STP 576-1976

GALVANIC AND PITTING
CORROSION-FIELD AND
LABORATORY STUDIES
Two symposia
presented at the
1974 Materials Engineering Congress
AMERICAN SOCIETY FOR
TESTING A N D MATERIALS
Detroit, Mich., 22-23 Oct. 1974
ASTM SPECIAL TECHNICAL PUBLICATION 576

Robert Baboian, W . D. France, Jr.,
L. C. Rowe, and J. F. Rynewicz, editors
List price $29.75

04-576000-27
American Society for Testing and Materials

1916 Race Street, Philadelphia, Pa. 19103
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© BY AMERICAN SOCIETY FOR TESTING AND MATERIALS 1976
Library of Congress Catalog Card Number: 75-2510
NOTE
The Society is not responsible, as a body,
for the statements and opinions
advanced in this publication.
Printed in Cockeysville, Md.

February 1976
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Foreword
The two symposia. Galvanic Corrosion and Pitting Corrosion, were
presented at the 1974 Materials Engineering Congress held in Detroit,
Mich., 22-23 Oct. 1974, respectively. The symposia were sponsored by the
American Society for Testing and Materials Subcommittees GO 1.05 on
Laboratory Corrosion Tests and GO 1.07 on Galvanic Corrosion of Com-
mittee G-1 on Corrosion of Metals. L. C. Rowe, General Motors Corpora-
tion, presided as symposium chairman and W. D. France, Jr., General
Motors Corporation, served as symposium cochairman of the Symposium
on Pitting Corrosion. For the Symposium on Galvanic Corrosion, J. F.
Rynewicz, Lockheed Missiles and Space Company, presided as symposium
chairman and Robert Baboian, Texas Instruments, served as symposium
cochairman.
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Related
ASTM Publications
Stress Corrosion Cracking of Metals—A State of the Art, STP 518 (1972),
$11.75,04-518000-27
Manual of Industrial Corrosion Standards and Control, STP 534 (1974),

$16.75, 04-534000-27
Corrosion in Natural Environments, STP 558 (1974), $29.75, 04-558000-27
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A Note of Appreciation
to Reviewers
This publication is made possible by the authors and, also, the un-
heralded efforts of the reviewers. This body of technical experts whose
dedication, sacrifice of time and effort, and collective wisdom in review-
ing the papers must be acknowledged. The quality level of ASTM publica-
tions is a direct function of their respected opinions. On behalf of ASTM
we acknowledge their contribution with appreciation.
ASTM Committee on Publications
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Editorial Staff
Jane B. Wheeler, Managing Editor

Helen M. Hoersch, Associate Editor
Charlotte E. DeFranco, Senior Assistant Editor
Ellen J. McGlinchey, Assistant Editor
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Contents
Introduction
GALVANIC CORROSION
Electrochemical Techniques for Predicting Galvanic Corrosion—ROBERT

BABOIAN 5
Laboratory Studies of Galvanic Corrosion of Aluminum Alloys—FLORIAN

MANSFELD AND J. V. KENKEL 20
Current Density Distribution on Composite Structures Under Cathodic Protec-

tion in Seawater—K. G. COMPTON 48
Electrochemical Examination of Fused Joints Between Metals—K. G. COMPTON

AND J. A. T U R L E Y 56
Galvanic Corrosion of Underground Power Distribution Cable Materials—

GEORGE SCHICK AND D. A. MITCHELL 69
Galvanic Coupling of Some Stressed Stainless Steels to Dissimilar Metals

Underground—E. ESCALANTE AND W. F. GERHOLD 81
Air, Soil, and Sea Galvanic Corrosion Investigation at Panama Canal Zone—
M. A. PELENSKY, i. J. JAWORSKI, AND A. GALLACCIO 94
PITTING CORROSION
Localized Corrosion Attack on Carbon Steel—Case Histories of Service

Failures—HENRY suss 117
Pitting of Galvanized Steel in Controlled Clean Air Environments—J. w.

SPENCE AND F . H . H A Y N I E 132
Pitting Corrosion of Titanium Tubes in Hot Concentrated Brine Solutions—

L. C. COVINGTON 147
Pitting Corrosion in Copper Tubes in Cold Water Service—F. J. CORNWELL,

G. WILDSMITH, AND P. T. GILBERT 155
Pitting Caused by Chlorides or Sulfates in Organic Media—FLORIAN MANSFELD 180
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Measurement and Evaluation of Pitting Corrosion—L. C. ROWE 203
Interpretation of Pitting Corrosion Data from Statistical Prediction Interval
Calculations—D. L. CREWS 217
Statistical Aspects of Crevice Corrosion in Seawater—D. B. ANDERSON 231
Solution Chemistry of Pitting of Iron in Artificial Seawater—c. w. PETERSEN 243
Use of Rapid-Scan Potentiodynamic Techniques to Evaluate Pitting and Crevice
Corrosion Resistance of Iron-Chromium-Nickel Alloys—p. E. MORRIS 261
Compilation of Literature References on Pitting Corrosion 276
Summary 295
Index 299
Copyright by
University of
Introduction
Galvanic and pitting corrosion are widely different forms of degrada-

tion; however, both lead to the same result, premature failure. Galvanic
corrosion is the accelerated corrosion of a metal due to an electrical con-
tact with a more noble metal or nonmetallic conductor in a corrosive
electrolyte. Pitting corrosion is attack of a metal surface at a point or
small area resulting in the formation of cavities (or pits).
The problems associated with galvanic and pitting corrosion have been
extensively investigated but are far from being solved. Therefore, ASTM
Committee G-1 on Corrosion of Metals sponsored a symposium from
which the papers form the basis of this STP. These papers, which cover
practical aspects, mechanisms, and testing techniques, will be useful to
those who need to prevent, understand, or test for galvanic and pitting
corrosion.
The galvanic corrosion papers include laboratory investigations and
field testing results. In addition to a review of electrochemical techniques
for predicting galvanic corrosion, laboratory studies include the behavior
of aluminum alloys coupled to iron, nickel, and titanium, welded materials
exposed to seawater, and cathodic protection of dissimilar metal assemblies.
Reports on field tests include such subjects as galvanic corrosion of under-
ground power cables, galvanic corrosion of stressed stainless steels exposed
in various soils, and the coupled behavior of structural materials ranging
from magnesium to titanium in atmospheric, seawater, and soil environ-
ments.
The pitting corrosion papers include descriptions of new test techniques
such as rapid scan potentiodynamic measurements and a multiple crevice
test assembly for statistical analysis. A review of the measurement and
evaluation of pitting corrosion provides a standardized approach to the
examination of this type of corrosion. Practical applications information
on pitting corrosion of copper tubing in cold water service and evaluation
of galvanized steel in corrosive atmospheres are included.
The information in the book should be useful to those involved with
materials research and development, material selection, materials processing.
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2 GALVANIC AND PiniNG CORROSION
and corrosion evaluation and test techniques. In addition to the wide range
of materials investigated, the broad range of conditions covered include
atmospheric, oil, and aqueous environments. In addition to being a
valuable guide for testing and evaluation of galvanic and pitting corrosion,
this STP provides practical information on these two forms of corrosion
and a direction for future investigation.
J. F. Rynewicz
Lockheed Missiles and Space Company,
Sunnyvale, Calif. 94088; chairman of
Galvanic Corrosion symposium.
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Galvanic Corrosion
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Robert Baboian1
Electrochemical Techniques for Predicting

Galvanic Corrosion
REFERENCE: Baboian, Robert, "Electrochemical Techniques for Predicting

Galvanic Corrosion," Galvanic and Pitting Corrosion—Field and Laboratory
Studies, ASTM STP 576, American Society for Testing and Materials, 1976,
pp. 5-19.
ABSTRACT: The various electrochemical techniques for predicting galvanic cor-
rosion behavior of metals are described. Each method is evaluated on the basis
of practicality using specific galvanic couples as examples. The paper describes
some serious shortcomings of the existing techniques and warns of the dangers of
their improper use.
KEY WORDS: corrosion, galvanic corrosion tests, metals, alloys, galvanic
series, zero resistance ammeter, localized corrosion, polarization measurements,
galvanic current, mixed potential
Corrosion of metals can be treated by application of the mixed potential

theory first described by Wagner and Traud [7].2 The theory is based on
two simple hypotheses. First, any electrochemical reaction can be divided
into two or more oxidation or reduction reactions, and second, there can
be no net accumulation of electrical charge during an electrochemical
reaction. That the various partial reactions can be treated separately, as
stated in the first hypothesis, can be demonstrated experimentally.
The oxidation (corrosion) and reduction reactions at a reversible elec-
trode are illustrated graphically in Fig. 1. The equation relating reaction
rate and overvoltage is
>?act = ±/8 log 4- (1)

lo
Equation 1 is called the Tafel equation and 0 is termed the Tafel constant or
slope. Notice that for high overvoltage values, the relationship is a linear
function on a logarithmic scale (Fig. 1). The value for @ is usually between
1
Manager, Electrochemical and Corrosion Laboratory, Texas Instruments Incorporated,
Attleboro, Mass. 02703.
2
The italic numbers in brackets refer to the list of references appended to this paper.
5
Copyright^ 1976 by ASTM International www.astm.org
Copyright by ASTM Int'l (all rights reserved); Fri Jan

University of Washington (University of Washington) pursuant to
6 GALVANIC AND PITTING CORROSION
• T- •
—T r —r
0.2 -
0.1
~
< ''^^r
^ EOUILIBRIUM
0.0 ^ * POTENTIAL -
0.1
0.2
• 1 1 1
10' lO-J
CUMENT DENSITY Ima/cm')
FIG. 1—Activation polarization curves for a reversible electrode system.
0.05 and 0.15 V. In Fig. 1, /3 is 0.1 V, so that for a 0.1 V change in over-
voltage, the reaction rate changes by one order of magnitude. At the
equilibrium potential, the net rate of oxidation, U, equals the net rate of
reduction.
Under the simplest circumstances, metallic corrosion would involve only
two reactions, oxidation and reduction. The corrosion of iron in sulfuric
acid involves the anodic dissolution of iron and the evolution of hydrogen.
This is demonstrated by the polarization curves for iron in 1.0 A'^ sodium
sulfate in Fig. 2. The first hypothesis of the mixed potential theory is
satisfied if one considers that each reaction has its own reversible potential
and polarization parameters. The second hypothesis, that the total rate of
oxidation equals the total rate of reduction, is only satisfied at the inter-
section ^corr the corrosion or "mixed" potential. At this point, the rate
of iron dissolution is equal to the rate of hydrogen evolution. The potential
is so displaced from the equilibrium potential that the reverse reactions
occur at a negUgible rate and do not influence the corrosion rate.
In Fig. 2, the data indicate that iron will corrode at a rate of about
5.0 mA/cm^ and will exhibit a potential of about —0.814 V versus the
saturated calomel electrode (SCE).
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BABOIAN ON ELECTROCHEMICAL TECHNIQUES 7
•o.rpr
10° 10 • 102
CURRENT DENSITY (ua/cmZ)
FIG. 2—Polarization behavior of iron in 1.0 N sodium sulfate.
One of the most important applications of the mixed potential theory to

corroding systems is the treatment of galvanically coupled metals [2].
When two different corroding metals are coupled electrically in the same
electrolyte, both metals are polarized so that each corrodes at a new rate.
In Fig. 3 the corrosion potentials and polarization parameters for un-
coupled Metals A and B are shown. Metal A is more noble than Metal B
in that the equilibrium potential is less negative. When the mixed potential
theory is applied to the individual reactions (A/A+, H2/H+, B/B+, H2/H+)
the uncoupled corrosion rates are /corr.A for Metal A and /"corr.B for Metal B.
When equal areas of Metals A and B are coupled, the resultant mixed
potential of the system Ecorr.AB is at the intersection where the total oxida-
tion rate equals the total reduction rate. The rate of oxidation of the
individual coupled metals is such that Metal A corrodes at a reduced
rate /'con-,A and Metal B corrodes at in increased rate /'corr.B-
Electrochemical techniques for predicting galvanic corrosion are based
on mixed potential theory. These include potential measurements, current
measurements, and polarization measurements.
These techniques have been used successfully in various applications;
however, caution must be taken not to depend exclusively on one tech-
nique for all circumstances. Frequently, the use of electrochemical tech-
niques leads to erroneous results. This is usually due to improper experi-
mentation or interpretation of the system. In some cases, more time
consuming, conventional investigations are required.
In general, it should be emphasized that in making the electrochemical
measurement, one does not disturb the system so that results are meaning-
•
TOTAL REDUCTION RATE
X.** 'corr.A X . ^ ^
^'corr.A \ ^ X \ .' ^
^ 3P *"• ^ ^*^°" '^^
11
^ X corr.B ^ ^
'o A
TOTAL OXIDATION RATE
'o B
LOG CURRENT DENSITY
FIG. 3—Mixed potential behavior of galvanically coupled Metals A and B.
less. Also, it is important that the measurements be conducted in the actual

corrosive environment or in one which closely simulates that environment.
Potential Measurements
The use of potential measurements for predicting galvanic corrosion is
based on the measurement of £'corr, the corrosion potential of metals.
When the metals are arranged according to their potential measured in a
particular environment (Table 1) the result is termed the galvanic series [3].
In general, the corrosion rate of the more noble metal in a galvanic
couple will be reduced and that for the more active metal will be increased.
In some cases, the separation between the two metals in the galvanic series
gives an indication of the magnitude of these effects.
When the polarization characteristics for metals are straightforward
such as demonstrated in Fig. 4 for lead, iron, and zinc, the galvanic series
is quite useful in predicting not only the relative galvanic behavior of the
metals but also the magnitude of the effects of coupling the metals. The
order and relative positions of these three metals in the galvanic series
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TABLE 1—Arrangement of metals and alloys in a galvanic series based on potential measure-
ments in seawater velocity of flow, 13 ft Is, seawater temperature, 25°C (J7°F)(Srom LaQue).
Zinc
Aluminum (Alclad 3S)
Aluminum 3S-H
Aluminum 61S-T
Aluminum 52S-H
Cast iron
Carbon steel
Stainless steel Type 430 (17C)
Nickel-resistant cast iron (20N)
Stainless steel Type 304 (18C, 8N)
Nickel-resistant cast iron (30N)
Nickel-resistant cast iron (20N -f Cu)
Naval-rolled brass
Yellow brass
Copper
Red brass
Composition G bronze
Admiralty brass
90-10 cupro nickel (0.8 Fe)
Nickel
Stainless steel Type 316 (18 C, 12N, 3M)
Inconel
Titanium (commercial)
Silver
Titanium (high purity from iodide)
Stainless steel Type 304 (18 C, 8N)
Hastelloy C
Monel
Stainless steel Type 316 (18C, 12N, 3M)
•
Pb
• Fe _
: •
Zn
•
-1.4 1 1
10 10' 10'
CURRENT DENSITY I \it/cm^ )
FIG. A^Potentiodynamic polarization curves for lead, iron, and zinc in 5 percent sodium
chloride solution i30°C).
(Table 1) is correct for the 5 percent sodium chloride environment. Meas-

urement of the corrosion potential for these metals is sufficient.
There are several factors which lead to drawbacks in the use of potential
measurements and the galvanic series. First, the formation of films on
the metal surface will influence the corrosion rate so that over a wide
range of potentials the surface remains passive [4]. This is illustrated
(Fig. 5) by the polarization curves for Types 310 and 434 stainless steel
in 5 percent sodium chloride solution. Their positions in the galvanic
series (according to Ecorr) may indicate what effects they may have on other
metals in a galvanic couple, but the reverse is not necessarily true due to
their wide passive potential ranges [5].
The potential variation with time in a particular environment is another
concern when constructing the galvanic series [4]. The relative position of
metals in the series may change, depending on the time of immersion.
For example, in Fig. 6 the measured corrosion potentials for Types 304
and 316 stainless steel vary considerably even after 10 or 15 months im-
mersion in seawater. The relative position of nickel. Type 304 stainless
steel, and copper-nickel alloy clearly depends on the time of potential
measurement.
The polarizability of metals varies according to the environment in
which they are subjected. Metals which are easily polarized have a lesser
affect than ones which are not readily polarized. Simple measurement of
the corrosion potential does not provide information on the polarizability
of the metal so that in many cases their relative positions and their separa-
tion in the galvanic series are not a valid basis for predicting galvanic
corrosion behavior.
lO-l 10» 10' 102

CURRENT DENSITY ||ia/cm2)
FIG. 5—Potentiodynamic polarization curves for Types 434 and 310 stainless steel in 5
percent sodium chloride solution (30°C).
BABOIAN ON ELECTROCHEMICAL TECHNIQUES 1 1
u
M
* 0.1
e
> 0.0
-I
S
&.
-0.2
S 10
EXPOSURE (MONTHS I
FIG. 6—Variation of corrosion potential with time for nickel 90 to 10 copper-nickel.

Types 304 and 316 stainless steel in seawater.
Current Measurements
Measurement of galvanic currents between galvanically coupled metals
is based on zero resistance ammeter techniques [6]. The basic zero re-
sistance ammeter circuit, which has been used extensively, is shown in
Fig. 7. The galvanic current is measured by an ammeter. A, by adjusting
the voltage, E, or resistance, R, so that the potential difference between
the two elements is zero as indicated by the electrometer, V. Since short
circuiting in a galvanic couple is indicated by zero potential drop, this
current is the true short circuit current. For continuous recording of
galvanic currents, the basic circuit is simplified to include a decade re-
sistance box adjusted so that a recorder, set to 1 mV full scale, indicates
the potential between the two elements [7]. The galvanic current is calcu-
lated knowing the resistance and the potential.
The data in Fig. 8 for galvanic couples of copper with 1006 carbon steel,
and Types 409 and 430 stainless steel were obtained using the basic zero
-^
T
R
I W^WvVv
FIG. 7—Schematic circuit of elementary zero resistance ammeter.
1.4
1.2 .^^^^
^ * * * * * * ' * . » ^ ^ 10O6C.S.
E
K 0.8
• 4)»«:T
oc
O 0.€
o
K
o °*
02
_ ^ 430SS
FIG. 8—Galvanic current versus time for 1006 carbon steel and 409 and 430 stainless steel
coupled to copper in 5 percent sodium chloride solution (30°C).
resistance ammeter circuit. The magnitude of the galvanic current provides

an indication of the severity of galvanic corrosion which occurs in the
specific 5 percent sodium chloride environment. Notice the slow drift to
lower galvanic currents for 1006 carbon steel with time. The sharp increase
in galvanic current for Type 409 stainless steel is due to the initiation of
localized corrosion. Initiation of localized corrosion is not indicated by
the galvanic current for Type 430 stainless steel. This effect is observed,
however, beyond the 60-h test time shown in Fig. 8.
The drawbacks of the basic zero resistance ammeter circuit shown in
Fig. 7 are (a) during time periods in which the circuit is not balanced,
polarization of the members in the galvanic couple occurs leading to
incorrect values or long recovery times or both and (Jb) the continuous
monitoring of the galvanic current requires constant attention. These
disadvantages have been the focal point of new developments and im-
provements in the zero resistance ammeter techniques.
The development of self balancing, zero resistance ammeters allows
continuous monitoring of galvanic currents. This was accomplished by
electronic automatic adjustment of either R [8^ or E [9] in the basic circuit.
High-input resistance voltage sensing systems placed across the galvanic
cell allow more accurate measurements in high-resistance electrolytes.
More recent developments include the use of a potentiostat incorporating
the operational amplifier circuitry [70]. In the arrangement in Fig. 9 [7/],
the control potential of the potentiostat is set to zero volt. One member of
the galvanic couple is connected to the working electrode terminal while
the other is connected to the reference electrode terminal. The auxiliary
electrode terminal is connected directly to the reference electrode terminal
whereby the galvanic current is indicated directly by the potentiostat current
meter, or, it is connected through an external feedback resistor (7?/ in
Fig. 9) and the galvanic current is measured by a voltmeter between the
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Potentlostol
WE RE AE
'^y,-^
^:
i It -vVVNAr
f. ff.
FIG. 9—Schematic circuit for use of a potentiostat as a zero resistance ammeter (iJe/11).
auxiliary and working electrode terminals. A null balance is thus main-

tained by means of the potentiostat solid state operational amplifier
circuit.
A commercial operational amplifier can be used as the voltage control
and will give the same results as a potentiostat. The use of a simple opera-
tional amplifier as an alternate to the potentiostat was described by Lauer
and Mansfeld [12] and later by Henry and Wilde [13]. The advantages
here include lower cost and smaller size. In Fig. 10 [12], one member of
the galvanic couple is connected, through ground, to the positive input
of the amplifier. The other is connected to the negative of the high-gain
operational amplifier. The members of the galvanic couple are maintained
at zero potential difference and the galvanic current is derived from Vo,
the voltage output of the amplifier, and /?„, the feedback resistance (stan-
dard resistor). This arrangement allows measurements to be made in high
resistivity electrolytes and continuous monitoring of the galvanic current
POTENTIAL
\ELECTROOE 2
^REFERENCE ELECTRODE
ÊLECTRODE I
FIG. 10—Schematic circuit of a zero resistance ammeter using an operational amplifier

