Naval Ship Research rosion Cracking Behavior of Maraging Steel Composites",
& Development Laboratory, Annapolis, Md. (March, 1970). Corrosion. ~l (12). 519-524 (December, 1971).

(153) Caplan, I. L., "Mechanical Properties and Seawater Be- (168) Crooker, T. W., et aI., "Influence of Experimental Factors
havior of Nitronic 50 (22Cr-13Ni-5Mn) Plate", Report on Corrosion-Fatigue Crack Growth Rate Characterization
DTNSRDC-4554 (AD A020974), Naval Ship Research and in 17-7PH Steel", Report of NRL Progress. Naval Research
Development Center, Bethesda, Md. (January, 1976). Labot'atory, Washington, D.C., 21-23 (May. 1976).

(154) Hack, H. 1'., "Mechanical, Corrosion, and Fatigue Properties (169) Kondas, K. R., "Influence of Microstructural and Load
of 15-5PH, Incone! 718, and Rene 41 Weldments", Report Wave Form Control on Fatigue Crack Growth Behavior of
NSRDC-4528 (ADAO I 0468), Naval Ship Research and Precipitation Hardening Stainless Steels". Dissertation,
Development Center. Bethesda, Md. University of Missouri, Columbia, Mo. (July. 1976).

(155) Lennox, Jr., T. J., and Peterson, M. H., "Corrosion Resist- (170) Hasan, S. Z., Ghali, E. L., and Dumais, J .. "Inf1uence of pH
ance of Recently Developed Stainless Steels in Sea Water", and Specimen Orientation on Corrosion Fatigue Behavior
Materials Performance, 1j (6), 24-32 (June, 1976). of 18% Ni(300) Maraging Steel in Chloride Environments",
SAMPE Quarterly, 7 (I), 20-27 (October, 1975).
(156) Bates, J. F., "Cathodic Protection to Prevent Crevice
Corrosion of Stainless Steels in Halide Media", Corrosion. (171) Sandoz, G., Fujii, C. T., and Brown. B. F .. "Solution
29 (1),28-32 (January, 1973). Chemistry Within Stress-Corrosion Cracks in Alloy Steels",
Corrosion Science, 10 (12), 839-845 (December. 1970).
(157) Ulanovskii, I. B., and Korovin, Yu. M., "The Reduction of
Oxygen Concentration Within Stainless Steel Slots", Pro- (172) l\iederberger, R. B., Ferrara, R. J .. and Plummer, F. A.,
tection of Metals, 11 (2), 188-189 (March-April, 1975). "Corrosion of Nickel Alloys in Quiet and Low Velocity
Seawater", .\1aterials Protection and Performance. 9 (8),
(158) Kowaka, M., et aI., "New Duplex Stainless Steel DP3 Re- 18-22 (August, 1970). -
sistant to Sea Water Corrosion", Sumitomo Metals, 28 (4),
423-436 (October, 1976). (173) Taylor, E., "Corrosion Resistance of Multiphase Alloys",
Materials Protection, 2.(3), 29-31 (MarcIl. 1970).
(159) Deel, O. L., and Mindlin, H., "Engineering Data on New
Aerospace Structural Materials", Final Report AFML-TR- (174) Efird. K. D., "The Inter-Relation of Corrosion and Fouling
72-196, Vol. I, Battelle-Columbus, Columbus, 0., Contract for Metals in Sea Water". Materials Performance. IS (4),
F33615-71-C-1262 (September, 1972). 16-25 (April, 1976). -

(160) Deel, O. L., and Mindlin, H., "Engineering Data on New (175) Anderson, D. B., and Efird, K. D.. "The Influence of
Aerospace Structural Materials", Final Report AFML-TR- Chromium on the Corrosion Behavior of Copper-Nickel
72-196, Vol. II, Battelle-Columbus, Columbus, 0., Contract Alloy.; in Sea Water". Proceedings of 3rd International
F33615-71-C-1261 (September, 1972). Congress on Marine Corrosion and Fouling. Gaithersburg,
Md., October 2-6, 1972; pp 264-276.
(161) Sandoz, G., "The Resistance of Some High Strength Steels
to Slow Crack Growth in Salt Water", NRL Memorandum (176) Ferrara, R. J., and Gudas, J. P.. "Corrosion Behavior of
Report 2454, Naval Research Laboratory, Washington, Copper-Base Alloys with Respect to Seawater Velocity",
D.C. (February, 1972). ibid, pp 285-298.

(162) Procter, R.P.M., and Paxton, H. W., "The Effect of Trace (177) Ulanovskii, I. B., et aI., "Corrosion of Steel. Titanium. and
Impurities on the Stress-Corrosion Cracking Susceptibility Copper at Various Depths in the Black Sea". Protection of
and Fracture Toughness of 18Ni (300 Grade) Maraging Metals, 12 (4), 394-395 (July-August. 1976).
Steel", Final Report, Metals Research Laboratories, Olin
Corporation, New Haven, Conn., and Carnegie-Mellon (178) Beachem, C. D.. and Meyn, D. A.. "The Effect of Thick-
University, Pittsburgh, Pa., Contract Nonr-760(l3) (Janu- ness Upon Sustained Load Crack Propagation in Ti-6AI-4V
ary, 1970). Alloy Tested in 3-1/2o/r NaCl Solution". NRL Report 7449,
Naval Research Laboratory, Washington. D.C. (August 8,
(163) Judy, Jr., R. W., Fujii, C. T., and Goode, R. J., "Properties 1972),
of 17-4PH Steel", Final Report 7639, Naval Research
Laboratory, Washington, D.C., (December 18, 1973). (179) Neu, C. E.. "Effect of Grain Orientation on Suscepti-
bility of Two Titanium Plate Alloys to Stress Corrosion in
(164) Bhangaonker, S. A., Banerjee, S., "Fracture Toughness of Aqueous Chloride Environments". Report NADC-72I 08-
AISI 420 Steel in a 3.5 Percent NaCI Solution in Water", VT. Naval Air Development Center. Warminster. Pa. (June
Transactions of the Indian Institute of Metals. 28 (I), 15,1972). •
53-57 (February, 1975).
(180) Vassel, A.. Metallurgical and Electro-Chemical Aspects of
(165) Webster, D., "The Stress Corrosion Resistance and Fatigue Stress Corrosion Cracking of Titanium Alloys", Report
Crack Growth Rate of a High Strength Martensitic Stainless ESRO TT-5, ONERA-P-145 (N74-2l142). European Space
Steel, AFC 77", Report 06-23973, The Boeing Company, Research Organization. Paris. France (January. 1974).
Renton, Wash., Contract NOOO 14-66-C-0365 (June, 1969).
 100
(181) Litvin, D. A., and Hill, B., "Effect of pH on Sea Water Bell Aerospace Textron, Buffalo, N. Y., and Ocean City
Stress Corrosion Cracking Behavior of the Ti-7AI-2Cb-ITa Research Corporation, Ocean City. N. J., paper presented
Alloy", Corrosion, 26 (3), 89-94 (March, 1970). at the Annual Conference of the Electrochemical Society,
Las Vegas, Nev., October 18-22, 1976,
(182) Chait, R., and Lum, P., "Factors Affecting Stress-Corrosion
Resistance of the Ti-8Mo-8V-2Fe-3AI Metastable Beta (194) Chu, H. P., Wacker, G. A., "Fracture Toughness and Stress
Titanium Alloy", Corrosion, 32 (II), 450-455 (November, Corrosion Properties of Aluminum Alloy Hand Forgings",
1976). Journal of Materials, 2(1), 95-99 (March, 1972).

(183) Cares, W. R., and Crooker, T. W., "Fatigue-Crack Growth (195) French, J. C., et aI., "Relationship Between Intergranular
of Ti-6AI-2Cb-lTa-0.8Mo Alloy in Air and Natural Sea Corrosion Susceptibility and Stress Corrosion Resistance of
Water Environments", NRL Memorandum Report 2617 Aluminum Alloy Forgings", Final Report TR-75-45 (AD
(AD 765318), Naval Research Laboratory, Washington, AO 17751), Hughes Helicopters, Culver City, Calif. (Septem-
D.C. ber, 1975).

(184) Crooker, T. W., et aI., "Effects of Flowing Natural Seawater (196) Hyatt, M. V., and Quist, W. E., "Effect of Exposure Time
and Electrochemical Potential on Fatigue Crack Growth in at 250 F on Stress-Corrosion Crack Growth Rates in 2024-
Several High-Strength Marine Alloys", NRL Report 8042, T351 Aluminum", Report 06-25218, Commercial Air-
U. S. Naval Research Laboratory, W'lshington, D.C. plane Group, The Boeing Company, Seattle, Wash., Con-
(August, 1976). tract NOOO 14-66-C0365 (March, 1970).