(Ref\l).
14 GALVANIC AND PIHING CORROSION
using Strip chart recorders. The reference electrode in Fig. 10 is only

used to measure the mixed potential of the galvanic couple.
Typical galvanic current data obtained by Mansfeld [75] with the
operational amplifier circuitry are shown in Fig. 11. The zero resistance
current is plotted versus time for five aluminum alloys coupled to Type
4130 steel in 3.5 percent sodium chloride solution. The data show that all
of the aluminum alloys are anodic to the steel in this environment. How-
ever, the relative position of the five alloys shifts with time as indicated by
the crossing of the galvanic current curves during the 24-h time period.
Longer test times are, therefore, required in many instances. This is espe-
cially true when localized corrosion such as pitting is possible in the
galvanic couple. Frequently, several weeks induction period is observed
before galvanic pitting is initiated [4].
The measured galvanic current is not always a measure of the true
corrosion current because it is the algebraic sum of the currents due to
anodic and cathodic reactions. When cathodic currents are appreciable
at the mixed potential of the galvanic couple, the measured galvanic current
will be significantly lower than the true corrosion current. Thus, large
difi"erences between the true corrosion rate calculated by weight loss and
the rate obtained by galvanic current measurements have been observed.
Calculation of the true corrosion current by correcting the measured
galvanic current in some cases involves more work than actually measuring
the corrosion rate by conventional weight loss techniques.
FIG. 11—Galvanic current versus time for aluminum alloys coupled to 4130 steel in 3.5
percent sodium chloride solution (Ref 13).
Polarization Measurements
Corrosion behavior of galvanically coupled metals was described pre-
viously (Fig. 3) using mixed potential theory. The information required
are anodic polarization curves for the individual metals in the galvanic
couple and the mixed potential £corr in the actual electrolyte environment.
Since the cathodic reactions also influence the mixed potential, measure-
ments must be made duplicating the environment (such as geometry and
area ratio) of the couple. It is important to note that this treatment can be
applied to two [4,5,14] or more [15] metals in a galvanic couple.
In this treatment, the corrosion potential of the galvanic couple is
measured, and the nature of corrosion in this potential region is deter-
mined for each metal from the individual polarization curves. For example,
anodic polarization curves for DHP copper and 1006 carbon steel in
5 percent sodium chloride solution are shown in Fig. 12. The corrosion
potentials of the isolated metals, obtained under actual corroding condi-
tions in aerated 5 percent sodium chloride solution, are used to determine
the rates of corrosion /corr.cu and /oorr.Fe from the polarization curves in
Fig. 12.
When copper and iron are coupled galvanically under these conditions,
the mixed potential is £'corr; and, from the polarization curves in Fig. 12,
the rate of corrosion of copper, i'corr.cu, is decreased and the rate of cor-
rosion of iron, /'corr.Fe, Is Incrcascd.
Increasing the copper/iron area ratio in the galvanic couple shifts the
mixed potential (£'oorr) to less negative values so that galvanic corrosion
of iron is accelerated.
An important application of the use of polarization measurements in
galvanic corrosion is in the prediction of localized corrosion. Polarization
techniques and critical potentials have been used widely as a measure of
pitting and crevice corrosion susceptibility of alloys in chloride solution
[16-19]. For example, a schematic potentiodynamic polarization curve
for a stainless steel in sodium chloride solution is shown in Fig. 13. The
solid line represents anodic polarization from active to noble potentials.
g 10» 10-2 10° 10= 10* lo' 10"

CURRENT DENSITY | (Ja/cmZ )
FIG. 12—Galvanic corrosion behavior of copper and iron in 5 percent sodium chloride
solution (30°C) using polarization measurements.
REGION m
10-1 10° 10' 10^ 10^

CURRENT DENSITY (M'/cni' I
FIG. 13—Schematic potentiodynamic polarization curve for stainless steel in 5 percent

solution chloride solution showing three corrosion potential regions.
The dashed line represents reverse polarization back to more active po-
tentials.
Polarization above the critical breakdown potential, Ec, results in a
marked increase in current density due to initiation of pitting. Reverse
polarization below Ec does not reduce the current density appreciably,
indicating that propagation of existing pits and crevice corrosion occurs.
At the critical potential, Ep, the current density approaches zero. Below E,,,
propagation of existing pits and crevice corrosion does not occur.
The corrosion behavior of stainless steel can be thus separated into
three potential regions: Region I, where protection from pitting and
crevice corrosion are observed; Region II, where propagation of existing
pits and crevice corrosion occurs; and Region III, where initiation of
pitting and crevice corrosion occurs.
Thus, galvanic couples of stainless steel can lead to three performance
categories in chloride containing environments.
In Fig. 14o, the mixed potential for the galvanic couple between stainless
steel A and Metal B lies in Region III where initiation of pitting and
crevice corrosion on the stainless steel occurs. This behavior is observed in
the presence of stray currents or sometimes in galvanic couples with
platinum group metals.
In Fig. \Ab, the mixed potential lies in Region II, the crevice corrosion
and pit propagation region for stainless steel. Types 430 and 304 stainless
steel undergo this type of corrosion when coupled to copper.
In Fig. 14c, stainless steel A and Metal B mixed potential lies in Region I
where protection from pitting and crevice corrosion occurs. Stainless
steels, such as Type 304, are protected from this type of localized corrosion
in galvanic couples with carbon steel because their mixed potentials are
in this region.
LOG CURRENT DENSITY
LOG CURRENT DENSITY
FIG. 14—Schematic polarization curves showing corrosion behavior oj stainless steel

A and Metal B in galvanic couple: (a) mixed potential is within Region III (b) mixed potential
is within Region II; and (c) mixed potential is within Region I.
LOG CURRENT DENSITY
FIG. 14—{continued).
Summary
The following electrochemical techniques are used in predicting the

galvanic corrosion behavior of metals: potential measurements, current
measurements, and polarization measurements.
The success of these techniques is based on making appropriate measure-
ments in the actual environment to which the galvanic couple is exposed.
In many cases, simple measurement of the potential of each member in a
galvanic couple is sufficient to predict the galvanic corrosion behavior.
The resulting galvanic series of metals for a particular environment can
be quite useful. However, frequently, more precise information is required.
Measurement of galvanic currents can furnish more useful information
regarding galvanic corrosion. Recent developments with zero resistance
ammeters allow continuous measurement of the galvanic current during
true short-circuiting conditions. This current, however, is not always
equivalent to the corrosion current because it is the algebraic sum of the
currents due to anodic and cathodic reactions. Thus, where cathodic
currents are significant, the measured galvanic current may be appreciably
smaller than the true corrosion current.
The use of polarization measurements in conjunction with the mixed
potential of a galvanic couple can provide precise information regarding
the behavior of galvanically coupled metals. This treatment has been
used successfully for three member couples as well as for predicting galvanic
localized corrosion.
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions au
References
[/] Wagner, C. and Traud, W., Zeitschrift fur Electrochemie, Vol. 44, 1938, p. 391.
[2] Fontana, M. and Greene, N. in Corrosion Engineering, McGraw-Hill, New York.
[3] LaQue, F. L. in Corrosion Handbook, Wiley, New York.
[4] Baboian, R. in Localized Corrosion—Cause of Metal Failure, ASTM STP 516, Ameri-
can Society for Testing and Materials, 1972, pp. 145-163.
[J] Baboian, R. and Haynes, G. S. in Corrosion in Natural Environments, ASTM STP 558,
American Society for Testing and Materials, 1974, pp. 171-184.
[6] Brown, R. H. and Mears, R. B., Transactions, Electrochemical Society, Vol. 74, 1938,
p. 510.
[7] Greene, N. D., "Experimental Electrode Kinetics," Rensselaer Polytechnic Institute,
Troy, N.Y., 1965.
[8] Godard, H. P., Corrosion, Vol. 7, 1951, p. 93.
[9] Maker, D. R. and Francis, H. T., Journal of the Electrochemical Society, Vol. 102,
1955, p. 669.
[10] Devay, J., Lenyal, B., and Meszaros, L., Acta Chimica Academiae Scientiarum
Hungaricae, Vol. 62, 1969, p. 157.
[11] von Fraunhofer, J. A. and Staheli, P. J., Corrosion Science, Vol. 12, 1972, p. 767.
[12] Lauer, G. and Mansfeld, F., Corrosion, Vol. 26, 1970, p. 504.
[13] Mansfeld, F., Werkstoffe und Korrosion, Vol. 25, 1974, p. 578.
[14] Baboian, R., Transactions, Society of Automotive Engineers, Vol. 81, 1972, p. 1117.
[15] Baboian, R., "Clad Metals in Automotive Trim Applications," Paper 710276, Society
of Automotive Engineers, Detroit, 1971.
[16] Horvath, J. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 115, 1968,
p. 791.
[17] Pourbaix, M., Klimzack-Mathieiu, L., Martens, C., Meunier, J., Vanleugenhaghe, C.,
DeNuncky, L., Laverys, J., Neelemens, L., and Warzee, M., Corrosion Science, Vol. 3,
1963, p. 239.
[18] Defranoux, J. M., Corrosion Science, Vol. 3, 1963, p. 75.
[19] Pourbaix, M., Corrosion, Vol. 26, 1970, p. 431.
Florian Mansfeld1 and J. V. Kenkel1
Laboratory Studies of Galvanic Corrosion

of Aluminum Alloys
REFERENCE: Mansfeld, Florian and Kenkel, J. V., "Laboratory Studies of

Galvanic Corrosion of Aluminum Alloys," Galvanic and Pitting Corrosion—Field
and Laboratory Studies, ASTM STP 576, American Society for Testing and
Materials, 1976, pp. 20-47.
ABSTRACT: In a systematic study of galvanic corrosion of aluminum alloys the

effects of the dissimilar metal, the solution composition, and area ratio have been
evaluated using galvanic current and weight loss measurements. In 3.5 percent
sodium chloride, galvanic corrosion rates of the aluminum alloys 1100, 2024, 2219,
6061, and 7075 decrease with the nature of the dissimilar metal in the order:
silver > copper > 4130 steel » stainless steel » nickel > Inconel 718 » Ti-6A1-
4V cs Haynes 188 > tin > cadmium. Coupling to zinc did not lead to cathodic
protection of the aluminum alloys as shown by weight loss data, although the
aluminum alloys were the cathode in the aluminum-zinc couple. The potential
difference of uncoupled dissimilar metals has been found to be a poor indicator
of galvanic corrosion rates. Dissolution rates of aluminum alloys coupled to a given
dissimilar material are higher in 3.5 percent sodium chloride than in tap water
and distilled water where they are found to be comparable. The effect of area ratio
AC/AA has been studied in 3.5 percent sodium chloride for area ratios of 0.1, 1.0,
or 10. The galvanic curent was found to be independent of the area of the anode,
but directly proportional to the area of the cathode. The galvanic current density
i„A with respect to the anode has been found to be directly proportional to the
area ratio (i„A = ki AC/AA), while the dissolution rate rA of the anode was related
to area area ratio by rA = fc2 (1 + AC/AA). The results obtained have been ex-
plained based on mixed potential theory. Electrochemical methods for measure-
ments of galvanic currents are described in the Appendix.
KEY WORDS: corrosion, aluminum alloys, galvanic corrosion
Accelerated corrosion of dissimilar metals which are electrically coupled

and exposed to a corrosive environment is one of the most common and
most severe forms of corrosion. Although the danger of galvanic corrosion
has been recognized generally, very little work has been done to quantita-
tively measure the extent of corrosion of various galvanic couples and
1
Member of technical staff and staff associate, respectively, Science Center, Rockwell
Internationa], Thousand Oaks, Calif. 91360.
20
Copyright by ASTM Int'l (all rights reserved); Fri Jan 1

University of Washington (University of Washington) pursuant to Lic
MANSFELD AND KENKEL ON CORROSION OF ALUMINUM ALLOYS 21
use such measurements as a basis for a ranking of galvanic couples. Usually

uncoupled metals and alloys instead of actual galvanic couples are ranked
in a galvanic series according to their corrosion potentials in a given
environment, for example, seawater [1].'^ While this type of classification
of metals and alloys might be quite useful as an indication of general
trends in galvanic corrosion, it cannot give an indication of the actual
extent of galvanic corrosion when dissimilar materials are coupled. As
pointed out recently [2,3], the magnitude of galvanic corrosion depends not
only on the potential difference of dissimilar metals, but also on kinetic
parameters such as corrosion rates or exchange current densities of the
uncoupled materials and Tafel slopes, and on area ratios.
In light of the rather complicated interaction of reduction and oxidation
reactions on coupled metals, it is important to measure directly the extent
of galvanic corrosion of those materials which may come in electrical
contact in various structures rather than rely on measurements of only
one of the parameters involved, for example, potential differences. Various
methods for measurements of galvanic current have been summarized in
the Appendix. The authors have been using the zero impedance ammeter
described by Lauer and Mansfeld [4] and applied in this laboratory to
evaluation of inorganic conversion coatings on aluminum alloys [5] and to
studies of the effect of metallic coatings on PH13-8Mo on galvanic cor-
rosion of aluminum alloys in sodium chloride [6].
This paper summarizes results of a systematic investigation of galvanic
corrosion in which the galvanic interaction of 20 metals and alloys have
been measured in order to establish a galvanic series based on quantitative
measurements of dissolution rates of the metals in a galvanic couple.
Results for the 95 galvanic couples in which an aluminum alloy is one of
the two dissimilar metals are summarized here for immersion in air-
saturated 3.5 percent sodium chloride [7]. Also included are results of
galvanic corrosion tests in tap and distilled water for some selected couples
[8] and studies of the effect of area ratio [9].
Experimental
Materials and Test Method
Table 1 lists the materials studied. The specimens were flat coupons
(1 by 3 in. by variable thickness). They were degreased for 5 min in boiling
benzene, cleaned by conventional chemical methods, if necessary, and
weighed to 0.1 mg. The specimens to be coupled were then placed into a
lucite holder with a J^ hy J^ by 3^ in. Incite spacer between the specimens
as described elsewhere [5,6]. About 20 cm^ of each specimen were exposed
to the electrolyte.' After assembly, the holder containing the specimens
' The italic numbers in brackets refer to the list of references appended to this paper.
' In studies of the effect of area ratio, this holder was not used.
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions author
TABLE 1—List of materials studied.
Ag (99.9%) Type 304L SS Ti-6A1-4V

Cu(OFHC) Type 347 SS Al 1100-0
Ni 270 PH13-8MO Al 2024-T851
Sn (99.9999%) A286 Al 2219-T87
Cd (99.98%) 4130 steel Al 6061-T651
Zn(99.9%) Haynes 188 Al 7075-T76
Type 301 SS Inconel 718
was placed in a solution of air-saturated 3.5 percent sodium chloride and

the corrosion potential of the two uncoupled materials followed for
15 min immediately after immersion (all potentials refer to the saturated
calomel electrode (SCE)). The specimens were then connected to the zero
impedance ammeter [4] (see Fig. 15 in the Appendix). The output of this
instrument, which is proportional to the galvanic current Ig, was connected
to a two-pen strip-chart recorder. The potential 4>g of the couple was also
recorded continuously for 24 h. From plots of galvanic current Ig versus
time t, the average galvanic current density ig = Ig/A, where A is the area
of the aluminum alloy tested, was calculated by graphical integration.
After the 24-h test, the aluminum alloys were deoxidized using a com-
mercial cleaner, washed, dried, and weighed again. The weight loss caused
by the deoxidizing treatment was also measured using separate uncorroded
aluminum specimens, and this correction was applied to the weight loss of
the corroded specimen. If necessary, the other materials were freed of
corrosion products using standard techniques (National Association of
Corrosion Engineers Laboratory Corrosion Testing of Metals for the
Process Industries (TM-01-69)). The corrected weight loss, the duration
of the test, and the specimen area were used to calculate the dissolution
rate r of the specimen in milligrams per square decimeters per day (mdd).
Results
Effect of the Dissimilar Metal [7]

Corrosion Parameters of Uncoupled Aluminum Alloys—All galvanic
couples studied include one aluminum alloy. In order to relate galvanic
couple data to corrosion parameters of aluminum alloys, the corrosion
rates of uncoupled aluminum alloys were determined in 24-h immersion
tests. Table 2 shows corrosion potentials $corr (average of 19 tests, 15-min
exposure) and corrosion rates ro (average of 3 tests, 24 h).
Galvanic Current Data—Typical galvanic current data are shown in
Figs. 1 and 2. Figure 1 shows that the galvanic current Ig is appreciably
higher when 7075 aluminum is coupled to copper than when it is coupled
to Type 304 stainless steel (SS) or Ti-6A1-4V. When coupled to zinc, the
TABLE 2—Corrosion potentials and corrosion rates of uncoupled aluminum alloys, 3.5
percent sodium chloride, 21 ± 1°C.
* corr millivolt
Al Alloy versus SCE ro, mdd
1100 - 756 ± 39 0.24

2024-T851 - 733 ± 4 5.25
2219-T87 - 724 ± 6 4.62
6061-T651 - 756 ± 28 0.56
7075-T76 - 814 ± 18 0.95
galvanic current is negative with respect to aluminum, because zinc was

the anode in the galvanic couple. After an initial period of 2 h, the galvanic
current remained more or less constant except for the couple involving
cadmium, where the current increased constantly.
Despite the appreciable initial potential differences between 7075 alumi-
num and copper, Type 304 SS or Ti-6-4, respectively, the galvanic potentials
of the corresponding couples with 7075 aluminum have similar values
which are only slightly more noble than the corrosion potential of the
uncoupled aluminum alloy (Fig. Xb) [7]. This is probably due to the fact
that the pitting potential is also only slightly more noble than the corrosion
potential of the aluminum alloys and the fact that the aluminum alloys
cannot be polarized more noble than to the pitting potential.
Figure 2 shows that similar results are obtained when the five aluminum
alloys are coupled to the same, more noble material, 4130 steel. A com-
parison of the curves in Fig. 2 with those in Fig. 1 shows that coupling of
aluminum alloys to copper leads to higher galvanic currents than coupling
to 4130 steel which in turn produces higher galvanic currents than the
stainless steel and the titanium alloy.
Based on the galvanic current Ig versus time t traces the galvanic current
density /„ with respect to the aluminum alloy in a galvanic couple has been
calculated. Tables have been prepared [7] for each of the aluminum alloys
studied in which the galvanic couples have been ranked according to the
value of /„. Table 3 is an example for such a galvanic series; in this case,
6061 aluminum has been coupled to 19 dissimilar metals and alloys. Also
listed in Table 3 are the corrosion potential differences Ac^" of the two
uncoupled metals before the start of the galvanic current test and the
dissolution rates TA based on weight loss data (see following section).
The overall ranking in the last column of Table 3 is obtained by a ranking
of all 95 couples studied (for details, see Ref 7).
Weight Loss Data—The dissolution rate VA of the aluminum alloy in the
galvanic couples as calculated from weight loss data has also been listed
in Table 3.
1 1 1
(a)
Al 7075
^ Cu
V.
^ SS304
' '"—- .
,~ T1-6-4 .,,-• —
' f——^ '
^ • '
^^ Zn
1 1 1
20 24
-800 {&!_
FIG. 1—Time behavior of the galvanic current Ig for aluminum 7075 coupled to copper,
Type 304L SS, Ti-6A1-4V^ cadmium, or zinc in 3.5 percent sodium chloride.
20 24
t(hours)
FIG. 2-—Time behavior of the galvanic current Ig for aluminum alloys coupled to 4130 steel
in 3.5 percent sodium chloride.
Only very small weight changes were recorded for silver, copper, nickel,
the stainless steels, Ti-6A1-4V, Haynes 188, and Inconel 718. The 4130 steel
was covered with rust after galvanic tests; after removal of corrosion
products, weight gains or weight losses were found ( — 7 to + 8 mdd). The
dissolution rates for tin ranged between 0 and 5 mdd, those for cadmium
between 5 and 22 mdd, and those for zinc between 90 and 175 mdd depend-
ing on the type of aluminum alloy to which these materials had been
coupled.
In all cases, silver, copper, and 4130 steel have the greatest accelerating
effect on corrosion of the aluminum alloys, followed by the stainless
steels, nickel, and Inconel 718. The group which has least effect includes
the titanium alloy, Haynes 188, tin, cadmium, and zinc. A ranking of
metals and alloys with respect to the corrosive damage aluminum alloys
suffer when coupled to these materials would be for all aluminum alloys
studied: silver > copper > 4130 ;i> stainless steels ~ nickel, Inconel 718 : ^
Ti-6-4 « Haynes 188 > tin > cadmium. It will be noted that for all
aluminum alloys, dissolution rates are increased when the aluminum
University of Washington (University of Washington) pursuant to License Agreement. No further rep
TABLE 3—Galvanic series for aluminum 6061-T651 in 3.5 percent sodium chloride, ro
0.56 mdd.
'o, a. A<t>' Overall