(185) Ailor, W. H., "Ten-Year Seawater Tests on Aluminum," (197) Hunsicker, H. Y., Staley, J. T., and Brown, R. H., "Stress-
9Jrrc)sion J1:1~ Natural Environmen~, ASTM STP 558, Corrosion Resistance of High-Strength Al-Zn-Mg-Cu Alloys
American Society for Testing and Materials, 1974, With and Without Silver Additions", Metallurgical Trans-
pp. 117-134. actions, 3 (I), 201-209 (January, 1972).

(186) Czyryca, E. J., and Hack, H. P., "Corrosion of Aluminum (198) Staley, J. T., "Investigation to Develop a High Strength
Alloys in Exfoliation-Resistant Tempers Exposed to Marine Stress-Corrosion Resistant Aluminum Aircraft Alloy",
Environments for 2 Years", Report NSRDC-4432 (AD Final Report, Alcoa Research Labs., New Kensington, Pa.,
A002234), Naval Ship Research and Development Center, Contract NOOOI9-69-C-0202 (January 20, 1970).
Annapolis, Md. (November, 1974).
(199) Staley, J. T., and Hunsicker, H. Y., "Exploratory Develop-
(187) Peterson, M. H., and Lennox, Jr., T. J., "The Effects of ment of High Strength, Stress-Corrosion Resistant Alu-
Exposure Conditions on the Corrosion of 6061-T6 Alu- minum Alloy for Use in Thick Section Application",
minum in Seawater", Naval Research Laboratory, Washing- Report AFML-TR-70-256, Aluminum Company of Amer-
ton, D.C., paper presented at the International Corrosion ica, New Kensington, Pa., Contract F33615-69-C-1644
Forum Devoted Exclusively to the Protection and Perform- (November, 1970).
ance of Materials, March 22-26, 1976, Houston, Texas.
(200) Staley, J. T., "Investigation to Develop a High Strength
(188) Lennox, Jr., T. J., et aI., "The Effects of Dissimilar Metal Stress-Corrosion Resistant Naval Aircraft Aluminum Alloy",
Couples and Toxicants from Antifouling Paints on the Final Report, Aluminum Company of America, New
Corrosion of 5086 and 6061 Aluminum Alloys and Their Kensington, Pa., Contract NOOO 19-70-C-0 118 (November
Response to Cathodic Protection", Report NRL Memo- 20, 1970).
randum 2444 (AD 746099), Naval Research Laboratory,
Washington, D.C., (May, 1972). (201) Hyatt, M. Y., and Schimmelbusch, H. W., "Development of
a High Strength Stress-Corrosion-Resistant Aluminum
(189) Davies, R. E., Nordmark, C. E., and Walsh, J. D., "Design Alloy for Use in Thick Sections", Final Report AFML-TR-
Mechanical Properties, Fracture Toughness, Fatigue Proper- 70-109, The Boeing Company, Seattle, Wash., Contract
ties, Exfoliation and Stress Corrosion", Final Report, AF 33(615)-3697 (May, 1970).
Aluminum Company of America, Alcoa Laboratories,
Alcoa Center, Pa., Contract NOOOI9-72-C-0512 (July, (202) Kaufman, J. G., Schilling, P. E., and Nordmark, G. E.,
1975). "Fracture Toughness, Fatigue, and Corrosion Characteris-
tics of X7080-T7E41 and 7178-T651 Plate and 7075-
(190) Mansfeld, F., and Parry, E. P., "Galvanic Corrosion of T6510, 7075-T73510, X7080-T7E42, and 7178-T6510
Bare and Coated Al Alloys Coupled to Stainless Steel 304 Extruded Shapes", Final Report AFML-TR-69-255,
or Ti-6Al-4V", Corrosion Science, II (8), 605-621 (August, Aluminum Company of America, New Kensington, Pa.,
1973). Contract F33615-67-C-1521 (November, 1969).

(191) Mansfeld, F., and Kenkel, J. V., "Galvanic Corrosion of (203) Dorward, R. c., and Hasse, K. R., "Flaw Growth of 7075,
AI Alloys-II. Effect of Solution Composition", Corrosion 7475, 7050, and 7049 Aluminum Plate in Stress-Corrosion
Science, li (3), 183-198 (March, 1975). Environments", Final Report, Kaiser Aluminum and Chem-
ical Corporation, Pleasanton, Calif., Contract NAS8-30890
(192) Davis, J. A., and Ghering, Jr., G. A., "The Effect of Velo- (October 15, 1976).
city on the Seawater Corrosion Behavior of High Perform-
ance Ship Materials", Materials Performance, 14 (4), 32-39 (204) Chu, H. P., "Fatigue Crack Propagation in a 5456-H117
(April, 1975). - Aluminum Alloy in Air and Sea Water", Report 4169
(AD 769467), Naval Ship Research and Development
(193) Davis, J. A., Watts, A. A., Gehring, Jr., G. A., "Pitting Center, Annapolis, Md. (October, 1973).
Behavior of Aluminum Alloys in High Velocity Sea Water",
 101
(205) Selines, R. J., Stoltz, R. E., and Pelloux, R. M., "Corrosion (218) Longo, F. N., and Durmann, G. J .. "Corrosion Prevention
Fatigue Crack Propagation in Aluminum Alloys-Part I-- with Thermal Sprayed Zn & Al Coatings",Er.~ceectillgLQ[
Effect of Cyclic Stress Wave Form on Corrosion Fatigue 3rd International Congress on Marine Corrosion and Foul-
Crack Propagation in AI-Zn-Mg Alloys-Part II-Mechanisms ir1g~Gaitj;~~b~g, Md-:;October
2-6.-197 2-:-pp-1I9-1 75.-
of Corrosion Fatigue Crack Propagation in AI-Zn-Mg
Alloys", Final Report AFML-TR-72-21. Massachusetts (219) Rynewicz, J. F., "Evaluation of Paint Coatings Tested in
Institute of Technology, Cambridge, Mass., Contract the Deep Atlantic and Pacific Oceans". Co.'!osi<.l.n_..1'~_
F33615-70-C-1785 (February, 1972). ti'!.tur:.aLI:r1.\'i.!_().r!l11ent~, ASTM STP 558. American Society
for Testing and Materials, 1974. pp. 209-235.
(206) Chanani, G. R., "Fundamental Investigation of Fatigue
Crack Growth Retardation in Aluminum Alloys", Report (220) Drisko, R. W., and Brouillette, C. V .. "Maintenance
AFML-TR-76-156, Northrop Corporation, Hawthorne, Painting of Steel Structures Between Tides and Below
Calif., Contract F33615-74-C-5 I 26 (September, 1976). Water", Materials Protection and Performance, l.Q (4),
32-35 (April, 1971).
(207) Nordmark, G. E., et ai., "Stress-Corrosion and Corrosion-
Fatigue Susceptibility of High-Strength Aluminum Alloys", (221) Pearlstein, F., and Teitell, L., "Corrosion of Nickel-Plated
Final Report AFML-TR-70-259, Alcoa Research Labora- Steel at Tropical Environments", Materials Protection and
tories, Aluminum Company of America, New Kensington, Performance, !Q (11),30-32 (November. 1971).
Pa., Contract F3361 5-67-C-I 922 (November, 1970).
(222) O'Brien, J. L., "Investigation of Metallide Coatings for
(208) Sprowls, D.O., et a!., "Evaluation of Stress-Corrosion Seawater Pump Components", Report 716, Arthur D.
Cracking Susceptibility Using Fracture Mechanics Tech- Little, Inc.. Cambridge, Mass., Contract 14-30-2638 (Sept-
niques", Final Report-Part I, Alcoa Technical Center, ember, 197 I).
Alcoa Center, Pa., Contract NAS 8-21487 (May 31, 1973).
(223) Meyer, Jr., F. H., "Claddings of Superior Corrosion Re-
(209) Hack, H. 1'., "Seawater Corrosion of Fasteners in Various sistance for High Strength Aluminum Alloys", Report
Structural Materials", Report DTNSRDC-76-0034 (AD AFML-TR-71-244, Air Force Materials Laboratory, Wright-
A022885), David W. Taylor Naval Ship Research and Patterson Air Force Base, O. (February, 1972).
Development Center, Bethesda, Md. (April, 1976).
(224) Greer, R. H., "Corrosion-Resistant Adhesive Bonding",
(210) Miller, R. N., Seeliger, G. G., and Boggs, W. A., "Full SAMPE Quarter/y, ~"(2), 51-60 (January, 1971).
Temperature Range Protective System for Fastener Areas
of Carrier-Based Naval Aircraft", Report LG76ER0029 (225) Coursen, J. W., et a!., "Design Mechanical Properties In-
(AD A024533), Lockheed-Georgia Company, Marietta, Ga., cluding Fracture Toughness and Fatigue, Fatigue Crack
Contract NOOOI9-74-C-0267 (February, 1976). Propagation Rates and Corrosion Characteristics of Alclad
7050-1'76 Sheet", Final Report, Aluminum Company of
(21 I) Patel, S., and Taylor, E., "New High-Strength Fastener America, Alcoa Laboratories, Alcoa Center, Pa., Contract
Materials Resist Corrosion", Metal Progress, 100 (3), 98- NOOOI9-74-C-0065 (January, 1976).
102 (September, 1971). ~
(226) Miller, R. N., and Seeliger, C. c., "Coating Aluminum
(212) Ballantine, W., "Choosing Corrosion-Resistant Fasteners Aircraft Alloys to Improve Resistance to Marine Stress
for Marine Applications", Sea Technology, 17 (2), 8-10 Corrosion Cracking", Materials Performance, 14 (10),
(February, 1976). 31-34 (October, 1975).