Coupled to MA/cm^ mdd mV Number
1 Ag 54.5 65.6 -721 2

2 Cu 43.6 47.7 -507 7
3 4130 24.3 27.0 -205 14
4 Ni 21.9 29.7 -481 16
5 PH13-8MO 16.0 19.8 -664 25
6 A286 14.7 18.7 -704 27
7 Type 347 SS 14.1 21.2 -653 28
8 Type 301 SS 12.4 17.3 -672 36
9 Type 304L SS 11.3 16.1 -679 42
10 Inco 718 8.1 7.0 -556 53
11 Ti-6-4 5.2 8.3 -510 59
12 Haynes 188 5.0 7.7 -543 60
13 Al 2219 3.1 -O.S" -99 66
14 Al 2024 1.95 10.0 -6 71
15 Sn 1.59 5.9 -183 72
16 Al 1100 0.66 3.7 -68 75
17 Cd 0.28 4.0 -95 77
18 Al 7075 -0.66 -1.4° +36 81
19 Zn -1.51 6.6 +298 85
" Negative values of r^ correspond to weight gain.
alloys are coupled to zinc, although galvanic currents are negative. A

ranking according to corrosion potentials of uncoupled alloys would have
led to: stainless steels > silver > Inconel 718 > nickel > copper >
Haynes 188 > Ti-6-4 > tin > 4130 > cadmium > zinc.
Effect of Corrosive Environment

Having studied the effect of the dissimilar metal, it seemed also of interest
to investigate the effect of the corrosive environment [8]. From the many
possible electrolytes tap and distilled water were chosen due to the obvious
practical applications involving galvanic couples. Distilled water was of
additional interest since only dissolved oxygen and the water molecule
can, at least initially, react on the surface of the dissimilar metals. The very
low conductivity of distilled water did not represent an experimental
problem; due to the characteristics of the zero impedance ammeter, the
potential difference of coupled dissimilar metals was less than 0.1 mV,
even in distilled water.
Galvanic Corrosion Data—Typical galvanic current data obtained in tap
water are shown in Fig. 3a for 2024 aluminum coupled to copper, Type
304L SS, Ti-6A1-4V, or zinc. Similar to the results in 3.5 percent sodium
chloride, higher galvanic currents were observed for all aluminum alloys
tested when the aluminum alloy was coupled to copper than when it was
coupled to Type 304L SS or Ti-6A1-4V. For the aluminum-zinc couples a
MANSFELD AND KENKEl ON CORROSION OF ALUMINUM ALLOYS 27
' I 1 1
1 ' 1 ' 1 ' 1
-
- Al 2024/Tapwatei- -
- -
Cu
V
. , ^ S 304 _ _ ^
=^ — . —' « L - =^
. ^ " ^ ^ " ^
1 , 1 , 1 '
1 1 1 1
12 16 20
t (Hours)
n I ^ I t \ 1 I 1 1-
Al 2024/Tapwater
00 I L. J 1 I 1 I > L
8 12 16 20 24
t (Hours)
FIG. 3—Time behavior of galvanic current Ig for (a) Aluminum 2024 coupled to copper.
Type 304L SS, Ti-6A1-4V, or zinc in tap water, and (b) for galvanic potential *g.
negative galvanic current Ig was observed due to the fact that zinc was the
anode in the galvanic couple.
Despite the appreciable potential differences between uncoupled alumi-
num alloys and copper, Type 304L SS or Ti-6A1-4V, the galvanic potentials
$„ of the corresponding couples were always very close to the corrosion
potential of an uncoupled aluminum alloy, Fig. 3a. The difference between
the corrosion potential of an uncoupled aluminum alloy and the initial
galvanic potential was found to be larger in tap water than in 3.5 percent
sodium chloride. For couples involving zinc, the galvanic potential was
found to be slightly more noble than the corrosion potential of the un-
coupled zinc. The changes of the galvanic potential <^(, in tap water with
time were small in all cases.
In experiments in distilled water, much larger changes of galvanic
current /„ and galvanic potential g as a function of time were observed
than in 3.5 percent sodium chloride or tap water. Figure 4a shows the
time dependence of the galvanic current Ig for galvanic couples involving
aluminum 2024 in distilled water. Similar to results in tap water (Fig. 3a),
the galvanic current decreases in the order copper > Type 304 SS >
Ti-6A1-4V, while for the aluminum-zinc couples the galvanic current was
negative. The time-dependence of the galvanic potential </>„ is very different
in distilled water compared to tap water, values of 4>g becoming more active
(negative) during the test and showing larger differences for different
cathode materials. The reason for the large shift of ^g (Fig. Ab) was found
to be due to large shifts of the corrosion potential of the aluminum alloys
in the negative direction during the galvanic current test. Similar behavior
was observed for 4130 steel and zinc, while the corrosion potentials of
copper. Type 304L SS, and Ti-6Al-4V did not change much.
Figure 5 shows a comparison of galvanic current data in tap water
(Fig. 5a) and distilled water (Fig. 5b) for aluminum alloys coupled to
4130 steel. In tap water the steel is the anode when coupled to aluminum
7075, while in distilled water it is the anode when coupled to aluminum
1100; in all other cases, it is the cathode material.
Figure 6 shows a comparison of galvanic current measurements for
aluminum 7075/copper in 3.5 percent sodium chloride, tap water, and
distilled water. The average galvanic current density ig is much higher in
3.5 percent sodium chloride than in tap water and distilled water. In the
latter two solutions, the average galvanic current density values of ig are
comparable. Note the different time behavior of the galvanic current in
tap water and distilled water.
The average galvanic current density ig with respect to the aluminum
alloy as determined from graphical integration of the ig versus time curves
and the initial potential difference A» between the two dissimilar metals
before coupling have been listed in tables for the five aluminum alloys
tested in tap water and distilled water in Ref 8.
MANSFELD AND KENKEL O N CORROSION OF ALUMINUM ALLOYS 29
"1—I—r 1 r
Al 2024/Dist. H,0
-200 J I I L J L
12
t (Hours)
T I I \ r 1—r
\
\
J 1 1 L
12
t (Hours)
FIG. 4—Time behavior of galvanic current for (a) aluminum 2024 coupled to copper. Type
304L SS> Ti-6A1-4V, or zinc in distilled water, and (b) galvanic potential <l>g.
1 1—I 1 \—r
1130 S t e e l / T a p w a t e r
/v/V
^y
J I L J I I L
12 16 20 24
t (Hours)
1 1 1 1 1 1 1 1 1 1
4130 Steel/Dist. HjO '
1 ^..1_100
J • - - . - - ^^^
/
^°s.
7075
. —
\ 2219
—
- -
—
_^
1 1 1 1 1 1 1 1 1 1
8 12 16 20
t (Hours)
FIG. 5—Galvanic current data for aluminum alloys coupled to 4130 steel: (a) tapwater
and (b) distilled water.
' 1 ' 1 ' \ ' 1 ' 1 ^

fll 7075/Cu
llapwater i = 9.0 pA/cm
V. . ^
y - 2
• ^ D i s t . llgO i = 8.2 ijA/cm
-/
ol L.
8 12 IG 20 24
t (Hours)
FIG. 6—Comparison of galvanic currents in 3.5 percent sodium chloride, tap water and
distilled water for aluminum 70751 copper.
Weight Loss Data—Table 4 is a summary of weight loss data recorded

for aluminum alloys coupled to 4130 steel in 3.5 percent sodium chloride,
tap water, and distilled water. The increase of dissolution rates TA — ro over
the corrosion rate ro of uncoupled aluminum alloys is very pronounced in
3.5 percent sodium chloride due to pitting attack of the aluminum alloys
caused by polarization in the noble direction. In tap water and distilled
TABLE 4—Increase of dissolution rates T\ — To (mdd) of aluminum alloys due to galvanic

coupling to 4130 steel in 3.5 percent sodium chloride, tap water, and distilled water.
3.5%NaCl Tap Water Distilled Water
A l 1100 30.0 3.4 8.1

Al 2024 32.8 -2.4" -4.7
Al 2219 34.1 0.5 4.7
A16061 26.4 -2.8 -1.4
Al 7075 25.0 -6.9 -3.7
" Negative values refer to weight gain.
water small weight losses or gains have been recorded, while galvanic
current measurements have shown (Fig. 5) that depending on the couple
and the environmental studied, the aluminum alloy can be either the anode
or the cathode.
Only very small weight changes were recorded for Type 304L SS, copper,
or Ti-6A1-4V. For 4130 steel the dissolution rates in tap water and distilled
water were higher than in 3.5 percent sodium chloride due to the lack of
cathodic protection by the aluminum alloys as discussed elsewhere [70].
The dissolution rates of zinc were high in all media studied since zinc
was the anode in all cases.
Ejfect of Area Ratio [9]

Materials and Test Methods—In the study of the effect of the area ratio
on galvanic corrosion of aluminum alloys, the aluminum alloys 2024-T841
and 7075-T76 were coupled to copper stainless steel Type 304L, 4130 steel,
Ti-6A1-4V, cadmium, or zinc in air-saturated 3.5 percent sodium chloride
at 21 ± 1°C. Flat specimens were prepared so that an area of about 2 or
20 cm^ was exposed to the electrolyte. Area ratios used were approximately
0.1, 1.0, or 10. Weight loss data for the materials in a given couple were
used to calculate dissolution rates of anode and cathode as a function of
area ratio.
Galvanic Current Data—Figure la shows galvanic current Ig minus time
traces recorded for the aluminum 2024-copper couple for area ratios
^c/Â = 0.1, 1, or 10. For area ratios of A^^'/A'^^ = 1 or 10 the area of
the copper electrode was kept constant at about 20 cm^ while fox A^"^/A^^ =
0.1 the area of copper was about 2 cm^. Figure la shows that under these
conditions the galvanic current /„ is independent of area ratio for A^^/ A^^ =
1 or 10, but decreases by about a factor of 10 for A^'^/A^^ = 0.1.
When the galvanic current data are replotted as galvanic current density
ig versus time, different behavior is observed for the galvanic current
density ig^^ = Ig/A'^^ and /'a"^" = Ig/A^'^. Figure lb shows that the galvanic
current density ig^^ with respect to the aluminum alloy (the anode) in-
creases by about a factor of 10 when the area ratio A^'^/A'^^ is increased
by a factor of 10. The galvanic current density 4^" with respect to copper
(the cathode) seems to be independent of area ratio (Fig. 7c); /j,*^" is nega-
tive, since copper is the cathode in the aluminum 2024-copper couple.
Similar results were obtained for the other galvanic couples studied.
Weight Loss Data—For all galvanic couples in which the aluminum
alloys were the anodes, the dissolution rate r^ calculated from weight loss
data increases with increasing area ratio A^/A^. For the couples aluminum
2024/cadmium, aluminum 2024/zinc, and aluminum 7075/zinc, in which
the aluminum alloy was the cathode, no systematic changes with area ratio
were observed for galvanic current or weight loss data. As observed earlier
(Table 3) coupling to zinc did not result in cathodic protection of aluminum

2024 or 7075, but accelerated corrosion.
Discussion
Theoretical Considerations
A general discussion of the factors determining the rate of galvanic
corrosion has been given earlier [2,5] for the cases of charge transfer and
diffusion control. A more detailed analysis will be given here for the case
of diffusion control in order to be able to discuss the experimental data.
For the discussion of galvanic corrosion under diffusion control of the
cathodic reaction it is assumed that the only reaction occurring on the
cathode at the galvanic potential <^g is reduction of oxygen. The galvanic
current Ig is then equal to the difference between the anodic and cathodic
currents for the anode and equal to the cathodic current for the cathode
at the potential of the couple <t>g
h = /a^(*.) - //(«^.) = Ic%ô) (1)

where /„'* and / / are the anodic and cathodic current for the anode and
I^'^ is the cathodic current for the cathode. Equation 1 can be written in
terms of current densities and area A^ and A'^ of anode and cathode,
respectively
ig^'A^ = ia^'A^ - icÂ^ = iJ'A" (2)
Due to diffusion control
ic^ = /c^ = /o^^ (3)
where ia^^ is the limiting current density for oxygen reduction.
Combined with Eq 2, this leads to
/•/ = ia^ - /O,^ = /0,^(^7^^) (4)
Since, for diffusion control
«02^ = ' c o r / (5)
Eq 4 can also be written as
•0 »a »corr \y)
According to Eq 6, the galvanic current density /„^ is a measure of the

galvanic effect, which is the increase of the anodic dissolution current
density ia^ of the anode due to galvanic coupling over its corrosion current
density /cor/. Equation 6 can be used to compare galvanic current data
with dissolution rates in the form
/ / = kQ-A - /-o) (7)
using Faraday's law.
1 1 1T 1 1 1 1 1 1 II 1 1 1 1 1 1 M 1 y 1 1 1 1
ii /
i
— —
! 1 '
" -
5 1 1
s ; ; = i /
?
-
=vK"" 1 i _
\
J /
/
/
/'
i y
(•
1 1 1 1 1 1 1 - > 1 1 1 1 1 1 1 ' v\ 1
Mill—I—I—71 r I I I—I—I—rT~l n I I I I I T—I 1 TT-
I I I J
l.....i*^ I 1 L_ I I I I J Li-J I 1_
IV
12 16
t (Hours)
(C)
FIG. 7—Galvanic current data for aluminum 2024/copper in 3.5 percent sodium chloride;
(a) galvanic current Ig, (b) galvanic current density ig'*' with respect to aluminum 2024, and
(c) galvanic current density ig''" with respect to copper.
Figure 8 shows a plot of the average galvanic current density ig with

respect to the aluminum alloy against the difference of dissolution rates
rA — ra for coupled {VA) and uncoupled (/-o) aluminum alloys determined
from weight loss data for the 95 galvanic couples studied in 3.5 percent
sodium chloride [7]. Each data point represents a different galvanic couple.
Most points fall close to a straight line with a slope of 0.8 Â/cm^ Xmdd.
The theoretical slope for pure aluminum would be 1.24 ;uA/cm^ X mdd.
The observed deviation is most likely due to the fact that aluminum alloys
containing copper (1 Â/cm^ = 2.85 mdd) and zinc (1 Â/cm^ = 2.93 mdd)
were studied rather than pure aluminum. A correction for aluminum-
copper or aluminum-zinc would move the theoretical slope closer to the one
observed experimentally. Similar correlations have been obtained in tap.
water and distilled water {8\
Rearrangement of Eq 4 leads to
ia^ = /o,^ + k.'Â'^/A^ = k,\\ + AÂ^) (8)
FIG. 8—Correlation between the average galvanic current density ig and increase of
dissolution rates TA — r^ due to coupling.
which is the so-called "catchment principle" according to which the

dissolution rate of the anode in a galvanic couple is proportional to the
area ratio A^/A^.
The relationship between the galvanic current density ig^ and the area
ratio is also given by Eq 4 as
/o,M7^^ (9)
From Eq 8 it follows that the galvanic current Ig is proportional to the
area A^ of the cathode and independent of the area of the anode
/ / ^ ^ = 4 = h,Â° (10)
Equation 10 explains the results in Fig. la, where for A^^/A^"^ = 0.1 and 1
the galvanic current Ig was independent of area ratio. For these two area
ratios the area of copper {A'^) had been held constant. To obtain an area
ratio y4^'//4'''' = 10 the area of copper was reduced by a factor of 10, and
consequently the galvanic current was lower by about a factor of 10.
According to Eq 9 the galvanic current density ig^ with respect to the
anode is directly proportional to the area ratio A^/A^. This is qualitatively
confirmed by the data in Fig. lb which show an increase of i',,^' with/l'^"//!-*^'.
A plot of log /g^' versus log A^/A^ according to Eq 9 results in a straight

line with a slope of one for both aluminum 2024 and aluminum 7075
(Fig. 9). The data for aluminum 2024/cadmium, aluminum 2024/zinc,
and aluminum 7075/zinc have been omitted from Fig. 9 since in these
couples the aluminum alloys were the cathodes. The different values of
/ j ^ ' at a constant value of A'^/A^ are assumed to result from the fact that
contrary to the normal assumption, that the limiting diffusion current
density io^^ is independent of cathode material (Eq 3), experimental values
of /'oj^ are found to be dependent on the nature of the cathode. Mansfeld
and Parry [5] have shown, based on potentiostatic polarization curves,
that in 3.5 percent sodium chloride /oj^ is larger for Type 304 SS than for
Ti-6Al-4V. The decrease of the galvanic current density 4^ at a given area
ratio in the order copper > 4130 > Type 304L stainless steel > Ti-6A1-4V
> cadmium is then related to a corresponding decrease of /oj^. Based on
experimental evidence, Eq 3 is not exactly fulfilled and Eq 9 has to be
rewritten as
A^
— lo. (11)
A^
where /oj^'^ is the material-dependent Hmiting current density for oxygen
diffusion.
The dissolution rates calculated from the weight loss data for the alumi-
num alloys in galvanic couples have been plotted versus 1 + A^/A"^ in
1 1 1 1 1 1M | 1 1 1 n 11 1 , 1 MM| I 1 1 l-nr
:
" -
al 7075/3.5% NoCI
• Cu
• /
• 4130
- iSS304L • / -
O Ti-6-4
ACd / A
I / A ;
- • y^
-
- -
m/
yi
— ~
/ ^
/ A
- -
- -
e/
1 1 1 i/l MI I.I 1 1
FIG. 9—Dependence of galvanic current density ig aluminum on area ratio A^/A^ for
aluminum 7075 in 3.5 percent sodium chloride.
log-log plots in Fig. 10 for aluminum 7075. The approximately straight line
relationship with a slope of one confirms Eq 8 since the dissolution current
density /„^ is related to the dissolution rate rA by Faraday's law. The
dependence of dissolution rates on cathode material at a constant area
ratio has to be explained as was shown in Eq 11. For material-dependent
cathodic current density io^^'^ the catchment principle has to be expressed
as
A<'
/a^ = io,"-^ + /o,^'^ (12)
Based on these relationships which are confirmed by the experimental

result presented here, the dissolution rate of an anode in a galvanic couple
can be calculated for any area ratio if it has been measured for one area
ratio, for example, of one.
FIG. 10—Dependence of dissolution rates tx on area ratio A'^/A^ for aluminum 7075.
Effect of Environment
The main difference between the elTect of sodium chloride, tap water, and
distilled water on galvanic corrosion of aluminum alloys seems to be the
fact that due to the high chloride content in 3.5 percent sodium chloride
the pitting potential of aluminum alloys is only slightly more noble than
the corrosion potential. Potentiostatic polarization studies with ohmic-drop
compensation in tap water [77] have shown that the pitting potential in tap
water is much more noble than in 3.5 percent sodium chloride while in
distilled water pitting does not occur. The aluminum alloys can, therefore,
not be polarized more noble than their pitting potential and consequently
dissolve with high rates due to pitting. In tap water and distilled water,
polarization to more noble potentials is possible, and changes in polarity
of the dissimilar metals in a galvanic couple are also possible as seen for
aluminum alloy/4130 steel couples (Fig. 5) [5].
Undoubtedly, some of the many substances contained in Thousand Oaks,
Calif., tap water can and will influence the rate of electrochemical reactions
occurring on the metals studied. The details of such effects have not been
studied, however.
Effect of Potential Difference Between Dissimilar Metals