(213) Kendall, E. G., and Dull, D. L., "Salt Water Corrosion Be- (227) "Indexed Bibliography on Corrosion and Performance of
havior of Aluminum-Graphite Composite", Report SAMSO- Materials in Saline Water Conversion Processes- - -I ",
TR-74-67, TR-0074 (9250-03)-2 (AD 777160), The Aero- "- - 15" Reports INT-OSW-RDPR-74-(947-959, inclusive):
space Corporation, EI Segundo, Calif., Contract F04701- PB Numbers 232474-232488, inclusive: Oak Ridge National
73-C-0074 (March 29,1974). Laboratory, Oak Ridge, Tennes,cc'. (December, 1968---
June. 1972).
(214) Fischer, 1'., and DeLuccia, J., "Effects of Graphite-Epoxy
Composite Materials on the Corrosion Behavior of Aircraft (228) Smith, C. A., and Compton, K. Goo "Potentials of Selected
Alloys", Report NADC-75031-30 (ADAOI0127), Naval Metal Alloys in Sea Water at Elevated Temperatures",
Air Development Center, Warminster, Pa. (April 3, 1975). Corrosion, :u(9),320-326 (September, 1975).

(2 I 5) Beaubien, L. A., et a!., "Behavior of Materials in a Subsur- (229) Fink, F. W., et a!., "Corrosion Control of Galvanically
face Ocean Environment", Final Report NRL 7447 (AD Incompatible Metals in Seawater", Materials Protection
747245), Naval Research Laboratory, Washington, D.C., and Performance, 10 (7), 17-22 (July, 1971).
(July 14, 1972).
(230) Schrieber, C. F., "Sea Water Corrosion Test Program:
(216) Singleton, Jr., W. 1'., "Performance of Various Coating Part Four", Summary Report (PB 248672), Dow Chemical
Systems in a Marine Environment", Materials Protection Company, Midland, Mich. (April, 1975),
and Performance, ~(1 1),37-43 (November, 1970).
(231) Behrens, H. C., Osborn, 0., and Rice, L., "Seawater Cor-
(217) Paton, W. J., Performance Characteristics of Zinc-Rich rosion Test Program-Second Report", Office of Saline
Coating Applied to Carbon Steel", Report NASA TN Water, Report 623, The Dow Chemical Company, Freeport,
D-7336, Kennedy Space Center, Fla. (July, 1973). Texas, Dept. of Interior Contract 14-01-0001-2150 (Decem-
ber, 1970).
 102
(232) Schrieber, C. F., and Coley, F. H., "Behavior of Metals in (246) Herrigel, H. R., "Corrosion Experience with Aluminum
Desalting Environments-Seventh Progress Report (Sum- Desalting Plants", Corrosion Performance, 15 (3), 43-45
mary)", Materials Performance, lj (7), 47-54 (July, 1976). (March, 1976).

(233) Pessall, N. and Nurminen, J. I., "Development of Ferritic (247) Taylor, W. H., "A Review Paper- Aluminum in Desalina-
Stainless Steels for Use in Desalination Plants". Corrosion, tion", Naval Engineering Journal, 87 (5), 69 (October.
30 (II), 381-392 (November. 1974). 1975),