It is often assumed that the rate of galvanic corrosion can be judged
based on the difference of the corrosion potential of uncoupled dissimilar
metals. For a diffusion controlled cathodic process the dissolution rate of
the anode in a galvanic couple should, however, be independent of the
nature of the cathode and therefore also independent of the potential
difference between anode and cathode. As pointed out previously, the
diffusion current density /oj^ has been found to be material dependent to
some extent, most likely due to the formation of surface films which change
the ratio D/h of diffusion coefficient D for oxygen and diffusion layer
thickness 5. Due to this fact, a material dependence of the rate of galvanic
corrosion could be experimentally observed, which in turn could be
interpreted incorrectly as being due to the difference of corrosion potentials
^' of the uncoupled dissimilar metals.
The experimental data of this study [7] have been plotted in Fig. 11 as
ig^ versus A<^'' = ^corr'^ — <^corr^ for the 95 galvanic couples studied in
3.5 percent sodium chloride. In Fig. 12 the relative increase of dissolution
rates (r^ — roVro due to coupHng has been plotted versus A^" using weight
loss data.
Figure 11, which represents the absolute increase of dissolution rates due
to coupHng {ig = k{rA — ro), Eq 7), and Fig. 12, which represents the
relative increase of dissolution rates with respect to the corrosion rate of
the uncoupled aluminum alloy, show that the initial potential difference
A</)' of uncoupled metals cannot be used as a reliable indicator of the extent
of galvanic corrosion. While one can distinguish two groups of data in
University of Washington (University of Washington) pursuant to License Agreement. No further reproduction
T r 1—\—\—3"\n—r
A 1100
D 2024
>Ag
• 2219
A 6061
0 7075
n A O >4130 steel
A O
D A".A4
A Ô<5>
^7^
-J \ L J \ L I I I I I
-0.2 -0.4
FIG. 11—Average galvanic current density i^ as a function of difference A<^" of corrosion

potentials of uncoupled materials.
Fig. 11 which show a general increase of the galvanic current density with
increasing potential difference A<^'', a measurement of A</)' alone cannot give
information about the rate of galvanic corrosion to be expected for a given
galvanic couple. Figure 12 shows that for A» values between —600 and
— 700 mV, the relative increase of dissolution rates can be between 3 and 5
for aluminum 2219 and 2024, but between 60 and 230 for aluminum 1100.
One can also find a relative increase of about 46 at A'<^ = — 200 m V and a
relative increase of dissolution rates of only 10 at A^' = —550 mV for
aluminum 6061. Galvanic series based on corrosion potentials of uncoupled
materials have, therefore, to be considered as only very qualitative guide-
lines.
The effect of the dissimilar metals is shown clearly if galvanic current
data, which represent the absolute increase of the dissolution rate of the
aluminum alloy over the corrosion rate of the uncoupled alloy, are con-
sidered. The large effect of silver, copper, and 4130 steel can be recognized in
Fig. 11 where the five aluminum alloys studied appear in clusters at Ac^' =
- 6 3 0 to - 7 2 0 mV (silver), at A0' = - 5 0 0 to - 5 7 0 mV (copper) and
A<^' = —90 to —340 mV (steel 4130). A second group of galvanic couples
MANSFELD AND KENKEL ON CORROSION OF ALUMINUM ALLOYS 4 I
"1 1 \ r
A 1100
a 2024
O 2219
A 6061
O 7075
A \
.1 A
A g A a o
^ a,n Og ^ ^°'
J L
+0.4 +0.2 0 -0.2 -0.4 -0.6 -0.3
« • ' (V)
FIG. 12—Relative increase TA — ro/fo of dissolution rates of aluminum alloys (weight loss
data) as a function of A0".
ranges from couples involving zinc and aluminum alloys of different

composition, where galvanic currents are negative with respect to the
aluminum alloys, to couples involving the stainless steels and nickel
(A<^'' = - 6 0 0 to - 8 0 0 mV). Couples involving Ti-6A1-4V, Haynes 188,
Inconel 718, tin, and cadmium fall between these two extremes.
Ranking of Galvanic Couples

The results obtained have shown that reliable classification of galvanic
couples can only be achieved if kinetic data such as galvanic current data
are collected for the couples of interest. The galvanic couples can then be
ranked according to the absolute increase of dissolution rates {ig) (see
Ref 7) or the relative increase of dissolution rates (/-^ — ro/ro = 'g/Zcor/)-
The continuous monitoring of galvanic currents has the advantage over
weight loss data that dissolution rates can be followed as a function of
time with great accuracy (fractions of microamperes to many milliamperes
can be accurately measured). Problems of removal of corrosion products
before reweighing after the test are avoided.
c
N
''^ as
izi :n izi
"zi u
rR
S8
• * &< - H _;•
(^ [y5 r * l ^
8g -a .J,
H r^ H Z
o
o " c ^ • *
CO
m oj m 3
0) •, M >> •.=
r~ H H CO H Z
8 S ^ 00
O ro .^
^ C « -(^ O
•a
, N S. on „ '
53
—c ^ > . CO 00 t/5
S g d^ q^S. d
o S°? &" _
(N C f^ H VD >.
- >>::: ^ °<! H
O I a- w < •=>•
C VO 00
(/5 . i - •
2 OS y
_ —< C3
" (N h-
2 ^ ^
I o _KM
^'2 < Z
a U3CS CL, M t/5
I
W so
J
m <
< CO 3'
S. " o >>U
H
X. c- UQ. o' 0m'
u^ N
r- „ 00 5
St vo" m to'
to
oo
<N
O
o ^^ ffi 0
Cl< en
to H <
a
E
o
E o
o
O a
General Classification
If the general compatibility of an aluminum alloy with other materials is
of interest, then the relative increases of dissolution rates should be con-
sidered. In Table 4 compatibility of the five aluminum alloys with the 15
other materials is indicated by placing the dissimilar materials in three
classes according to relative increases of dissolution rates rA — ro/ro =
ig/iôTT^ below 5 (Class I), between 5 and 15 (Class II), and above 15
(Class III).
Table 5 shows that under this classification aluminum 1100 is compatible
only with cadmium, aluminum 6061 only with the aluminum alloys 7075,
2219, and 2024, while aluminum 7075 is compatible only with zinc and the
other aluminum alloys tested. The aluminum alloys 2024 and 2219 are
compatible with most materials tested, borderhne cases involve 4130 steel,
copper, and silver (and nickel and zinc for aluminum 2219), no combina-
tions have been found to be incompatible based on the present criteria.
These criteria have been arbitrarily selected and might have to be modified
for special applications.
Acknowledgments
This work has been funded by the Rockwell International IR & D
Interdivisional Technology Panel under sponsorship of the Corrosion
Panel.
APPENDIX
Instrumentation for Measurements of Galvanic Currents
The following describes some of the methods which can be used to measure the
galvanic current flowing between two dissimilar metals which are electrically
coupled and immersed in an electrolyte.
Voltage Drop Across a Resistor
Galvanic currents have been measured in the past by placing a small resistor
between the two dissimilar metals to be coupled and measuring the voltage drop
AK across the resistor R^ (Fig. 13a). This simple technique is not satisfactory be-
cause the two dissimilar metals in the galvanic couple are not at the same potential,
but are separated by the voltage AF = !„' 7?„, where Ig is the current flowing
between the two metals and R,^ is the measuring resistor. The current /„' measured
is, therefore, always smaller than the galvanic current Ig.
An improved approach would limit the voltage drop AK to a fixed maximum
value; for example, 1 mV, by adjusting R^ as the galvanic current changes by orders
of magnitude. A difficulty might arise, however, when voltages smaller than 1 mV
have to be accurately measured and recorded.
Similar objections can be raised against the use of a galvanometer, which gener-
ally has high internal resistance. In addition, it is desirable to record continuously
the galvanic current with greater sensitivity which requires the use of amplifiers.
(a) (b) (c)

Rm = measuring resistor B = battery OA = operational amplifier
AV = potential drop Rx = variable resistance A = microammeter
EI, EII = dissimilar test S1/S2 = switches RB = standard resistor
materials A = ammeter
G = galvanometer
FIG. 13— Various techniques for galvanic current measurements: (a) voltage drop across
resistor, (b) manual null balancing zero resistance ammeter [13]; and (c) electronic zero
resistance ammeter with instantaneous null characteristics [14].
In the past few years a number of new methods of electrochemical measurements

of the galvanic current have been introduced which are summarized in the following.
Earlier Zero Resistance Ammeter Circuits {Manual Null Balancing)

Earlier attempts to eliminate the effect of a measuring resistor have been de-
scribed by Brown and Mears [12] as shown in Fig. 136 [13]. If switch Si is closed,
no potential difference exists between the electrodes and the galvanometer G reads
zero deflection. The galvanic current /„ is measured by closing the switch 52 and
adjusting the variable resistor Rx in such a way that the galvanometer G reads
zero millivolts potential difference. The current flowing through the ammeter A
is the galvanic current /„.
Automatic Zero Resistance Ammeters

The manual zero resistance ammeters (ZRA) circuit has the disadvantages that
for the time at which the circuit is not balanced, the galvanic couple is polarized,
which leads to errors and in many cases to long periods of recovery. It is also not
possible to monitor continuously the galvanic current, a basic necessity in many
applications. Godard [13] and Henry and Wilde [14] have made attempts to over-
come these disadvantages. Godard [13] described an "automatic galvanic corrosion
current apparatus," while Henry and Wilde [14] developed "an electronic zero
resistance ammeter with instantaneous null characteristics." The circuit of Henry
and Wilde [14] is shown in Fig. 13c.
The principle of operation is based on the use of an operational amplifier to

replace the manual balancing of the ZRA described previously. With the switch 5
in the zero position, the operational amplifier OA is adjusted so that the voltage
drop across Rs is zero millivolts between the positive input and the output. With the
switch in the read position, the current flow through R^ is counteracted within the
rise time of the amplifier ( ~ 1 MS) by a reverse current from the amplifier to maintain
the voltage drop across R, at zero millivolts. This current which represents the
galvanic current / , is measured on the microammeter A. Henry and Wilde developed
a compact and portable unit which is fully described in their paper [14].
Use of Potentiostats
The method of using a potentiostat for the measurement of galvanic corrosion
currents was first described by Devay, Lengyel, and Meszaros [15] and applied to
measurements of galvanic corrosion currents in dental amalgam by von Fraunhofer
and Staheli [16]. Figure 14 [17] shows the experimental arrangement. One electrode
is connected to the working electrode terminal (WE) the other one to the reference
electrode terminal (REF) which is connected directly to the auxiliary electrode
terminal (AUX). With the potentiostat set at exactly zero millivolts applied poten-
tial, the galvanic current is read directly on the current meter of the potentiostat.
Note that von Fraunhofer [16,17] uses a feedback resistor R; between REF and
AUX, which can introduce an error depending on the gain of the potentiostat and
the output potential. The use of Rj was not found necessary with Wenking or
Princeton Applied Research potentiostats.
Use of an Operational Amplifier

By far simpler and more economic is the use of an operational amplifier as first
described by Lauer and Mansfeld [4]. Figure 15 shows the experimental arrange-
ment [4].
One of the electrodes of the couple is grounded. The other is connected to the
negative input of a high-gain operational amplifier. The output of this amplifier
is given by
Vo = GV, (13)
Potentiostat
FIG. 14—Potentiostat wired as zero impedance ammeter.
GALVANIC CURRENT
ÊLECTRODE 2
^REFERENCE ELECTRODE
ÊLECTRODE I
FIG. 15—Instrumeni for monitoring galvanic current and potentials [4].
where V, is the voltage, referred to ground, of the electrode and G is the open loop
gain, > 101 Thus, values of Vo up to the amplifier output limit (~12 V) correspond
to negligible V^ values.
The impedance of the amplifier is much greater than feedback resistance Rm-
At the amplifier input
U + // = 0 (14)
where ic is the cell current and if the feedback current. The value of the feedback
current is given by
(15)
Rm
Since, from Eq 13 and the value of G, V, = Vo, then
If = - i c (16)
Rm
Since, for Electrode 2 in Fig. 13, K, = 0, the potential difference between Electrode
1 and Electrode 2 is essentially zero. Thus, output voltage Vo is directly proportional
to the cell current, so that we have a "zero impedance" ammeter.
The time-dependent galvanic current is measured using an operational amplifier.
The potential of the couple is measured with respect to a SCE connected to an
electrometer amplifier wired as a high impedance (lO''' n) unit gain follower. The
galvanic current and the potential were simultaneously recorded as a function of time
on strip chart recorders. This arrangement allows continuous monitoring of the
galvanic current over many orders of magnitude with no internal resistive loss
using strip chart recorders. It can be used even in distilled water, since irrespective
of the conductivity of electrolyte the amplifier will always provide zero millivolts
potential difference between the members of the couple. Mansfeld [5-8] has used
this zero impedance ammeter for studies of galvanic couples in sodium chloride,
tap water, and distilled water [7,8], of inorganic conversion coatings on aluminum
alloys coupled to Type 304 SS or Ti-6A1-4V [5] and of metallic coatings on alumi-
num alloys [6].
References
[1] LaQue, F. L., Proceedings, American Society for Testing and Materials, Vol. 51, 1951,
p. 495.
[2] Mansfeld, F., Corrosion, Vol. 27, 1971, p. 436.
[4] Lauer, G. and Mansfeld, F., Corrosion, Vol. 26, 1970, p. 504.
[5] Mansfeld, F. and Parry, E. P., Corrosion Science, Vol. 13, 1973, p. 605.
[7] Mansfeld, F., Hengstenberg, D. H., and Kenkel, J. V., Corrosion, Vol. 30, 1974, p. 343.
[8] Mansfeld, F. and Kenkel, J. V., Corrosion Science, Vol. 15, 1975, p. 183.
[9] Mansfeld, F. and Kenkel, J. V., Corrosion Science, Vol. 15, 1975, p. 239.
[JO] Mansfeld, F. and Kenkel, J. V., Corrosion, Vol. 31, 1975, p. 298.
[iJ] Mansfeld, F., Myers, R. L., and Lauer, G., "Instrumentation for Corrosion Studies in
Low Conductivity Media," Technical Report, Rockwell International, 1973.
IJ2] Brown, R. H. and Mears, R. B., Transactions, Electrochemical Society, Vol. 74, 1938,
p. 495.
[13] Goddard, H. P., Corrosion, Vol. 7, 1951, p. 93.
[J4] Henry, W. D. and Wilde, B. E., Corrosion, Vol. 27, 1971, p. 479.
[15] Devay, J., Lengyel, B., Jr., and Meszaros, L., Acta Chimica Academiae Scientiarum
Hungaricae, Vol. 62, 1962, p. 157.
[16] von Fraunhofer, J. A. and Staheli, P. J., Corrosion Science, Vol. 12, 1972, p. 767.
[17] von Fraunhofer, J. A. and Banks, C. H., Potentiostat and its Applications, Butterworths,
London, 1972.
K. G. Compton1
Current Density Distribution on Composite

Structures Under Cathodic Protection in
Seawater
REFERENCE: Compton, K. G., "Current Density Distribution on Composite

Structures Under Cathodic Protection in Seawater," Galvanic and Pitting Cor-
rosion—Field and Laboratory Studies, ASTM STP 576, American Society for
Testing and Materials, 1976, pp. 48-55.
ABSTRACT: The distribution of cathodic protection current between members
of copper-steel and stainless steel-aluminum galvanic couples was found to vary
by ratio of 940 to 0.05 as the relative areas were varied from 100:1 to 1:100.
Polarization curves and the distribution of current are given. Above a 1:1 ratio
of cathode to anode, cathodic protection does not appear to be practical.
KEY WORDS: corrosion, bimetallic couples, cathodic protection, polarization,
dissimilar metal corrosion, composite structures, current density
Very often dissimilar metals must be used in electrical contact for

structural or functional purposes and are exposed to seawater. There is a
considerable body of literature on the subject; however, very little definitive
information is available on the cathodic protection of such a composite
structure because the ratio of the areas of the two metal surfaces is varied.
In the present work, the polarization behavior of each metal and of the
couple was determined, and the division of the "protection" current
between the two members was measured. Copper and carbon steel were
selected for one couple and aluminum and stainless steel for the other.
These combinations are of practical interest in the marine field.
The polarization curves were prepared by the usual standard galvano-
static technique using a time interval of 3 min. The measurement of current
to the individual members was accomplished by use of the zero resistance
ammeter technique while holding the polarized couple potential constant
by means of a polaristat. In this case, the "protection voltage" was arbi-
trarily set at —0.80 V to the saturated calomel reference electrode for both
1
Professor of Ocean Engineering, University of Miami, Miami, Fla. 33149.
48

University of Washington (University of Washington) pursuant to Licen
COMPTON ON CURRENT DENSITY DISTRIBUTION 49
couples. This value seems to satisfy a consensus of opinion and is given

elsewhere [7].^
No attempt was made to determine rates of corrosion of either the
individual members or of the anodic members of the couples since this was
not within the scope of the program. The objective was to determine the
feasibility of cathodically protecting systems where the cathode area might
be large compared to that of the anode and to establish the relationship
between area ratios and polarization behavior.
The carbon steel contained 0.16C, 0.63Mn, and O.OlOCu. The copper
content was 99.976 with some silver. The aluminum was mill product 5052,
and no analysis was made. The stainless steel was Type 316 with 0.06C,
1.8Mn, 2.15Mo, and 12.9Ni. Both the Type 316 and the carbon steel were
supplied by Armco with their heat analysis. All materials were in sheet
form, 0.040 to 0.050 in. thick, and in the as-rolled condition with no
consideration given to temper or hardness.
The seawater was drawn from Bear Cut, a channel connecting lower
Biscayne Bay with the Atlantic Ocean and was normal with respect to
salinity and pH. As used, it was essentially saturated with air at the ambient
temperature. The seawater was pumped into a large shallow tank for
settling of any silt and piped to the various laboratories on a continuous
flow basis.
Procedure
The specimens were cut to the desired size and abrasively cleaned with
600 grit waterproof silicon carbide paper. Leads were attached and the
backs and edges, and part of the front surfaces were coated with wax. The
size of the panels plus the wax masking permitted a ratio of areas from
100:1 to 0.01:1.
All specimens were allowed to stand in a tank of seawater for 24 h prior
to testing. While this was a short exposure period, it was observed that the
specimens tended to become relatively stabilized in this period of time as
compared to erratic behavior for initial short periods. They were not
connected as couples during this conditioning period.
The first polarization run was made on the composite structure (couple)
starting about 5 min after they had been coupled together. After the
composite run, the specimens were allowed to depolarize to their initial
potentials, and then polarization runs were made on the uncoupled indi-
vidual metals. They were again allowed to depolarize to their initial po-
tentials, then recoupled and cathodically polarized to —0.80 V saturated
calomel electrode (SCE). Initial current measurements (to each member)
were made by the zero resistance ammeter method. The potential was held
constant for 24 h and the currents measured again.
2 The italic numbers in brackets refer to the list of references appended to this paper.
-O. 2
-1 .2
- ^ Both Steel and
-1 . 4 - Composice S t u c t u r e
AREA RATIO I-.100 (CU: STEEL)
.Ol •OS .1 , .5^, '•

Cui-rent Density (ma/in }
FIG. 1—Polarization curves of copper and steel.
Results
Where the area ratio of copper to steel is 1:100, the polarization curves
are as shown in Fig. 1. Here the copper is so highly polarized that the
polarization curve for the composite structure^ is identical to that of
carbon steel alone. Increasing the relative area of copper to 1:10 and 1:1
as shown in Figs. 2 and 3 produces a slight decrease in the polarization of
the composite with a crossover below the protection potential in the case of
the equal areas. However, an increase in the protection current has been
required. As the relative copper area increases as shown in Figs. 4 and 5,
the composite structure curve begins to resemble the copper curve, and the
protective current is further increased. From Fig. 1 to Fig. 5, the pro-
tective current is increased about 5.5 fold.
The division of the protective current in terms of current density when
the couple is held at a potential of 0.80 V (SCE) was measured with the
"zero resistance ammeter" and is shown in Fig. 6. It is clear from this
figure that at high ratios of copper to steel, the copper draws an excessive
amount of current when the steel is polarized to protection, but at low
ratios the "wasted" current is relatively insignificant. In the former case
the current density ratio is about 56 and in the latter, about 0.05.
Where the ratio of aluminum to stainless steel is 1:100, the polarization
of the couple is identical to that of stainless steel. Decreasing the ratio by a
factor of 10 permits the couple to polarize more like aluminum at low
current densities. This is shown in Figs. 7 and 8. The polarization of the
couple is about midway between stainless steel and aluminum as shown in
Fig. 9 and approaches that of the aluminum in Fig. 10. In Fig. 11, the
' The current density figure used is the current divided by the total area of the couple
and is not strictly a true "current density" as this varies on the two parts of the couple.
The true current densities are given in Figs. 6 and 12.
-0.2 -(
-0.4
-0.6
-0.8 -
-l.O -
-1 .2
D Composite S t u c t u r e
-1 A AREA RATIO 1:10 fOJ-STEEL)
.0) 5i !i ' S~
Current Density ('ma'^n')
-0.2
a Compoeite S t u c t u r e
AREA RATIO l : i (CU: STEEL)
"T 1 1 1 1 1
.oi .05 .1 .5 1 .0
Current Density (ma/in")
-0.2
-0.4
-0.6 t
-0.8
-l.O
-1.2
D a Composite S t u c t u r e
-1.4 AREA RATIO lO: 1 (CU : STEELl
.Ol .05 .1 .5 l.O

Current Density (ma/in)
u, - u - ^ 1
^ * ""^"^^
^^X.
Z -0.6 -
P -0.8
Z
^ - , . 0 . ' > Copper
* ~ ^ ~ ^ ^ \
\ -^Tll^^
a <J Stêel ^^—•

-1.2 J
o p C o m p o s i t e St;ucCure
-1 . 4 . AREA RATIO too: 1 (CU : STEB.)
.01 .05 .1 .6 I.O

C u r r e n i ; Oensitiy (rna/jn't
30-
/TO .64
/
/
20- INITIAL COPPER x" _ - -a
^ / copper
,' IniCisI /
a-
^^ ^
stBel
/
/'
in -
Pinal ^ ^ v ^ ' ^ ^ - ^
sceel
-0
100 10 1 .1 .01
Area Racio (Cu /Sceet I
FIG. 6—Current density distribution of exposed copper and steel couples.
-0.2
-S-o.e
0
•2^.8
<-i.o
' St:alnlees Composite

-1 .4 -
AREA RATIO l-.IOO (AL;ST>
1 1 1 1 1
£>S .1 .B 1.0
C u r r e n t Density (ma/irf)
FIG. 7—Polarization curves of aluminum and stainless steel.
COMPTON O N CURRENT DENSITY DISTRIBUTION 53
EXPOSED SAMPLES
.OS .1 TB 1 ;o
C u r r e n t ; Density Crria/in')
.oe .1 .5 i.o
C u r r e n t Oen8lt:y (ma/inV
Figure 9
FârHzsCion C u r v e s o f Akmlnunn and
Stalnlees S t e e l
-0.6 -
1 -1 .o
S -1.2 -
111
1 1 1 1 ~\—
XJ6 .1 .6 1.0
Current Density (ma/inf)
-0.2
-OA
-o.e
-0.8
-l.O
-1.2
—• St:ain(ees
-1 .4
—^ Aluminum and Composite
-Ol
Current Density (ma/jn")
polarization of the couple is identical to that of the aluminum. It is apparent

from the polarization curves that as the ratio of the area of stainless steel
to aluminum decreases, the amount of protective current decreases.
Figure 12 gives the current densities of each member of the couple as
measured with the zero resistance ammeter when held at a potential of
— 0.80 V (SCE). Here again the big difference in current required to
polarize the couple when the stainless steel area is large compared to that
of the aluminum is shown in contrast to that when the stainless steel area
is small. The stainless steel takes about 940 times as much current as the
aluminum in the former case and only 0.05 when the area is small.
The differences between the current densities when the couples are first
immersed (5 min) and after 24 h, indicates that any adjustment of a cathodic
I
S -OS
i Initial and Final

/Aluminum
100 lO 1 .1 .Ol
AREA RATIO (ST/AL)
FIG. 12—Current density distribution of aluminum and stainless steel.
University of Washington (University of Washington) pursuant to License Agreement. No further reprodu
protection system should be accompanied by a suitable stabilization

period. In these tests, the stainless steel and aluminum appeared to be
more stable with time than the copper and carbon steel.
Conclusions
The widely held opinion that the cathodic member of the couple tends
to control the polarization has been confirmed. This was discussed by
Hill [2], Waber [3], Wagner [4], Miller [5], and by the principal authorities,
Mears and Brown [6], but not in specific terms such as the data obtained in
this study. From the curves presented here, one can estimate whether
cathodic protection of the system is feasible when these couples are en-
countered or ones of similar characteristics. The ratio of the currents,
cathode to anode, are given by the following.
Ratio of Areas Ic^/lc, ISS/IAI
100:1 56.0 940

10 1 7.8 23.1
1 1 1.66 4.5
1 10 0.527 0.62
1 100 0.05 0.50
NOTE—I = current, C, = carbon steel, and SS =

stainless steel.
It is apparent from the preceding table that in any system where the ratio of
areas is greater than 1:1 a very significant waste of protective current
would occur, unless it was felt that the cathode needed protection.
Acknowledgments
The author wishes to express his appreciation to the Anaconda American
Brass Company, the Armco Steel Company, and Reynolds Metals Com-
pany for supplying the materials used and their analyses. Many of the
laboratory measurements were made by H. A. Murphy, while a graduate
student at the University of Miami.
References
[/] Morgan, J. H., Cathodic Protection, Leonard Hill Limited, London, 1959, p. 172.
[2] Hill, G. R., "The Corrosion of Copper and of Metals in Bi-Metallic Systems," Corrosion,
Vol. 8, 1952.
[3] Waber, J. T. and Rosenbluth, M., Journal of the Electrochemical Society, Vol. 102,
1955, p. 344, and Waber, J. T., Corrosion, Vol. 13, 1957, p. 25.
[4] Wagner, C , Journal of the Electrochemical Society, Vol. 98, 1951, pp. 116-128.
[5] Miller, "Galvanic Couples and Cathodic Protection," Petroleum Engineer, Vol. 19,1946.
[6] Brown, R. H., and Mears, R. B., Journal of the Electrochemical Society, Vol. 81, 1942,
pp. 455-483.
K. G. Compton1 and J. A. Turley2
Electrochemical Examination of Fused Joints

Between Metals
REFERENCE: Compton, K. G. and Turley, J. A., "Electrochemical Examination

of Fused Joints Between Metals," Galvanic and Pitting Corrosion—Field and
Laboratory Studies, ASTM STP 576, American Society for Testing and Materials,
1976, pp. 56-68.
ABSTRACT: Nine combinations of butt welded plates were studied in seawater
for galvanic couple, dissimilar metal type behavior. The potential differences and
corrosion currents were determined for the filler material, heat affected zone,
and parent metal. In seven of the nine cases, the heat affected zone was found to
be anodic to the parent metal. In only one case was there a prospect of cathodic
protection from the parent metal to the weld.
KEY WORDS: corrosion, welded joints, weld decay, galvanic couples, heat
affected zone
Scattered through the literature one finds references to "knife-line"

corrosion and intergranular corrosion. Nowhere does one find a careful and
in-depth study of the corrosion associated with welds or the electrochemical
behavior of welds. This paper records some preliminary results of investi-
gations of the electrochemistry of welds in natural seawater by the senior
author and his students.
Basically, a weld consists of a filler material (FM) in the "as-cast" con-
dition; a zone containing diffusion products of the FM and the parent
material (PM) and the PM that has been affected by the heat of welding,
and the unaffected PM. The heat affected zone (HAZ) may suffer many
metallurgical modifications of the PM, but the most common is segregation
of certain components at the crystal boundaries. For instance, copper rich
material segregates at the grain boundaries in the copper bearing aluminum
alloys (2000 Series, Aluminum Association standards) and chromium
carbides segregate at the grain boundaries in stainless steels. Various
aspects of the problem have been considered by Ketcham [7],3 Guy [2],
1
Professor of Ocean Engineering, University of Miami, Miami, Fla. 33149.
2
Petroleum engineer, Marathon Oil Company, Findlay, Ohio.
3
56

COMPTON AND TURLEY ON FUSED JOINTS BETWEEN METALS 57
Henthorne [i], and Schumaker [4] but the basic electrochemical studies of
segregation in welds have not progressed very much beyond the early
work of Mears and Brown [5].
Procedure
Measurements were made of the open circuit potentials of the filler
material, several parts of the HAZ, and the PM. The polarization char-
acteristics of these same areas were determined, and then the current
interchange between areas was measured. As a result, some concept of the
corrosion forces at work in a welded structure has been obtained.
All of the studies were made in fresh seawater which was renewed in
the test chamber at a rate of about 3 gal per day. This rate was estimated
as an optimum in keeping down velocity, yet ensuring the removal of
corrosion products. Earlier work by Snodgrass [6] and Smith [7] had
indicated the sensitivity of electrochemical measurements to velocity in
seawater. It was felt that the seawater was replenished but essentially
quiescent.
Specimens supplied by various metal suppliers were prepared as butt
welded plates (Fig. 1) which were cut into four units; three were intended
for electrochemical studies and one for metallographic examination. The
welding technique was supposed to represent the best practice of the
supplier. No study of variation in welding technique was intended. The
materials used are listed in Table 1. The actual analysis of most of the
materials was obtained but is not given here in the interest of brevity.
Insulating coatings were applied to all the surfaces of the specimen except
the area being studied as shown in Figs. 2 and 3. Measurements of the
WELDED STOCK
INDIVIDUAL SPECIMEN
r \ »
i T'
FIG. 1—Welded specimens.
TABLE 1—List of specimens giving the PM and FM.
Specimen PM FM
1 aluminum 6061 T6 4043 aluminum

2 aluminum 5083 HI 12 5356
3 aluminum 5086 HI 12 5356
4 aluminum 7002 T6 5356
5 aluminum 6061 (pipe)
6 Monel K-500 Monel WE 134
7 INX-50" Atomark 8018
8 T-IA" Atomark 8018
9 HY 130/150 not specified
" Two plates of the indicated steel welded together with Atomark 8018.
potentials of the various areas were made to a saturated calomel reference

electrode as shown schematically in Fig. 2 using a recording electrometer.
The addition of an auxihary electrode and a power supply permitted the
determination of conventional polarization curves of potential plotted
against the log of the current.
In measuring the galvanic couple corrosion current between the diiferent
zones, a "zero resistance ammeter" circuit was employed as shown in
Fig. 3. Different combinations of areas having approximately the same
surface area were exposed which provided a current measurement between
the HAZ and the F M ; the HAZ and the P M ; and the FM and the PM.
During the study, the temperature, salinity, and pH were monitored. The
pH remained relatively constant at 8.2, the temperature range was approxi-
mately 4°C with an average of 23°C, and the salinity was 33 ± 2 percent.
None of these minor fluctuations would affect the reliability of the data, as
SATURATED CAUIMEL
REFERENCE ELECTRODE
„WELD SPEOMEN
'^ INSULATED COATING
MATER
"LEVEL
FIG. 2—Arrangement of apparatus for measuring single potentials and polarization

resistance.
C O M P T O N A N D TURLEY O N FUSED JOINTS BETWEEN METALS 59
^J. VARIABLE RESISTOR
-±- DCPOWER
^ SUPPLY <d MILLWMMETER
SPECIMENS A AND B
FROM SAME
WELDED STOCK
FIG. 3—Arrangement of apparatus for measuring galvanic currents.
the variability in the specimens would have a greater influence. The dis-
solved oxygen was not monitored, but was presumed to be near saturation
under the conditions of the experiments.
Specimen Preparation
Cleaning and surface preparation of the specimens appeared to be
important in obtaining reproducibility. In order to minimize the effect of
mill scale, oxide coatings, and old corrosion products on the surface of the
specimens, and in order to ensure duplication of test-surface cleanliness, the
following cleaning procedure was employed on every test surface prior to
measurement.
1. Lightly file the surface to a smooth finish and polish with 280- and
400-grit silicon carbide paper, respectively.
2. Wash the surface with Alconox to remove loose particles, dirt, and
oil films.
3. Then thoroughly rinse with tap water to remove all traces of the
cleaning compound.
4. Rinse with distilled water and with acetone.
5. Immediately submerge the cleaned surface in the test tank.
The potential data presented in Figs. 4 to 6 quite vividly illustrate the
anode/cathode relationships between the different zones of each weldment
«<-CSCE) CORROSION CURRENT

CVOLTS SPECIMEN (MAMP/CM?
6061 W / 4 0 4 3
-0.71
-0.7*
•0 7 4 5083 W/5356
•0.75
•0.76
•0.77
•0.78
•0.79
•0.7*. 5086 W/5356

•0.75^
•0.76.
•0.77
•0.78
•0.79.
0 a \- r 3- i: ^•
FIG. 4—Potentials and galvanic currents of and between various segments of the welded
specimens.
Studied. The potential differences shown between the HAZ and associated
PM readily indicate the necessity for knowledge of the corrosion char-
acteristics of HAZ.
In seven of the nine cases studied, the HAZ was found to be electro-
negative (anodic) to the parent metal. No attempt was made to precisely
define the HAZ of any of the metals tested. In every case the one-half inch
0-(SCE) CORROSION CURRENT
(.VOLTS) SPECIMEN (•MAMP/CM*;
•0.77 7002 W535A

0.78
0.79
0.80
0.81.
0.82-
6061 AL PIPE
0.70.
0.71-
0.72.
•0.73
0.74
•0.75
•019- MONEL K-500

0-20-
•0.21
022-
-023
0-24
RMen HBU.
0 >4 r 2' 3" 4" 5'
specimens.
0-(SCE) CORROSION CURRENT

IVOLTS) SPECIMEN (MAMP/CM')
-0.71 INX-50
-072 •
073
-0.74
-0.75
-0.76
-Qjbl
T-IA
-0.70
-0,7 1
-0.72
-0.73
-0.74 .
-065 HYI3CH50
-0.66
-0.67
-0.68
-0.69
-0.70
0 }i c r s e 5'
specimens.
immediately adjacent to the weld (on either or both sides) was designated
and treated as the HAZ. The HAZ of any particular specimen might have
been more or less than the arbitrary one-half inch, but the data revealed
only one exception (Fig. 5, 6061 aluminum pipe). As can be seen from the
potential measurements, the HAZ extends out over an inch and a half
from the weld or filter material.
The potential data (Figs. 4 to 6) also show the relationship between the
weld metal and the rest of the weldment. The data indicate that nearly half
of the weldments studied are in the highly unfavorable condition of the
weld or filter material being the most electronegative area. The importance
of this relationship will be more apparent after consideration of the asso-
ciated bimetallic galvanic corrosion currents.
The potential data reveal what was expected with respect to the existence
of galvanic couples. The zone combination on a particular specimen with
the greatest driving potential would seem likely to have the highest corrosion
rate of the possible combinations, but the magnitude of any of the rates
was impossible to predict based solely on the potential data. The inter-
relationship of the potential data and the measured galvanic corrosion
currents also is presented in Figs. 4 to 6.
Polarization data for each zone of interest in a typical specimen is pre-
sented in Fig. 7. An estimation of the corrosion rate based on the inter-
section of the extension of the Tafel section of the cathodic protection
curve with the corrosion potential gives an interesting indication of the
local action corrosion current. The corrosion rates obtained by polarization
techniques are helpful in describing the relative corrosion susceptibility of
6 0 6 I R W E N T METAL
W/4043 FILLER MATERIAL
-o.«
J-0.9
-OPEN oncuiT
i-u
05 5,0 laO 50,0 100.0

cuHFEr^ DegsiTY (MAMR/tM^)
FIG. 7—Cathodic polarization curves of different segments of the welded specimens from
which corrosion rates can be estimated by the Tafel extrapolation method.
the different zones comprising a weldment; but like the potential data, their
use has limited application. For example, Fig. 7 presents the zonal corro-
sion currents for an aluminum alloy weldment (6061 PM and 4043 FM).
The cathode polarization curve for the weld metal indicates a corrosion
current of 6.5 /tmA/cm^. This is to say that if a portion of the weld material
was exposed to quiescent seawater and if the zone were completely isolated
from any galvanic couples the corrosion rate would be proportional to the
noted corrosion current. Actually, the weld does have multiple galvanic
couples, and its corrosion rate is greatly influenced by them.
The local-action corrosion rates of the PM and the HAZ for the same
example indicate that both zones are less susceptible to local-action cor-
rosion than the weld metal. The limitations of the data with respect to
actual field conditions where all three zones are connected galvanically
are obvious, and the individual local-action rates are practically meaning-
less when the overall galvanic action is considered. In this example, the
weld is the inherent cathode and its corrosion rates, as influenced by cathodic
protection (from the other zone corroding), would be significantly lower
(or even nil) than its inherent local-action rate. Conversely, the other two
zones, with the higher resistance to corrosion than the weld, would suffer
accelerated corrosion because of the cathodic action at the weld.
Galvanic Corrosion Currents

A multiplicity of galvanic couples exists on a weldment, and one can
only measure the corrosion currents of representative couples. Using the
zero resistance ammeter technique and isolating various parts of the weld-
ment some of these galvanic corrosion currents have veen measured. In
every case studied, the galvanic corrosion currents correlated with the
observed interrelationship of the zonal open-circuit potentials. Figures 4
to 6 present the observed galvanic corrosion currents and the respective

zonal potentials.
All galvanic corrosion current data were taken using equal anode and
cathode areas and presented on a microinch per ampere per centimeter
squared basis. The areas of the weld metal and the HAZ are limited as
compared to the area of the PM. If the same data were taken, but the ex-
posed area of the PM was increased to a size more indicative of actual
conditions, the results of the galvanic corrosion data would be affected
as follows.
1. If the PM was the most electropositive area of the specimen, the
corrosion rate of the inherent anode would be greatly increased. The
maximum corrosion rate of the anodic zone would depend on its relative
area ratio with respect to the PM and on the polarization characteristics
of both zones.
2. If the PM was the most electronegative area of the weldment, its
corrosion behavior would tend towards its local-action corrosion char-
acteristics as its area ratio was increased. The larger the PM area, the
more extensive would be the cathodic protection of the rest of the specimen.
In both these cases the magnitude of the corrosion current is limited by
the area of the cathode. For the cathode-controlled specimens in this
investigation, the maximum galvanic corrosion current possible (with
increasing cathode/anode area ratio) is governed mainly by the concentra-
tion polarization characteristics of the environment; the effect of anode
polarization towards limiting the maximum current density would be
evident to a somewhat lesser extent.
An actual field specimen is shown in Fig. 8 for which data are given in
Fig. 5. The same and other field specimens are shown in Figs. 9 and 10.
In this case, the weldments (6061 with an unknown filler material said to be
unsatisfactory) were removed from a pipeline that had been in service for
several years. During this time, the bare external surface of sections of
the pipe at the welds were exposed to seawater. It is obvious from the
pictures, and supported by the experimental data, that the HAZ of this pipe
are prone to selective corrosion while the weld metal and the parent metal
remain relatively unharmed. Ultimate failure of the pipe system several
miles in length occurred because of extensive destruction of HAZ material
at various weld areas. This shows what can happen if the wrong combinations
of PM and FM are used. Many examples of the proper selection of ma-
terials could be cited to show satisfactory performance.
Another example of the significance of data on open circuit potentials
of the three areas of interest is shown in the weldment of 5086 aluminum
alloy with 5356 FM as shown in Fig. 4. Here, the PM and the HAZ are
considerably positive to the FM. This information indicates that the weld
area would suffer accelerated corrosion as influenced by the large cathode
f\)
I
O
FIG. 10—Three specimens from Figs. 8 and 9 showing the corrosion in the HAZ and the
lesser attack on the FM.
area, but no quantitative analysis can be made without additional infor-

mation.
Galvanic corrosion of the weld material was influenced directly by the
open-circuit potentials and the polarization characteristics of all three
zones. Figure 4 illustrates the magnitude of the galvanic corrosion currents
associated with corrosion of the weld area. The most prominent reaction
was between the PM and the weld. According to the data, the weld would
corrode at a rate proportional to the current density noted (—1.6 nA/cm'')
and would be directly influenced by the ratio of the PM area to the weld
area. This area-ratio influence could be as high as one order of magnitude
before concentration-polarization eff'ects began to predominate. This is to
say that the corrosion of the weld associated with galvanic action could be
as high as 16 /um A/cm^ depending on the environment and the anode
polarization characteristics of the weld metal.
Because the weld area was found to be the most electronegative area,
none of the associated galvanic couples have the possibility of affording
University of Washington (University of Washington) pursuant to License Agreement. No further reproducti
the weld cathodic protection, and the uhimate rate of the weld's destruction
would be a direct sum of its local-action corrosion rate and the galvanically
induced corrosion rate.
An attempt to summarize the results in terms of relative behavior is pre-
sented in Table 2. The maximum galvanic susceptibility is 2.5 mpy. The
local-action corrosion rate of the same zone is 0.9 mpy. By summation, its
total corrosion rate would be 3.4 mpy. This total rate is, obviously, a
minimum corrosion rate. Many factors can act to accelerate the corrosion
TABLE 2—Potentials and galvanic currents between various segments of the specimens.
6061 5083 5085 7002 6061

4043 5356 5356 5356 Pipe
Potential (V-SCE)"
PM -0.715 -0.750 -0.745 -0.790 -0.730
HAZ -0.720 -0.755 -0.750 -0.800 -0.740
weld metal -0.695 -0.785 -0.785 -0.785 -0.735
Local-action corrosion
rate (mpy)
PM 1.7 0.9 1.1 0.5 6.8
HAZ 0.9 0.9 1.0 0.3 1.0
weld metal 2.8 1.6 2.8 2.7 1.6
Maximum galvanic
susceptibility
zone HAZ weld weld HAZ HAZ
rate 2.5 2.8 3.5 1.8 1.2
Total corrosion rate,
most susceptible zone
zone HAZ weld weld HAZ HAZ
rate (mpy) 3.4 4.4 6.3 2.1 2.2
Monel INX HY
K-500 50 T-IA 130/150
Potential (V-SCE)"
PM -0.205 -0.755 -0.705 -0.680
HAZ -0.215 -0.750 -0.730 -0.660
weld metal -0.225 -0.725 -0.725 -0.685
Local-action corrosion rate (mpy)
PM 0.7 5.3 4.6 3.2
HAZ 0.3 5.6 6.8 5.5
Weld metal 1.5 4.8 4.5 6.4
Maximum galvanic susceptibility
zone weld PM HAZ weld
rate 1.6 7.7 9.0 7.3
Total corporation rate, most
susceptible zone
zone weld PM HAZ weld
rate (mpy) 3.1 13.0 15.8 13.7
' V-SCE = voltage per saturated calomel electrode.
of the susceptible zone, the most important, in the case of immersion in

quiescent seawater, being the area effect of the large PM.
Conclusions
The corrosion of welds in quiescent seawater has been investigated by

electrochemical laboratory techniques and the investigative procedures
described in this paper are adequate to allow characterization of the
following: (a) relative anode/cathode behavior of each zone comprising the
weldment, namely, the PM, the HAZ, and the weld metal; (b) inherent
corrosion properties of each zone, including polarization characteristics
and local-action corrosion rates; (c) magnitude of galvanic action between
zones; and (d) corrosion rate of zone with greatest susceptibility to corrosion
as influenced by its local-action corrosion rate and by its galvanic action
with the rest of the weldment.
Acknowledgments
The welded specimens were provided by the Naval Applied Science
Laboratories in Brooklyn, New York, the Huntington Alloys Division of
the International Nickel Company, the Inland Steel Company, and the
Reynolds Metals Company. Most of the laboratory work was performed
by J. A. Turley in connection with his thesis research leading to the Masters
Degree in Ocean Engineering.
References
[/] Ketcham, S. J. and Haynie, F. H., Corrosion, Vol. 19, 1963, pp. 242t-246t.
[2] Guy, A. G. in Elements of Physical Metallurgy, Addison-Wesley London, 1960, pp.
32-35.
[3] Henthorne, M., Corrosion, Vol. 30, 1974, p. 39.
[4] Schumaker, M. B., Kelsey, R. A., Sprowls, D. O., and Williamson, J. G., in Stress
Corrosion Testing, ASTMSTP425, American Society for Testing Material, 1967, p. 317.
[5] Mears, R. B., and Brown R. H., Industrial and Engineering Chemistry, Vol. 33, 1941,
p. 1003.
[6] Snodgrass, J. S., "The Effects of Velocity on the Polarization of Low Carbon Steel in
Sea Water," thesis, University of Miami, 1969.
[7] Smith, C. A., "The Effect of Aerobic Marine Bacteria on the Corrosion of Steel in Sea
Water: A Preliminary Study," thesis. University of Miami, 1968.
George Schick1 and D. A. Mitchell2
Galvanic Corrosion of Underground Power