(234) Henrikson, S., Olsson, J., and Arvesen, J., "Corrosion (248) Grandstaff. C. M. and Craig, Jr., H. L., "Offshore Testing of
Tests of Stainless Steels in Flowing Baltic Sea Water", Aluminum Anodes", Materials Protection and Performance,
Report CONF-710520-1, paper presented at the 6th 10 (5), 29-33 (May, 1971).
Scandinavian Corrosion Congress, Gothenburg, Sweden,
(May 24, 1971). (249) Reding, J. T., et aI., "Aluminum Anodes Provide Cathodic
Protection in Seawater", Power Engineering, 80 (10),
(235) Kothari, N. c., "Effect of Sea Water on Corrosion Behavior 46-49 (October. 1976).
of Austenitic Stainless Steel (Type 304) at High Tempera-
ture", Journal of the Australian Institute of Metals, 18 (4), (250) Lennox. T. J.. Groover, R. E., and Peterson, M. H., "Elec-
161-166 (December, 1973). trochemical Characteristics of Six Aluminum Galvanic
Anode Alloys in the Sea". Materials Protection and Per-
(236) Moller, G. E., "Designing with Stainless Steels for Service formance. 10 (9),39-44 (September. 1971).
in Stress Corrosion Environments", Materials Performance,
16 (5),32-44 (May, 1977). (251) Lennox, T. F., Jr., "Electrochemical Properties of Mag-
nesium, Zinc. and Aluminum Galvanic Anodes in Sea
(237) Kiessling, R., "A New Ferritic-Austenitic Stainless Steel Wa t er". J)roc_e~clil}gS_ _oL 3 nLll1jclllatiQI1:JLC.oJlgre;i'--Sl.L1
for Combatting Stress-Corrosion Cracking", Scandinavian Marine Corrosion and Fouling. Gaithersburg, Md., October
Journal of Metallurgy, 1 (4), 185-189 (1972). 2-6 ~T972-:l)pI76:] 90:---

(238) Christensen, c., Danish Ship Res. Lab., "The Int1uencc of (252) Vreeland. D. C., and Bedford, G. T., ''Effects of Cathodic
Polluted Sea Water on the Corrosion of Copper Alloys", Protection on Crevice Corrosion in Seawater", Material
Paper from 7th Scandinavian Corrosion Congress, Trondheim, Protection and Performance, 9 (8), 31-34 (August, 1970).
403-417 (1975).
(253) Lennox, Jr., T. J.. and Peterson, M. H., "Marine Corrosion
(239) Walston, K. R., "Materials Problems in Salt Water Cooling Studies-Cathodic Protection of 304 Stainless Steel and
Towers", Materials Performance, 14 (6), 22-26 (June, Copper Crevices in Salt Solutions.., NRL Memorandum
1975). Report 2374 (AD 736(17), Naval Research Laboratory
(October. 1971).
(240) Henrikson, S. and KnuLsson, L., "Corrosion Tests in Baltic
Sea Water on Heat Exchanger Tubes of Various Metallic (254) Moller, G. E., "The Successful Use of Austenitic Stainless
Materials", British Corrosion Journal, 10 (3), 150-154 Steels in Sea Water", Society of Petroleum Engineers
(1975). Journal, 17(2), 101-110 (April, 1977).

(241) Litvin, D. A. and Smith, D. E., "Titanium for Marine (255) Vreeland. D. C., "Cathodic Protection in Seawater
Applications", Naval Engineers Journal, 83 (5), 37-44 Precipitation Hardening Stainless Steel", Materials Pro-
(October, 1971). tection, 9 (1).32-35 (January, 1970).

(242) Minkler, W. W., "'74 Called Year of Records in Titanium (256) Southwell, c. R. and Bultman, J. D., "Corrosion of Metals
Metal Industry", Feature Section, Am. Metal Mkt., 82, 12, in Tropical Environments: Part 10-Final Report of Sixteen-
July 3,1975. - Year Exposures", Final Report NRL-7834 (AD A003909),
Naval Research Laboratory, Washington, D.C. (January 2,
(243) Posey, F. A., et aI., "Reactions and Transport Phenomena 1975).
at Surfaces", Report Int-OSW-RDPR-73-852 (PB 220644),
Union Carbide Corporation, Oak Ridge National Labora- (257) Di Gregorio, J. S. and Fraser. J. P.. "Corrosion Tests in the
tory, Oak Ridge, Tenn., U.S. Dept. of the Interior Contract Gulf Floor", Corrosion in Natural Environments, ASTM
14-01-0001-937 (May. 1973). STP 558, AmerTc-all----s0cicty-f()r Testmg-;;j(fM ate rials,
1974, pp. 185-208.
(244) Verink, Jr., E. D. and George, P. F., "Long Term Tests of
Aluminum Alloys for Desalination Service", Paper 58, (258) Lennox, Jr., T. J., Groover, R. E., and Peterson, M. H.,
University of Florida, Gainesville, Fla., and The Dow "Corrosion Characterization and Response to Cathodic
Chemical Company, Freeport Tex., paper presented at the Protection of Eight Wire-Rope Materials in Sea Water",
International Corrosion Forum Devoted Exclusively to the Final N RL Report 7584. Naval Research Laboratory,
Protection and Performance of Materials, Anaheim, Calif., Washington, D.C., (September J 2, ]973).
March 19-23,1973.
(259) Materials Protection and Performance, 12 (II). 18-43
(245) Bonewitz, R. A., "An Electrochemical Evaluation of Alum- (November. 1973).
inum Alloys for Desalination", Paper 66, Aluminum
Company of America, Alcoa Technical Center, Pa., paper (260) Morgan, J. H., "Cathodic Protection, Iron Injection, and
presented at the International Corrosion Forum Devoted Chlorination in Marine Heat Exchangers", !,~()(;eedj!1.g;;
Exclusively to the Protection and Performance of Materials, QL]£cLJ~_eJ'nat19naLS~!1.g~~~~.-M'!.rin_~COif9siQ l1.-aJ1J.1
Anaheim, Calif., (March, 1973). Fouling. Gaithersburg, Md., October 2-6, 1972. pp 322-330.
 103
(261) Dittmeier, G. and Byrne, P., "Impressed Current Cathodic
Protection as Applied to Desalting Plants", ibid., pp. 338-
356.

(262) Groover, R. E., and Peterson, M. H., "Cathodic Protection

of Internal Surfaces of Pipes Containing Sea Water",
Materials Performance, 13 (11), 24-29 (November, 1974).
 APPENDIX

DESIGNATIONS AND COMPOSITIONS OF

SELECTED COPPER AND ALUMINUM ALLOYS
 A-2

TABLE A-I. STANDARD COPPER DEVELOPMENT ASSOCIATION DESIGNATIONS

FOR SELECTED COPPER AND COPPER ALLOYS

CDA
No. Previous Trade Name Nominal Composition(a), weight percent

102 Oxygen-free 99.95 Cu + Ag

110 Electrolytic tough pitch 99.90 Cu + Ag
122 Phos. deoxidized .015-.040 P, bal Cu
172 Beryllium-copper 1.8-2 Be, 0.6 (Fe + Ni + Co), bal Cu
192 lron-phos.-copper 2.1-2.6 Fe, .01-.04 P, bal Cu

Brasses

230 Red brass, 85% 84-86 Cu, .05 Pb, .05 Fe, bal In
240 Low brass 78.5-81.5 Cu, .05 Pb, .05 Fe, bal In
260 Cartridge brass, 70% 68.5-71.5 Cu, .07 Pb, .05 Fe, bal In
280 Muntz metal, 60% 59-63 Cu, 0.3 Pb, .07 Fe, bal In
420 (Tin Brass) 88-91 Cu, 1.5-2 Sn, 0.25 P, bal In
442 Admiralty, uninhibeteJ 70-73 Cu, .07 Pb, .06 Fe, 0.8-1.2 Sn, bal In
443 Admiralty, arsenical 70-73 Cu, .07 Pb, .06 Fe, 0.8-1.2 Sn, .02-0.1 As, bal In
464 Naval Brass, uninhibeted 59-62 Cu, 0.2 Pb, 0.1 Fe, 0.5-1 Sn, bal In

Bronzes

505 Phos. bronze, 1.25% E .05 Pb, 0.1 Fe, 1-1.7 Sn, 0.3 In, .03-0.35 P, bal Cu
510 Phos. bronze, 5% A .05 Pb, 0.1 Fe, 3.5-5.8 Sn, 0.3 In, .03-0.35 P, bal Cu
518 Phos. bronze .02 Pb, 4-6 Sn, 0.1-0.35 P, bal Cu
521 Phos. bronze, 8% C .05 Pb, 0.1 Fe, 7-9 Sn, 0.2 In, .03-0.35 P, bal Cu
608 (Aluminum bronze) 0.1 Pb, 0.1 Fe, 5-6.5 AI, 0.35 As, bal Cu
614 Aluminum Bronze D 1.5-3.5 Fe, 6-8 AI, I Mn, bal Cu
637 (Aluminum bronze) .05 Pb, 0.3 Fe, 0.6 Sn, I In, 6.5-8.5 Sn, 0.15 As, 1.2-2.2 Si, 0.25 Ni, bal Cu