Distribution Cable Materials
REFERENCE: Schick, George and Mitchell, D. A., "Galvanic Corrosion of

Underground Power Distribution Cable Materials," Galvanic and Pitting Cor-
rosion—Field and Laboratory Studies, ASTM STP 576, American Society for
ABSTRACT: Bare concentric neutral conductors of buried power cables have
failed due to corrosion in several areas of the United States. Galvanic corrosion,
between the neutral conductor anode and a "semiconducting polyethylene" tape
cathode, was investigated as one of the possible corrosion mechanisms. The
results indicate that the rate of the galvanic corrosion is controlled by the cathode
and in the present cable design contributes little to the neutral wire failure. If a
semiconducting polyethylene jacket is extruded over the neutral conductors, the
contribution of galvanic corrosion at jacket defects may become significant.
KEY WORDS: corrosion, galvanic corrosion, power lines, conductors
Power cables with bare concentric neutral wires are used extensively
in buried power distribution networks throughout the United States. In
the past two years there was an increasing awareness of the fact that the
neutral wires are corroding to the point of complete failure (see Fig. 1).
As a result of these failures, alternating currents of high intensity can leak
into the earth or onto other buried structures, such as telephone cables,
which are not designed to carry these currents. Since the earth is a rela-
tively good conductor, the neutral wire failure often goes unnoticed by the
power companies and power consumers. However, on at least two occa-
sions in New Jersey, 20 to 37 A of alternating current caused service
affecting failures of the buried telephone plant in joint use trenches as
reported by McLellan and Schick [2].3 As a result of an inquiry at 31
power companies, Huston 4 surmised that between 1965 and 1973, these
companies found 155 corrosion areas on 59 216 miles of cables with tinned
1
Member of the technical staff, Bell Laboratories, Whippany, N.J. 07981.
2
Metallurgical engineer, General Public Utilities, Reading, Pa.
3
4
Huston, G. H., General Public Utilities, Parsippany, N.J., private communication.
69

a
o
E
SCHICK AND MITCHELL ON UNDERGROUND POWER DISTRIBUTION 71
copper neutral wires and 18 corrosion areas on 1520 miles of cables with
bare copper neutral wires. Zastrow [2-4] and Puschel [5] have studied this
corrosion problem by conducting field measurements and attempting to
correlate their findings with environmental factors. As of this date, a
number of failure mechanisms have been proposed, that is, stray currents,
long line corrosion cell current, galvanic corrosion, corrosion by sulfides
in anaerobic soils, cathodic protection interference currents, alternating
current corrosion, and differential aeration. The present study investigates
galvanic corrosion in detail and its consequences on a factory applied
protective system.
Materials in the Concentric Neutral Power Cable

Two different cables were examined in this study. The first one has 19
stranded AWG 4/0 EC aluminum center conductors insulated with 0.2-in.
(0.51-cm) thick polyethylene. The outer surface of this insulation is covered
by a 0.040-in. (0.1-cm.) thick semiconducting polyethylene (SCPE) layer.
The SCPE is not a semiconductor in the classical physical sense. It is
polyethylene containing carbon particles which render it a modest con-
ductor. The outside diameter of this cable is 1 in. (2.54 cm). There are
19 helically wound 14-gage tinned copper neutral wires in direct contact
with the SCPE layer. The tinning on the neutral wires of this cable is
actually 50 /uin. (1.27 X 10~^ cm) thick alloy of the following composition:
84 percent lead, 13 percent tin, 2 percent antimony, and 1 percent
bismuth [6].
The second type of cable construction is basically the same as the first
one with some exceptions. It has seven stranded AWG 2 EC aluminum
center conductors. The outside diameter of this cable is 0.75 in. (1.9 cm)
and the neutral wires are ten helically wound l2-gage bare copper con-
ductors.
Experimental Procedure
The present investigation used the galvanostatic polarization technique
to establish the corrosion potential and corrosion current density of the
galvanic cells operating between the SCPE cathode and copper or lead-tin
alloy anode. This technique has been described by Fontana and Greene [7].
The neutral wire electrodes were prepared by enclosing 12-in. (30.48-cm)
long wire sections in pyrex tubes with epoxy resin, leaving approximately
1-in. (2.54-cm) long wire to be exposed to the corrosive environment. The
wire ends were also masked with epoxy resin filled glass cups (see Fig. 2).
The SCPE was hot pressed on 0.003 in. (0.0076 cm) thick, 0.5 in. (1.27 cm)
wide copper ribbons and the edges trimmed 0.125 in. (0.317 cm) beyond the
edges of the copper. The copper ribbon and a small portion of the SCPE
I
I
were tightly enclosed between two Lucite blocks in which a 0.5 in. (1.27 cm)
wide, 0.004 in. (0.01 cm) deep channel was machined. This channel is
0.75 in. (1.9 cm) wide and 0.030 in. (0.076 cm) deep at one end to accom-
modate a small segment of the SCPE. In order to assure that the copper
ribbon does not get in contact with the corrosive environment, the channel
in the Lucite was precoated with silicon grease, and the two blocks were
tightened together with nylon screws (Fig. 3).
The polarization experiments were conducted in 0.1 M sodium sulfate
(NaaSOO + 0.01 M sodium chloride (NaCl) solutions at three different
pH (2.85, 6.4, and 10). The original pH of the solution was 6.4; the other
two were prepared by an addition of sulfuric acid (H2SO4) or sodium
hydroxide (NaOH). The experiments were carried out in both air contain-
ing and nitrogen (N2) gas deaerated solutions. Polarization experiments
were also carried out in a moist soil that was collected at one of the cor-
rosion failure sites in Parsippany, N.J. The analysis of this soil is listed in
Table 1.
TABLE 1—Chemical analysis of soil from the Parsippany, N. J. failure site.
Chemical Components in 100-g Soil
Ca++ 1.0 mg
Mg++ 1.0 mg
Na+ and K+ as Na+ 4.0 mg
CI- 7.0 mg
SO4— <5.0mg
NH4+ ND
CO3-- ND
NOTE—ND = not detected, and

pH = 6.4 based on 100-ml water extract of 1-g soil.
The test electrodes were cleaned in acetone for 3 min at room tempera-
ture before placing them in the corrosive media. The neutral wire electrodes
were exposed for 24 h and the SCPE electrodes for 48 h before the applica-
tion of polarizing currents. The open circuit potentials were measured
during the last 2 h of these time periods. The applied galvanostatic current
step rate was 50 min/decade. All experiments were carried out at 22 ± 1°C.
Another series of experiments were carried out to measure the galvanic
currents, resulting from the anodic and cathodic reactions, with a zero
resistance milliammeter. The circuit of this instrument was previously
described by Henry and Wilde [8\ For this experiment, 6-in. (15.24-cm)
long sections were cut from actual power cables. The neutral wires were
removed and a 0.5-in. (1.27-cm) wide copper tape was tightly strapped
around the SCPE surface on one end of the specimen and electric lead wire
was soldered on this tape. The copper tape was then insulated with several
^41 r
, r^ m
layers of black electric tape. A similar thickness of black electric tape was
also wound around the other end of the specimen to serve as an insulating
spacer. The neutral wires were soldered onto a copper wire ring on both
ends forming a circular cage. An electric lead wire was also soldered on
one of the wire rings. The neutral wire cage was then positioned around
the cable touching only the insulating tape. The cable ends and electric
contacts were cast in epoxy resin so that only known surface areas of the
electrically isolated components could be exposed to the corrosive liquid
(Fig. 4). The cable and neutral wire leads were then connected to a series of
switches, which in one position short circuited the galvanic cell through a
12-gage copper conductor, and in another position measured the galvanic
current with the zero resistance milliammeter.
All neutral wire electrodes of the cable specimens were cleaned with
acetone for 3 min at room temperature before the start of the experiments.
The environments in which the zero resistance milliammeter experi-
ments were conducted are the previously mentioned air containing solutions
the soil from Parsippany, N.J. thoroughly saturated with distilled water,
and a mixture of 990 cm' 1 percent NaCl solution with 10 g of agar-agar.
Results and Discussion

The results of the galvanostatic polarization experiments in the pH 2.85,
6.4, 10 solutions and in the moist Parsippany, N.J. soil are listed in Tables 2,
3, 4, and 5, respectively. Although the open circuit potentials {E"') of the
SCPE electrodes reached a stable value after 48-h exposure to the test
solution, this potential was as much as 100 mV different from one electrode
to another tested under identical conditions. This is not surprising since
the polyethylene-carbon mixture in the SCPE may be quite inhomogeneous
and the contribution of voltage drop at the electrode surface can be con-
TABLE 2—Data from galvanostatic polarization measurements in O.IM NaiS02 + O.OIM

NaCl, pH adjusted to 2.85 with HiSOt.
Eoc v e r s u s /corr
Solution Electrode Calomel, V ^corr"' V MA/cm''
Air SCPE +0.180

0.492 3.9
Air Pb/Sn alloy -0.499
Air SCPE +0.180 0.047 0.073
Air Cu -0.048
N2 SCPE -0.037
0.430 0.1
N2 Pb/Sn alloy -0.431
N2 SCPE -0.037
0.123 0.000:
N2 Cu -0.127
FIG. 4—Galvanic corrosion specimen made of concentric neutral type power cable.
TABLE 3—Data from galvanostatic polarization measurements in 0.7M Na^SO^ + O.OIM

NaCl, pH 6.4.
Eoe v e r s u s loorr
Solution Electrode Calomel, V V MA/cm*
Air SCPE -0.006

Air -0.393 -0.347 1.91
Pb/Sn alloy
Air SCPE -0.006
Air -0.211 0.042
Cu -0.228
Nj SCPE +0.025
-0.477 -0.470 0.21
Nj Pb/Sn alloy
N2 SCPE +0.025
-0.137 0.027
Cu -0.154
TABLE 4—Data from galvanostatic polarization measurements in O.IM Na^SOt + O.OIM

NaCl, pH adjusted to 10 with NaOH.
Eoc versus icon

Solution Electrode Calomel Econ" V Â/cm^
Air SCPE -0.057 -0.348 2.25

Air Pb/Sn alloy -0.452
Air SCPE -0.057 -0.133 0.006
Air Cu -0.140
Na SCPE -0.096 -0.450 0.053
Nj Pb/Sn alloy -0.465
N2 SCPE -0.096 -0.159 0.0015
N2 Cu -0.165
TABLE 5—Data from galvanostatic polarization measurements in a soil from Parsippany,

N.J.
Eoc v e r s u s Joorr
Environment Electrode Calomel, V E^^'", V MA/cm*
Soil SCPE +0.019 _o47o ^029

Soil Pb/Sn alloy -0.485 ""^'^ "'"'^'^
S°!! SCPE +0.019 _oo7o 00004
Soil Cu —0.078
Copyright by ASTM Int'l (all

University of Washington (University
siderable. A similar but smaller (50 mV) inconsistency of E" on the lead-tin
alloy coated copper electrodes was also observed. This can be attributed to
the fact that the SO-ûin.-thick coating is quite porous, and variation in this
thickness can change even further the area of exposed copper at the pore
sites. Although the measured potential is primarily due to the lead tin
alloy coating, it is also influenced by the mixed potential of the lead-tin
alloy-copper galvanic cell. Of the three different electrodes, copper showed
the most consistent E°' values from specimen to specimen tested under
identical conditions.
Comparison of the open circuit potential of the individual electrodes
and the corrosion potential of the galvanic couple (Econ"') indicates that
the galvanic corrosion reactions in all the environments are cathodically
controlled.
The effect of dissolved oxygen in the solution as a cathodic depolarizing
agent is obvious when the corrosion current densities (j'corr) are compared
for the galvanic couples in air containing and deaerated solutions. The
presence of oxygen increases the corrosion rate by orders of magnitude
in most cases.
As expected, /corr of the SCPE-lead-tin alloy is larger than the SCPE-
copper couple in all environments used in this study. The amphoteric
lead-tin alloy corrodes at a higher rate in acidic and alkaline solutions
than in the neutral solution while the corrosion rate of copper is the
highest in the acidic and lowest in the alkaline solution. The relatively
low icorr values in the Parsippany, N. J. soil are probably due to the fact
that the soil in the galvanostatic polarization experiments was only moist
and not saturated with water.
The galvanic corrosion current data, obtained with the zero resistance
milliammeter, are listed in Table 6. The galvanic corrosion current densities
TABLE 6—Galvanic cell currents measured with zero resistance milliammeter on cable
specimen.
Galvanic Current Density,

Environment Galvanic Couple iiA/cm^
pH 2.85 solution -I- air SCPE, Pb/Sn alloy 0.297

pH 2.85 solution + air SCPE, Cu 0.063
pH 6.4 solution + air SCPE, Pb/Sn alloy 0.024
pH 6.4 solution -|- air SCPE, Cu 0.009
pH 10 solution + air SCPE, Pb/Sn alloy 0.039
pH 10 solution + air SCPE, Cu 0.002
Parsippany, N. J. soil SCPE, Pb/Sn alloy 0.056
Parsippany, N. J. soil SCPE, Cu 0.033
1 % NaCl solution
+ agar-agar mixture SCPE, Pb/Sn alloy 0.44
" Electrodes are the same type as those used in the galvanostatic polarization experiments.
measured in the solutions are lower than those calculated from the galvano-
static polarization curves. This is partially due to the difficulty of making
good electric contact on the SCPE surface of the cable and, partially,
because the long term current measurements are conducted with anodes
where corrosion products build-up contributes to the polarization of the
lead-tin alloy or copper anodes. In the Parsippany, N.J. soil environment
the zero resistance milliammeter measurements produced higher current
densities than the galvanostatic polarization data, because the former soil
specimens were thoroughly saturated with distilled water while the latter
soil specimens were only moist. The relative corrosion rates are also indi-
cated in the zero resistance milliammeter measurements; that is, lead-tin
anodes corrode at a higher rate in any of the environments than copper
and for both types of specimens the corrosion rate is the highest in the
acidic solution. The lowest corrosion rate in these experiments is also
indicated in the alkahne solution for copper and in the neutral solution
for the lead-tin alloy.
Calculations based on Faraday's law indicate that 1 Â/cm^ corrosion
current density can remove 1.16 mil (2.95 X 10"^ cm) lead-tin alloy or
0.46 mil (1.17 X 10"' cm) copper in one year. Comparison of these data
to the measured corrosion current densities indicate that although galvanic
corrosion between SCPE and lead-tin alloy or copper can contribute to the
corrosion of the power cable neutral wires, these corrosion rates are too
low to cause the type of failures encountered in the field.
The cathodic control aspect of galvanic corrosion of concentric power
cable neutrals merit some further discussion in view of the proposal made
by Marwick [9] to use SCPE outer jacket over the neutral wires to control
corrosion. It is conceivable that such an outer jacket will reduce the number
of occurrences of long cell current, stray current, or alternating current
leakage induced corrosion. However, at areas where the outer SCPE
jacket is damaged, the cathode/anode surface area ratio of the galvanic
corrosion cell will be strongly increased and, consequently, the presently
negligible galvanic corrosion rate will be increased to the point of playing
an important role. Similar type of corrosion failures have been discovered
on galvanized high strength steel armor wires jacketed with carbon black
containing neoprene [10].
Conclusions
1. The galvanic corrosion between SCPE cathode and lead-tin alloy or
copper anode is cathodically controlled.
2. Air in the corrosive media acts as a cathodic depolarizer and increases
/corr of the galvanic cell compared to the same data measured in deaerated
corrosive media.
3. Both the lead-tin alloy and copper anodes of a galvanic cell, with
SCPE cathode, corrode at the highest rate in an acidic solution. The cor-
rosion rate of the same type of cells is the lowest in neutral solution for
lead-tin alloy and in alkaline solution for copper.
4. Comparison between measured z'corr values and calculations based on
Faraday's law indicates that although galvanic cells can contribute to the
neutral wire corrosion, the currents produced by these cells in the present
cable construction cannot explain the failures encountered in the field.
However, if the cable is redesigned using a SCPE jacket over the neutral
wires, defects on this outer jacket may increase the galvanic corrosion
efi"ect by several orders of magnitude. This implies that the neutral wires
should be individually surrounded by such a SCPE layer so that at any
given defect only one or two neutral wires could be affected.
References
[1] McLellan, D. W. and Schick, G., "Corrosion of Concentric Neutrals on Buried Power
Distribution Cables—A Preliminary Report," presented at the Institute of Electrical
and Electronic Engineers Power Engineering Society Conference and Exposition on
Underground Transmission and Distribution, Dallas, Tex., 3 April 1974.
[2] Zastrow, O. W., "Copper Corrosion in High Resistivity Soil," U.S. Department of
Agriculture, Rural Electrification Administration Staff Report, 31 Oct. 1972.
[3] Zastrow, O. W., "Soil Corrosion of Copper Concentric Neutral Wires on Underground
Electric Cable," U.S. Department of Agriculture, Rural Electrification Administration
Status Report, 8 Aug. 1973.
[4] Zastrow, O. W., "Copper Corrosion in Moderate and High Resistivity Soils," presented
at the National Association of Corrosion Engineers' Corrosion/74, Chicago, 111.,
4-8 March 1974.
[5] Puschel, M. A., "URD Cables Cannot be Buried and Forgotten," presented at the
National Association of Corrosion Engineers Corrosion/74, Chicago, 111., 4-8 March
1974.
[6] Marwick, I. J. and McNamara, J. H., Underground Engineering, Vol. 2, No. 3, April/
May, 1971, pp. 17-24.
[7] Fontana, M. and Greene, N. in Corrosion Engineering, McGraw-Hill, New York, 1967,
p. 342.
[8] Henry, W. D. and Wilde, B. E., Corrosion, Vol. 27, No. 11, 1971, pp. 479-482.
[9] Marwick, I. J., Electrical World, Vol. 182, No. 2, 15 July 1974, p. 60.
E. Escalante1 and W. F. Gerhold1
Galvanic Coupling of Some Stressed

Stainless Steels to Dissimilar Metals
Underground
REFERENCE: Escalante, E. and Gerhold, W. F., "Galvanic Coupling of Some

Stress Stainless Steels to Dissimilar Metals Underground," Galvanic and Pitting
Corrosion—Field and Laboratory Studies, ASTM STP 576, American Society for
ABSTRACT: Stainless steels, Type 301 half hard and Type 301 full hard, have
been found susceptible to failure by hydrogen embrittlement when stressed as
low as 40 percent of their yield strength and cathodically charged above 1 MA/cm2
by galvanic coupling to a dissimilar metal in four years of exposure at six under-
ground test sites. However, stainless steels Type 304 and alloys 26Cr-lMo and
26Cr-6.5Ni were resistant under similar conditions. Failures by stress-corrosion
cracking were not observed in any of the materials. Electrochemical measure-
ments made periodically above ground are correlated with the subsequent visual
examination of the specimens.
KEY WORDS: corrosion, galvanic corrosion, hydrogen embrittlement, soils,
stainless steels, stresses, stress corrosion, underground corrosion
Increased interest in the use of stainless steels for underground applica-

tions has activated a number of programs directed at learning more about
the behavior of these materials in such an environment [1,2].2 Data from a
14-year program studying the corrosion of several stainless steels under-
ground has been published by the National Bureau of Standards (NBS) [3].
Of particular interest, however, is that situation where the stainless steel is
under stress such as can occur, for example, when stainless steel pipe clamps
are used to join or repair underground utility services. Often, the circum-
stances are further aggravated by planned or accidental galvanic coupling
of the stainless steel to a dissimilar metal.
This paper is a presentation of some of the work that is being carried out
by NBS in order to gather data and develop a better understanding of the
1
Metallurgist and materials engineer, Institute for Materials Research, National Bureau
of Standards, Washington, D. C. 20234.
2
81

associated phenomena observed such as the effects of stress and current

density on the failure of stainless steel.
Materials
The four types of stainless steel used in this study are listed in Table 1
with their chemical compositions. Table 2 gives the conditions and me-
chanical properties of the alloys. Austenitic stainless steel Type 301 was
exposed in both the half-hard and full-hard condition, exhibiting the
highest strength levels of the materials in this portion of the study with
tensile strengths well over 150 ksi (1035 MPa). This higher strength for the
Type 301 stainless steel is due to the presence of martensite formed during
the cold working process. Type 304 austenitic stainless steel was used in the
annealed condition and had lower tensile properties. Alloy 26Cr-lMo, a
ferritic single-phase stainless steel, was exposed in the annealed condition
TABLE I—Chemical composition of materials major elements', weight percent.
Stainless
Steel* Cr Ni Si Mn Mo
301 HH 17.43 7.14 0.10 0.34 0.016 0.030 1.02 0.22

301 FH 16.98 7.23 0.13 0.54 0.013 0.020 0.86
304 18.2 9.8 0.048 0.50 0.012 0.030 1.46 0.17
26Cr-lMo 26.18 0.10 0.002 0.21 0.011 0.010 0.01 0.94
26Cr-6.5Ni 26.5 6.2 0.015 0.40 0.02 0.022 0.49 0.04
" Balance iron.

" H H = half hard, and
F H = full hard.
TABLE 2—Mechanical properties and applied stress.
Yield %
Tensile Strength Elongation Applied Stress,
Stainless Strength, 0.2% 5.08-cm % Yield
Steel Condition" ksi'' Offset, ksi'' gage Hardness Strength, ksi""
301 HH 162 116 25 R„34 36 42

301 FH 203 175 9 R„44 22 38
304 annealed 87 46 52 RB85 93 43
26Cr-lMo annealed 72 54 26 RB88 76 41
26Cr-6.5Ni partial anneal 132 121 14 R„31 34 41
" H H = half hard, and

F H = full hard.
' To convert from ksi to MPa multiply by 6.9.
ESCALANTE AND GERHOLD ON GALVANIC COUPLING 83
as was the two-phase stainless steel alloy 26Cr-6.5Ni which had tensile
properties almost twice those of the 26Cr-lMo alloy.
The metals chosen for galvanic coupling to stainless steel were mag-
nesium, zinc, and iron, commercially available in the forms described.
A 1.2 m length of extruded magnesium, having a 2 by 1-cm cross section
with a 0.3-cm-diameter iron core, was used as an electrode. The zinc elec-
trode was similar in that it too was extruded over a 0.3-cm iron core, but
had a 1.5 by 2-cm diamond cross section and was 30 cm long. The iron
electrode consisted of a 30 cm length of a cold finished AISI 1017-1018 steel,
hexagonal-shaped 2-cm bar.
Soils
Six test sites have been used in this investigation and were selected on the
basis of their physical and chemical makeup as being most representative
of soils that are found throughout the United States [4]. The locations and
soil properties of these areas are listed in Table 3. The following is a brief
description of the character of each site.
Site A
Sagemoor sandy loam is a well drained alkaline soil with a minimum
resistivity of 400 0/cm and is typical of that found in vast areas of eastern
Washington and Oregon. The soil is consistent in composition to a depth
of at least 2 m and supports abundant growth of sage brush.
Site B
Hagerstown loam (soil 55 [3]) is a well drained soil representative of the
majority of well developed soils found in the eastern part of the United
States. The soil consists of a brown loam about 30 cm deep, underlain by
reddish-brown clay that extends 1.5 m or more to underlying rock. The soil
has an average resistivity of 21 000 fi/cm.
Site C
Clay is located on a large clay pit on level land consisting of a plastic
gray clay to a depth of 15 cm, underlain by a gray clay mixed with patches
of brown clay to a depth of 30 cm. This is underlain by a poorly drained,
very heavy plastic clay. The soil has an average resistivity of 700 0/cm.
Site D
Lakewood sand is a white, loose sand with some black streaks occurring
in places. The site is located on a well drained rolling area which is not
subject to overflow from the ocean except under unusual flood conditions.
The sand supports the growth of beach grasses and has an average re-
sistivity of 39 000 n/cm.
II O
00
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o
• ^
• •*
o o
• fNI OO
• « —.
oo n^ r o ( ^ ^^ O
Xo,
00 >rj -^ w-i r~- \ o
8 ^ 8 81
I
CM C
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CN r1 ^
^
II o o
o o 2
o o 2 o
o o o
OD 00 D. 60 O- D<
ft.
1-1
II
OQ
3- SS 5 o o -
li
•a S "2 T3 S
e^ S
o
1/3
•-
o *o "3
2
II11
n
^ CO
in K T5 >J
<mu QwO HO
Site E
Coastal sand is a typical white coastal beach sand located approxi-
mately 60 m from the ocean and has an average resistivity of 27 000 n/cm.
Site G
Tidal marsh is a soil typical of the poorly drained marsh soils that are
found along the Atlantic and Gulf coasts. The site is located along a creek
that empties into the Chesapeake Bay. The soil contains hydrogen sulfide
and has an average resistivity of 4500 fi/cm.
Specimen Preparation
Specimens were supplied by several companies in 2.54 by 30.5-cm strips
sheared from 0.162-cm sheet with the rolling direction parallel to the long
axis of the specimen. The 26Cr-lMo specimens were also supplied with the
rolling direction perpendicular to the long axis. The 26Cr-6.5Ni alloy
specimens were prepared with machined edges. Identification numbers
were stamped on the specimens on arrival using chromium-plated steel dies.
An oblong hole, 0.63 by 1.3 cm, was punched at each end to allow bolting
of the specimen in a U-bend configuration. In addition, a 0.24-cm hole was
drilled 0.6 cm from the end and side for electrical contact. Insulated 14-gage
stranded copper wire was soldered through the small hole on the end, and
the solder area was coated with coal tar epoxy. Specimens were bent
initially around a 3.2-cm diameter mandrel to about a 20-deg angle, then
degreased in trichloroethylene vapor and passivated in 30 percent by
volume concentrated (67 percent) nitric acid at 60°C for 25 min. This was
followed by rinsing in water and air drying. Finally, the preformed speci-
mens were bent and secured with Type 316 stainless steel fasteners so that
the applied strain was in excess of the prestrain, and the sides of the speci-
men were essentially parallel. Stress determinations were made with the
use of strain gages mounted on specimens taken at random from each
system. The strain gage was positioned on the flat unstressed stainless steel
specimen in such a way that during stressing, the gage was on the outer
surface and at the apex of the U-bend where the applied stress was highest.
The applied stress for each material is listed in Table 2. Specimens picked
for the stress analysis were not used in the burial program.
Stressed stainless steel specimens not coupled to a dissimilar metal were
used as controls in the study. The control specimens were prepared in the
same manner as those that were to be galvanically coupled.
Electrode Preparation
Electrical connection to the magnesium electrode was made by soldering
the electrical lead to a 2-cm extension of the iron wire core and over-coating
the joint area. To extend the life of the magnesium electrode, both 2-cm
sides were coated so that only the 1-cm sides were exposed to the soil.
Electrical contact to the zinc electrode was made in the same manner as
with the magnesium. Electrical contact was made to the iron electrode at a
point midway between its ends where a small diameter hole was drilled
through for inserting and soldering the electrical lead. Again, as in all
contact joints, the area was coated with coal tar epoxy. All wires were
carefully labeled for identification.
Exposure
Two specimens from each system were buried at every test site about
30 cm apart in trenches approximately 0.8 m deep and 0.6 m wide. The
specimens and their corresponding electrodes were placed parallel to the
trench and approximately 30 cm apart with the electrical leads extending
above ground. The 1.2-cm magnesium anodes were bent into a horseshoe
shape with the specimen at its center. The wires were attached to a 10 cm
by 10 cm by 2 m wooden post prior to backfilling. After backfilling, the
electrical leads were connected to terminal strips on the post and corre-
sponding couples were connected electrically above ground. The stainless
steel control specimens had their electrical leads attached to a post, but
were not connected to a dissimilar metal.
Electrical Measurements
Electrochemical potentials of the couples versus a copper-copper sulfate
(CU-CUSO4) half cell were measured using a high precision portable pH
meter as a millivoltmeter. The half cell was placed in a remote area (approxi-
mately 15 m away) and shielded from the light to minimize photopotential
effects. Couple currents were measured using a zero impedance circuit
employing an operational amplifier (Fig. 1) or a commercially available
zero resistance ammeter for larger currents. Electrochemical measurements
were made at the time the specimens were buried and three times a year
thereafter when possible with the exception of Site A where measurements
were usually made once a year. Soil resistivities were also determined
regularly at the sites with the 4-pin Wenner bridge [5], again, with the
exception of Site A where the Shepard cane [6] was used.
Removal
On excavation from the soil, the stressed stainless steel specimens were
examined for indications of gross fracture failures. Materials were then
returned to the laboratory for cleaning and a more careful laboratory
examination. In the laboratory the specimens were rinsed in tap water to
remove adhering soil particles and visually examined prior to further
cleaning. The U-bend specimens were disassembled then by removing the
stainless steel fastener and unsoldering the copper wire. Ultrasonic cleaning
ESCALANTE AND GERHOID ON GALVANIC COUPLING 87
I Mj^ (IO"'A)
>M» - • 100 mV OUTPUT AT
lOOKyvdO'T 10"'; 10"*, 10"', lO"* 1CT',I0"2 A
lOK^dO"')
IKy^dO"*)
IOOJI. (10'')
1 0 ^ (10 '
V*i
100 pf
—II—
CURRENT
: 10/1
SIGNAL IN
AMPLIFIED mV
SIGNAL OUT
t $
-I5V +I5V
22K/
POWER
SUPPLY COMMON
FIG. 1—Zero impedence current amplifier.
of the stainless steel in a 10 percent nitric acid solution heated to 50°C for
30 min was followed by rinsing in water and then air drying. After the
acid bath, the stainless steel specimens were visually examined thoroughly.
Results and Discussion—Galvanically Coupled Specimens

The data obtained from Site G appear in Fig. 2. It illustrates the type of
information gathered at each site over the four-year period. The upper
portion of the figure shows the average potential versus time for the ma-
terials indicated. With this potential measurement the stability of the
galvanic couple could be monitored. For example, the potential of the
stainless steel-magnesium couple is seen to drop steadily as the magnesium
corrodes away within the first year of exposure wih a corresponding drop
in galvanic current. On the 16th month, the magnesium wax replaced with
a larger electrode which maintained a fairly steady potential of 1.5 V versus
Cu-CuSOi for the remaining 30 months. The same figure reveals that both
the zinc and the iron, when coupled to stainless steel, maintained a reason-
ably steady potential, 1.0 and 0.65 V versus Cu-CuS04 respectively, with a
drop of approximately 100 mV each over the 48-month period. Galvanic
current alone is a poor monitor for determining the eff"ectiveness of the
galvanic electrode because of its sensitivity to changes in soil characteristics
as reflected in the fluctuating galvanic current plots of Fig. 2. This figure is
« SS-Mg
SS (noncoupted)
TIME, MONTHS
FIG. 2—Average potential and galvanic current data as a function of time from Site G.
based on average readings for specimens at Site G and illustrates the effect
of time on electrochemical measurements because it was at this site that
anode maintenance problems were greatest. Note further that at this site
the noncoupled stainless steel specimens in the four year study became
progressively more active in potential with time changing from —300 to
— 500 mV versus Cu-CuS04 as shown in the upper portion of the figure.
Galvanic Current Measurements

While the potential measurement gave a quick and reliable qualitative
evaluation of the condition of the counter electrode connected to the
stainless steel, the galvanic current gives a quantitative measurement of
the capacity of the couple to generate current and indicates its direction.
Table 4 lists the average galvanic current for each material and the number
of failures that occurred over the period of exposure at the six test sites.
A material was considered failed if inspection disclosed a crack anywhere
on the specimen. A hand lens (X7) was generally used for examination,
and at questionable areas, a low power binocular microscope (X30) was
employed as a final arbiter. From the data obtained it is evident that two
of the stainless steel materials in this study. Types 301 full-hard and 301
half-hard, have a tendency to stress crack. It is shown in Table 4 that
every stressed Type 301 full-hard stainless steel specimen and all but one of
the Type 301 half-hard specimens connected to magnesium failed in the
University of Washington (University of Washington) pursuant to License Agreement. No further reproductions a
ESCALANTE AND GERHOLD O N GALVANIC COUPLING 89
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four years of exposure. The Type 301 stainless steel was generally more
resistant to failure when connected to iron with failures occurring only at
Site C and one at Site G. Zinc generally did cause failure of the stressed
Type 301 stainless steel except at Site A where no failures were observed.
It is apparent that the likelihood for failure increases with increasing
cathodic current on the stainless steel. At any given test site, the largest
currents are generated by magnesium, followed by zinc, and then iron.
Figure 3 illustrates this current-failure relationship. Note that below
1 /[iA/cm^ no failures occurred for the Type 301 stainless steel alloys. As
the current density increases the number of failures increases to the degree
that above 8 /iA/cm^ all Type 301 full-hard specimens failed and above
20 fiA/cm^ all 301 half-hard specimens failed. The fact that the number of
failures increases with increasing cathodic current strongly suggests
hydrogen embrittlement as the mode of failure.
As Table 4 indicates, no failures were observed for the stressed Type 304,
or alloys 26Cr-lMo, and 26Cr-6.5Ni stainless steels when coupled to
magnesium, zinc, or iron at any of the sites in the times indicated. Figure 4
is included to illustrate clearly the fact that these materials were exposed to
the full range of cathodic current with no adverse effects.
The alloys that did not fail were exposed, for the most part, at higher
levels of stress as listed in Table 2 than the Type 301 stainless steels that
tooo
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a
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FAILURES PER SET
(FOUR YEARS)
FIG. 3—Galvanic current density versus failures for Type 301 full-hard and Type 301 half-
hard stainless steels. Each data point represents two specimens.
304 26 Cr-6.5 Ni
ll-YRSI (3-YRS) (3-YRS)
c
o
N
=1.
I
I
• Zn
O Mg
FAILURES PER SET
FIG. 4—Galvanic current density versus failures for Type 304, and alloys 26Cr-IMo, and
26Cr-6.5Ni stainless steels. Each data point represents two specimens.
failed. The results indicate that those materials that, in general, did not
fail were inherently resistant to cracking under the conditions of this study.
Of course, the site with the lowest soil resistivity develops the highest
current densities. Such a situation was noted at Sites C and G where the
highest current densities were found. At first glance. Site A did not appear
to follow this trend. That is, its resistivity (Table 3) was very low, yet the
measured current densities (Table 4) were, likewise, low. The reason for
this apparent discrepancy is that the measurement at Site A was made on
water saturated soil at a nearby stream, thus, leading to an abnormally low
resistance reading. Actually, the resistivity at Site A is quite high because
of the semiarid nature of the area which would account for the low galvanic
currents observed.
Results and Discussion—Noncoupled Specimens

The noncoupled specimens were of interest not only in their own right,
but also because they served as controls for the galvanically coupled
specimens. These controls were identical to the coupled specimens in every
respect except that they were not connected to another metal. Table 5
reveals that there were no failures observed on any of the specimens in
the exposure times given.
92 GAIVANIC AND PITTING CORROSION
TABLE 5—Results ofnoncoupled specimens.
Site A SiteB Site D Site E

Washing- Loch SiteC Wildwood, Wildwood, SiteG
ton Raven Cape May dry sand wet sand Patuxent
System Specimen" Failures Failures Failures Failures Failures Failures
67 301 HH» 0 0 0 0 0 0
70 301 FH» 0 0 0 0 0 0
72 304* 0 0 0 0 0 0
21 26Cr-lMo« 0 0° 0 0 0 0
30 26 Cr-6.5Ni' 0 0 0 0 0 0
« HH = half hard, and

FH = full hard.
' Four year exposure.
' Three year exposure.
'' One specimen missing.
Summary and Conclusions

The results of this study indicate that the stressed Type 301 half-hard
and full-hard stainless steels have a tendency to fail with increasing cathodic
charging suggesting failure by hydrogen embrittlement. Certainly there is
considerable evidence for this phenomenon as has been observed under
laboratory conditions [7-9] and at last one reported service failure [70].
Furthermore, no failures were observed for the Type 304, or alloys
26Cr-lMo, and 26Cr-6.5Ni stainless steels under similar conditions of
stress and environment. It is also important to note that the noncoupled
specimens did not fail, thus, indicating their resistance to failure when at
open circuit potential.
Acknowledgments
The authors are grateful for the help and financial support of the Ameri-
can Iron and Steel Institute and the Committee of Stainless Steel Producers.
Special thanks are extended to R. J. Carpenter, Chief of the Electronics
Instrumentation Section, NBS, for his design of the current amplifier, and
to members of the Corrosion and Electrodeposition Section, specifically
W. P. Iverson and W. J. Schwerdtfeger for their helpful discussions and
assistance, and B. T. Sanderson and J. L. Fink who have helped gather
data at various phases in the program.
References
[/] Steinmetz, G. F. and Hoxie, E. C , Materials Protection and Performance, Vol. 12,
No. 9, 1973, pp. 41^M.
[2] Branch, H. C , Materials Protection and Performance, Vol. 12, No. 3, 1973, p. 9-14.
[3] Romanoff, M., "Underground Corrosion," NBS Circular 579, National Bureau of
Standards, Department of Commerce Clearinghouse, April 1957.
[4] Romanoff, M., Journal of the American Water Works Association, Vol. 56, No. 9,
Sept. 1964, p. 1129.
[5] Wenner, F., "A Method of Measuring Earth Resistivity," Bulletin 12, National
Bureau of Standards, 1915-1916, p. 469.
[6\ Shepard, E. R., NBS Journal of Research, National Bureau of Standards, Vol. 6, No.
4, 1931, p. 683.
[7] Rhodes, P. R., Corrosion, Vol. 25, 1969, p. 462.
[8\ Wilde, B. E., Corrosion, Vol. 27, 1971, p. 326.
[9] Logan, H. L. in The Stress Corrosion of Metals, Wiley, New York, 1966, p. 100.
[10] Raymond, L. and Kendall, E. G., Metal Progress, Vol. 69, Jan. 1968, p. 103.
M. A. Pelensky,1 J. J. Jaworski,1 and A. Gallaccio1
Air, Soil, and Sea Galvanic Corrosion

Investigation at Panama Canal Zone
REFERENCE: Pelensky, M. A., Jaworski, J. J., and Gallaccio, A., "Air, Soil,
and Sea Galvanic Corrosion Investigation at Panama Canal Zone," Galvanic and
Pitting Corrosion—Field and Laboratory Studies, ASTM STP 576, American
Society for Testing and Materials, 1976, pp. 94-113.
ABSTRACT: Various combinations of metals are used widely in military and

industrial equipment. Many of these are deployed worldwide and in many situa-
tions under aggressive natural environmental conditions. The object of this study
and this paper relates to the effects of subtropical environment on coupled, dissimilar
structural metals of military interest. These include aluminum, brass, magnesium,
Monel, steel, stainless steel, and titanium alloys. The environments are the
atmosphere at Fort Sherman, soil (burial) at Fort Sherman, and seawater (total
immersion) at Coco Solo, Panama Canal Zone. Results of this study should
have significance in the selection of materials for design of equipment for use in
these environments. The atmospheric specimens are rectangular, directly coupled,
and offsetted. Offsetting was employed since this would lead to variability in
galvanic effects over the exposed surfaces and edges. End grain attack, particularly
at the edges of the tempered and aged light alloys, is of interest. For soil burial and
seawater immersion, cylindrical specimens connected through a polyacrylate resin
cylinder were used. These were selected as suitable and convenient for this purpose.
The atmospheric specimens were placed at site in April 1973, and the soil and
seawater specimens were located during Oct. 1973. Atmospheric tests are expected
to continue for a total period of four years and soil, five years; seawater tests are
likely to continue for a total of three and one half years.
Atmospheric, soil, and seawater specimens are returned to the laboratory
periodically during the test for examination and weight loss determination to assess
the effects of each of the environments on the various galvanic couple combina-
tions.
Only limited results are available at this early stage of the investigation. Ac-
cordingly, no final determination can be made at this time of the significance of
results.
KEY WORDS: corrosion, galvanic corrosion, pitting, crevice, alloys, atmos-

pheric exposure, soil burial, seawater, Panama Canal Zone
1
Chemical engineer, research chemist, and chief, respectively, Materials Applications
Branch, Materials Engineering Division, Pitman-Dunn Laboratory, Frankford Arsenal,
Philadelphia, Pa. 19137.
94