Miscellaneous Alloys

655 High-silicon Bronze A .05 Pb, 0.8 Fe, 1.5 In, 1.5 Mn, 2.8-3.8 Si, 0.6 Ni, bal Cu
675 Manganese bronze 57-60 Cu, 0.2 Pb, 0.8-2 Fe, 0.5-1.5 Sn, 0.25 AI, .05-0.5 Mn, bal In
687 Aluminum brass, arsenical 76-79 Cu, .07 Pb, .06 Fe, 1.8-2.5 AI, .02-0.1 As, bal In
704 Copper-nickel, 5% .05 Pb, 1.3-1.7 Fe, I In, 4.8-6.2 Ni, 0.3-0.8 Mn, bal Cu
706 Copper-nickel, 10% .05 Pb, 1-1.8 Fe, 1 In, 9-11 Ni, I Mn, bal Cu
707 (Copper-nickel) .05 Fe, 9.5-10.5 Ni, 0.5 Mn, bal Cu
711 (Copper-nickel) .05 Pb, 0.1 Fe, 0.2 In, 22-24 Ni, 0.15 Mn, bal Cu
715 Copper-nickel 30% .05 Pb, 0.4-0.7 Fe, I In, 29-33 Ni, I Mn, bal Cu
732 (Nickel-silver) 70 Cu, .05 Pb, 0.6 Fe, 3-6 In, 19-23 Ni, I Mn
745 Nickel-silver, 65-10 63.5-68.5 Cu, 0.1 Pb, 0.25 Fe, 9-11 Ni, 0.5 Mn, bal In
752 Nickel-silver, 65-18 63-65 Cu, 0.1 Pb, 0.25 Fe, 16.5-19.5 Ni, 0.5 Mn, bal In

(a) Maximum contents shown unless a range is indicated.

Source: Application Data Sheet, "Standard Designations for Copper and Copper Alloys (Wrought Products Only)",
Brochure 107/8, Copper Development Association, Inc., New York, N. Y.
 A-3

TABLE A-2. COMPOSITION LIMITS FOR SELECTED ALUMINUM ALLOYS

Alloy Chemical Composition(a), weight percent

Designation Si Fe Cu Mn Mg Cr Zn Ti Others
1100 I (Si + Fe) 0.2 0.05 0.1 0.15 total

2014 0.5-1.2 1 3.9-5 0.4-1.2 0.2-D.8 0.1 0.25 0.15

2024 0.5 0.5 3.8-4.9 0.3-D.9 1.2-1.8 0.1 0.25
2219 0.2 0.3 5.8-6.8 0.2-D.4 0.02 0.1 0.02-0.1 0.05-D.l5 V

3003 0.6 0.7 0.2 1-1.5 0.1 0.15 total

3004 0.3 0.7 0.25 1-1.5 0.8-1.3 0.25 0.15 total

5050 0.4 0.7 0.2 0.1 1-1.8 0.1 0.25 0.15 total
5052 0.5 (Si + Fe) 0.1 0.1 2.2-2.8 0.15-D.35 0.1
5056 0.3 0.4 0.1 0.05-D.2 4.5-5.6 0.05-D.2 0.1 0.15 total
5083 0.4 0.4 0.1 0.3-1 4-4.9 0.05-D.25 0.25 0.15
5086 0.4 0.5 0.1 0.2-D.7 3.5-4.5 0.05-D.25 0.25 0.15
5154 0.45 (Si + Fe) 0.1 0.1 3.1-3.9 0.15-D.35 0.2 0.2 0.15 total
5356 0.5 (Si + Fe) 0.1 0.05-D.2 4.5-5.5 0.05-0.2 0.1 0.06-D.2
5454 0.4 (Si + Fe) 0.1 0.5-1 2.4-3 0.05-D.2 0.25 0.2 0.15 total
5456 0.4 (Si + Fe) 0.1 0.5-1 4.7-5.5 0.05-D.2 0.25 0.2

6061 0.4-D.8 0.7 O.l5-D.4 0.15 0.8-1.2 0.04-D.35 0.25 0.15

7001 0.35 0.4 1.6-2.6 0.2 2.6-3.4 0.18-D.4 6.8-8 0.2

X7002 0.2 0.4 0.5-1 0.05-D.3 2-3 0.1-D.3 3-4 0.15
X7005 0.35 (Si + Fe) 0.1 0.2-D.7 1-1.8 0.06-D.2 4.2-5 0.15 0.08-D.2 Zr
X7006 0.35 (Si + Fe) 0.1 0.5 1.7-2.8 0.3 3.7-4.8 0.15
7039 0.3 0.4 0.1 0.1-D.4 2.3-3.3 0.15-0.25 3.5-4.5 0.1 0.15 total
7072 0.7 (Si + Fe) 0.1 0.1 0.1 0.8-1.3 0.15 total
7075 0.5 0.7 1.2-2 0.3 2.1-2.9 0.18-0.4 5.1-6.1 0.2
7079 0.3 0.4 0.4-D.8 0.1-D.8 2.9-3.7 0.1-D.25 3.8-4.8 0.1
7178 0.5 0.7 1.6-2.4 0.3 2.4-3.1 0.18-D.4 6.3-7.3 0.2

(a) Maximum values except for ranges indicated.