PELENSKY ET AL ON GALVANIC CORROSION INVESTIGATION 95
Military materiel is deployed and used worldwide under varied and

sometimes severe environmental conditions. Consequently, under such
use and particularly in tropical or marine environments, significant galvanic
corrosion problems usually are encountered.
In the design and fabrication of equipment requiring the joining of dis-
similar metals, the use of electrochemically similar metals is desirable.
That this is not feasible in many instances because of structural, electrical,
or other important design criteria is recognizable and appreciated. But,
where efforts are not applied toward mitigating the dissimilar metal
(potential) effects, galvanic corrosion is likely to ensue and sometimes with
dire consequences.
Specific data relative to galvanic interactions, in tropical and marine
environments, of certain metal combinations frequently encountered in
military equipment often is incomplete, if not totally lacking. There is a
continuing and specific need for this type of information to be made avail-
able to the design engineer, to aid him in the selection of metal combina-
tions, to achieve maximum corrosion resistance. This is the intent of this
study.
This report, however, is only introductory and preliminary, presenting
the limited results available at this early stage of investigation (exposures
of eight months and less). Up to four additional years of exposure are
anticipated and subsequent reports are planned during the progress of and
after completion of this investigation.
Eight different alloys were selected for this investigation: two aluminum
alloys, one brass, one magnesium alloy, one Monel, one titanium alloy,
one steel, and one stainless steel. The specimens designed for this investi-
gation were machined to provide smooth and close fitting surfaces and
equal areas of the coupled members. These were subjected to atmospheric,
soil (burial), and seawater (immersion) environments at the U.S. Army
Tropical Testing Station, Panama Canal Zone. Seven periods of exposure
or inspections were designated, covering a duration period of approxi-
mately five years. The extent of corrosion was based on determined weight
loss and on observed conditions of the specimen surfaces after removal of
the corrosion products. Controls, that is, couples of Hke metals, also were
included.
The form and size of the individual metal specimens and the design and
fastening of the dissimilar metal couples are as follows.
1. Atmospheric couples are flat, rectangular parts partially offsetted

when coupled. This is considered to offer some variability in surface
galvanic effects, both on "free" surfaces, that is, surfaces not in close
proximity to the actual contacting surfaces, and the edges closest to the
contact region. End-grain attack at the edges, particularly in the aged

light (aluminum or magnesium) alloys is expected to become evident.
2. Couples buried in soil or immersed in seawater consist of members
which are cylindrical with flat ends, electrically joined, but separated by
means of a polyacrylate resin cylinder.
Experimental
Materials
The alloys included in this study are 6061-T6 and 7075-T6 aluminum,
360 brass, AZ-31 magnesium, 400 Monel, 4340 steel. Type 316 stainless
steel, and titanium 6A1-4V.
Atmospheric specimens illustrated in Fig. 1 are flat rectangular plates,
about 0.55 by 2.54 by 3.81 cm (0.215 by 1.0 by 1.5 in.), machined from
0.63-cm (0.25-in.) thick flat strips. The plates are coupled by means of an
0.31 cm (0.125 in.) diameter by 5.0 cm (2.0 in.) stainless bolt, through an
off" center 0.47-cm (0.185-in.) drilled hole, and are in direct contact. (The
bolt also serves for mounting the coupled specimen on a mounting bar.)
The fastener is insulated from the faces of the specimen by interposing a
"sf.ST.NUT ' '"i
HOLE ST. ST. .WASHER
PHENOLIC WASHER
1 8 " ST. ST. BOLT
1.00"
O oo
FIG. 1—Atmospheric specimens.
1.27 cm outside diameter by 0.31-cm (0.50 by 0.125-in.) reinforced phenolic

washer under stainless steel washers at the head and nut side of the fastener.
In coupling the atmospheric exposure specimens, the anodic specimen was
in all cases positioned on top of the cathodic specimen to avoid contamina-
tion of the anode by cathode corrosion products.
Specimens for soil burial and seawater immersion, illustrated in Fig. 2,
are 2.54 cm diameter by 1.27 cm (1.0 by 0.5 in.), machined from round bars.
One flat face of the cylinder is drilled to provide a cavity of about 0.70 cm
diameter by 0.94 cm (0.275 by 0.375 in.) deep, which is tapped to accom-
modate a 0.67 cm (0.25 in.) diameter cold-rolled, fully threaded steel screw
by which the coupling is eff'ected. In the completed coupled assembly, the
metal cylinders are separated by a 2.54 cm diameter by 2.54 cm (1.0 by
LUCITE
INSULATOR SPECIHEN
1 8 " ST. ST.

MOUNTING ROD
FIG. 2—Soil burial and seawater immersion specimens.
1.0 in.) length plexiglass rod, with a lengthwise drilled hole to accommodate
the fastening screw. Further, the plastic separator contains a tapped hole
to receive a 0.31 by 5.0 cm (0.125 by 2.0 in.) stainless steel screw. This is
used for mounting the seawater specimens on a bar for racking. In the case
of the soil specimens, a shorter screw, 0.47 cm (0.185 in.), is inserted to
which a dacron thread is fastened to space (5.0 cm, 2.0 in.) and maintain
sequential arrangement and to facilitate emplacement of the coupled
specimens.
All flat and cylindrical metal members were machined from "as-received"
stock so as to remove worked or distorted microstructure, and were
machine ground to a 20 to 50 /zin. scratch free surface finish.
Procedure
Prior to exposure, specimens were degreased with trichlorethylene and

individually cleaned according to the procedure in Table 1. Specimen
weights were then determined to the nearest milligram.
ASTM exposure test racks fabricated from Monel are employed for the
atmospheric exposures. However, aluminum alloy adapter bars were
designed and utilized for mounting of couples (5 cm between centers) to
the test racks (Fig. 3). The couples on the racks face south and are at a
30-deg angle from horizontal. The atmospheric couples are exposed at the
Fort Sherman, Panama Canal Zone, open field site (see Fig.4), approxi-
FIG. 3—Atmospheric exposure rack mounting.
TABLE 1—Chemical cleaning of specimens before exposure.'
Material Pickling Solution Remarks
AZ31-magnesium HNOsSOml/l
Type 316 stainless (litre quantity) temperature, 140 to 160°F
steel HNO3 400 m)
HCl 100 ml
H3PO4 100 ml
CH3COOH 400 ml
Ti-6A1-4V HNO3 180 ml/1 time should not exceed 30 s
H F 30 ml/1
400 Monel (litre quantity)
H2O 400 ml
H2SO4 400 ml
HNO3 200 ml
6061-T6 aluminum (litre quantity)
7075-T6 aluminum H2O 375 ml
USOi 250 ml
HNO3 125 ml
HsPO, 125 ml
CH2COOH 125 ml
360 brass (litre quantity)
HjO 400 ml
H2SO4 400 ml
HNO3 200 ml
4340 steel HCl 300 ml/1 rinse in 5% Na2C03 after
pickling and rinsing in water
4340 steel (litre quantity) after pickling and rinsing
(alternate method) HNO3 100 ml with water, scrub with cleanser
HiSOi 200 ml to neutralize acid
' Temperatures are room temperatures except where noted.
mately 600 m from the sea at the nearest point and 1250 m away in the
direction of prevailing winds. Temperature at this site is fairly constant
and uniform, with the average temperature approximately 81°F with a
daily range of 9°F. The average relative humidity is 87 percent and the
annual rainfall 130 in. with four months dry and eight months rainy. A
total of 144 couples are exposed for each exposure period (36 couple
combinations, 4 replicates each). This exposure was initiated in April 1973
and 7 exposure periods are planned, namely: 2, 4, 8, 15, 24, 36, and 48
months.
After each exposure period, specimens are returned to the laboratory
and cleaned according to the procedure in Table 2 to remove contaminants
and corrosion products. Specimens are visually examined for type and
uniformity of surface attack, such as etching, pitting, crevice, etc., and
1 00 GALVANIC AND PIHING CORROSION
FIG. 4—Fort Sherman open field site.
final weights recorded for weight loss determinations, expressed in milli-

metres per year. Preliminary visual observations and weight loss deter-
minations are included in this report of the 2, 4, and 8 months' atmospheric
exposures.
Soil burial couples, approximately 5 cm (2 in.) between couples (Fig. 5)
are installed at the water table, buried at a depth of 1.2 m (4 ft) below the
soil surface. The soil is clay type with the soil water having a pH of 7.6
and conductivity of 6.88 X 10~^ mho. The soil burial area is adjacent to
the atmospheric open field site (Fig. 6). The same number of couples are
exposed as for atmospheric exposure. The soil burial was initiated Oct. 1973
and seven exposure periods are planned, namely: 2, 6, 12, 24, 36, 48, and 60
months. Preliminary results are included of the 2 and 6 months' exposures.
Seawater couples are mounted 6.2 cm (2.5 in.) between centers on
exfoliation resistant experimental aluminum alloy (MA009) bar frame
racks, 0.91 by 1.22 m (3 by 4 ft) (Fig. 7).
The seawater couples are suspended from a concrete pier completely
immersed on the racks horizontally suspended and are approximately
1.3 m (4.5 ft) below the water surface at low tide and approximately 1.6 m
(5.5 ft) below the surface at high tide in Manzanillo Bay at the Coco Solo
Naval Station, Panama Canal Zone (Fig. 8). Water temperature averages
approximately 82°F. The same quantity of couples are exposed as for
atmospheric and soil burial exposures. The seawater exposure was initiated
in Oct. 1973, and seven exposure periods are planned, namely: 2, 4, 7, 12,
TABLE 2—Methods for cleaning specimens after exposure.
Material Chemical Time Temperature Remarks
AZ-31 magnesium 15%Cr03 1 to 4 h room

Type 316 stainless H3PO4160 ml/1 15 min to 1 h 75°C
steel CrOs 84 g/1
Ti-6A1-4V
400 Monel
6061-T6 aluminum concentrated Ih room if corrosion products
7075-T6 aluminum HNO3 persist use 5%
H3PO4 + 2 % CrOa
at 85 to QCC for 30
360 brass 20% HCl 15 min room

4340 steel H3PO4160 ml/1 1 to 3 h 90 to 100°C used to initially re-
CrOa 84 g/1 move heavy corro-
sion products
4340 steel 3.5 M HCl 2 to 4 h room used to remove cor-
0.2 M SnClj rosion products from
Rodine (AMCHEM) atmospheric speci-
No. 213 1 g/l" mens and as final
treatment for sea and
soil exposed speci-
mens
4340 steel METSO 200 10 to 24 h room steel specimens, cath-
(alternate method) 20% (by weight) ode ; stainless steel
anode; current den-
sity 40 to 60 amp/
ft^; used when time
is not a factor
" Materials Protection, Vol. 6, No. 3, pp. 45-46.

' ASTM Recommended Practice for Preparing, Cleaning, and Evaluating Corrosion
Test Specimens (G 1-67).
18, 28, and 42 months. Preliminary results are included of the 2 and 4
months' exposures.
To adjust for effects of crevice and general corrosion, like metals were
coupled and results compared with those of dissimilar metal coupling were
taken as galvanic corrosion. It is recognized, however, that crevice and
uniform corrosion buildup can affect galvanic corrosion results.
Discussion of Results
Visual Observations
Visual examination of the specimens was made after removal from
mounting bars and disassembling of the couples. A large number of the
^:m
' • J y - ?• • ;£ Js IT ^K
FIG. 5—Soil burial specimens.
atmospheric couples were stuck together by means of a film of corrosion

products and had to be forced apart. Steel couples were the most difficult
to separate.
Only observations following the most recent exposure period are re-
ported. It can be assumed that the effects for earlier exposure periods are
similar but less severe.
AZ31-Magnesium—In the atmosphere, white corrosion products were
present on the magnesium specimens in contact with all alloys; the speci-
mens were hghtly etched, and pitting was observed on the border of the
interface. The sea specimens in contact with Type 316 stainless steel,
Monel, and steel were completely consumed after two months. Specimens
in contact with the other alloys exhibited a heavily pock-marked surface
with penetration ranging from 0.031 in. (0.075 cm) to 0.25 in. (0.64 cm).
The soil specimens had the same type of pock-marked surface as the sea-
water specimens, but not as severe.
Type 316 Stainless Steel—The atmosphere specimens had incipient
pitting on the interface. The sea specimens exhibited crevice corrosion
attack when coupled to themselves, Monel, and titanium. There was no
attack on the soil specimens.
4340 Steel—The atmosphere specimens were etched uniformly showing
a pock-marked surface with deep pits along the border of the interface;
there was hardly any attack when coupled to magnesium. The sea and
soil specimens exhibited a heavily pock-marked surface; hardly any attack
PELENSKY ET AL ON GALVANIC CORROSION INVESTIGATION 1 03
FIG. 6—Soil burial site.
appeared when the specimens were coupled to magnesium and the alumi-
num (6061 and 7075 alloys).
6061-T6 Aluminum and 7075-T6 Aluminum—The 6061-T6 aluminum
alloy corroded to a lesser extent than the 7075-T6 aluminum alloy.
White corrosion products were present on the atmospheric specimens;
pitting was observed on border of interface of the aluminum specimens in
contact with all metals except magnesium and the controls. Pitting occurred
in the sea specimens when they were in contact with all alloys except the
controls and other aluminum alloy; heavy scaling and exfoliation was
observed when the specimens were coupled to magnesium. The soil speci-
mens showed localized pitting.
360 Brass—Surface dezincification and staining was observed in all
environments.
400 Monel—The atmosphere specimens exhibited slight staining and the
sea specimens, pitting when coupled to themselves, Type 316 stainless steel,
and titanium. A slight crevice attack occurred on the soil specimens when
the Monel was coupled to itself, Type 316 stainless steel, brass, and titanium.
Ti-6Al-4V—No attack occurred in any of the environments.
Corrosion Weight Losses
The degrees of corrosion are shown in Table 3 for atmospheric exposure.
Table 4 for soil burial, and Table 5 for sea water immersion.
FIG. 7—Seawater immersion rack.
From Table 3, atmospheric exposure, little or no attack to date is

evident of the Type 316 stainless steel, 6061-T6 aluminum, 7075-T6 alumi-
num, 360 brass, 400 Monel, or titanium 6A1-4V specimens.
General corrosion of the 4340 steel is evident in all couples but pro-
tection to the steel is afforded by coupling with AZ31 magnesium. Galvanic
attack of the steel in all couples is not apparent.
Magnesium, as expected, suffers galvanic attack when coupled to each of
the other alloys. This attack appears generally to be at a decreasing rate
after 8 months of exposure.
From Table 4, soil burial, little or no corrosion is evident of the Type 316
stainless steel, 360 brass, 400 Monel, and titanium 6A1-4V alloys.
General corrosion of the 4340 steel is evident in all couples and the rate
of attack appears to be increasing with time. Protection of the steel is
afforded by the magnesium, but galvanic attack of the steel appears to
occur as a result of coupling to Type 316 stainless steel, 7075-T6 alumi-
num, 360 brass, 400 Monel, and titanium 6A1-4V.
Magnesium is galvanically attacked by coupling with each of the other
alloys. The attack is least in aluminum alloy coupling and greatest in
coupling to steel. The galvanic attack in all cases, however, appears to be
at a decreasing rate.
Coupling of the 6061-T6 aluminum alloy to brass and Monel results in
galvanic attack of the aluminum. Coupling of the 7075-T6 aluminum
alloy to Type 316 stainless steel, brass, Monel, and titanium results in
FIG. 8—Seawater immersion.
galvanic attack of the aluminum. Coupling of the 6061-T6 and 7075-T6

aluminum alloys to magnesium results in increased attack of the aluminum
alloys.
From Table 5, seawater immersion, it may be observed for the mag-
nesium galvanic couples that all the magnesium specimens originally
coupled to Type 316 stainless steel, 4340 steel, and 400 Monel were lost
and essentially all consumed.
Where coupled to the other alloys, the rate of attack to date appears to
be decreasing except where the magnesium is coupled to titanium 6A1-4V.
No galvanic attack of Type 316 stainless steel is indicated. However,
crevice attack is evident where the stainless steel is coupled to Monel and
titanium. This crevice attack is evident also where stainless steel is coupled
to itself. Crevice attack is not apparent when coupled to the more anodic
specimens where cathodic protection is afforded to the stainless steel. This
cathodic protection tendency with stainless steel galvanic couples in
seawater has been investigated and previously reported.^
The rate of attack of steel to date appears to be decreasing where coupled
with cathodic alloys. Protection is afforded, as expected, by coupling to
magnesium and aluminum alloys.
Coupling of 6061-T6 aluminum with the other alloys results in galvanic
attack, except when coupled to 7075-T6 aluminum; and the rate of attack
^ Lennox, T. S., Groover, R. E., and Peterson, M. H., Materials Protection, Vol. 8,
No. 5, May 1969, pp. 41-48.
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appears to be decreasing. The greatest attack of the aluminum is evidenced

where coupled to magnesium.
Coupling of 7075-T6 aluminum with the other alloys results in galvanic
attack, except when coupled to 6061-T6 where some protection appears to
be afforded. The rate of attack in coupling to all the other alloys appears
to be decreasing. The greatest attack of the aluminum is evident where
coupled to magnesium in which case severe attack and delamination of the
7075-T6 aluminum results.
Galvanic attack, at a decreasing rate, of brass is evident from coupling
to Type 316 stainless steel and 400 Monel. Protection is afforded by cou-
pUng to AZ31 magnesium, 4340 steel, 6061-T6 aluminum, and 7075-T6
aluminum.
Galvanic attack of the Monel is not apparent to date. However, early
pitting of Monel in seawater has been observed in some instances where the
Monel is coupled to itself, stainless steel, and titanium. This pitting appears
to be only limited and not the high density pitting attack of Monel sub-
jected to seawater reported elsewhere.'
No galvanic attack of the titanium is evident.
Heavy buildup of barnacle growth on the seawater immersion specimens
develops rapidly. It is expected that this buildup will afford some protection
and result in retardation of corrosion as reported elsewhere.^
Conclusions
Only limited results are available at this early stage of the investigation;
however, some tentative conclusions can be offered.
In general, comparison of the results of atmospheric, soil, and seawater
exposures indicates that least attack occurs in the atmosphere and the
most attack occurs in seawater. Titanium was not attacked in any of the
three test environments. Monel and Type 316 stainless steel were found
resistant in the atmosphere and in the soil. Pitting of Monel occurs in
seawater but is retarded by coupling with the more anodic alloys (mag-
nesium, aluminum, brass, and steel). Crevice corrosion of stainless steel
occurs in seawater but this is also retarded by coupling with the more
anodic alloys (magnesium, aluminum, brass, and steel). Based on available
data, the 6061 and 7075 aluminum alloys appear to offer sacrificial pro-
tection to the steel in seawater, but not in the soil nor in the atmosphere.
There is insufficient data at this time to distinguish any difference in the
rate of attack of aluminum couples in atmospheric and soil exposures.
Magnesium, as expected, affords protection to the other alloys in all three
'Southwell, C. R. and Alexander, A. L., Materials Protection, Vol. 8, No. 3, March

1969, pp. 39-44.
* Southwell, C. R., Butterman, J. D., and Hummer, C. W., "Influence of Marine Orga-
nisms of the Life of Structural Steels in Sea Water," NRL Report 7672, Naval Research
Laboratory, Washington, D. C , 19 March 1974.
PELENSKY ET Al ON GALVANIC CORROSION INVESTIGATION 113
environments except where coupled to the 6061 and 7075 aluminum alloys
in the seawater in which case severe attack and delamination, especially of
the 7075 aluminum, results. The cause of the damaging effect on aluminum
is not known but will be investigated.
Acknowledgments
We wish to thank Anthony Gressel, Tropic Test Center, Panama Canal
Zone, for his invaluable assistance in assembling exposure racks, in
preparation of the soil burial site in installation and subsequent removal
of specimens, and in the packaging and return shipment of exposed speci-
mens to this laboratory. Careful packaging has resulted in virtually no
physical damage to the coupled specimens returned.
We wish to thank R. S. Haskin of Pitman-Dunn Laboratory, who was
extremely helpful in the cleaning, weighing, identification, and assembling
of the specimens prior to shipment to Panama Canal Zone for exposure.
Also, we wish to thank W. F. McTeague, also from Pitman-Dunn, for
his aid in identifying and assembling the specimens.
Pitting Corrosion
Henry Suss1
Localized Corrosion Attack on Carbon

Steel—Case Histories of Service Failures
REFERENCE: Suss, Henry, "Localized Corrosion Attack on Carbon Steel—Case

Histories of Service Failures," Galvanic and Pitting Corrosion—Field and Labora-
tory Studies, ASTM STP 576, American Society for Testing and Materials, 1976,
pp. 117-131.
ABSTRACT: Four case histories of service failures attributable to some form of
localized corrosion attack are reviewed. The initial case history covers a problem
that developed because of the failure to follow operational procedures and be-
cause the wrong chemical was used for the inhibitor. The second case history covers
an instance where the conjoint actions of the environment and cyclic loading
(fatigue) promoted accelerated localized pitting attack rather than the usual loss
in fatigue strength generally associated with corrosion fatigue. The third case
history presents the potential concerns in using an improperly controlled cor-
rosion protection system. The final case history reveals the perils of allowing
systems to remain partially filled with stagnant solutions.
A major concern is the possibility that the same type of failures will recur. An
approach for possible actions in programs for the prevention of premature cor-
rosion failures is recommended.
KEY WORDS: corrosion, failure analysis, corrosion prevention, carbon steels,
protective coatings control, corrosion fatigue
In an article published recently,2 the percentage of equipment failures,

as related to specific modes of corrosion attack, is listed in Table 1. Much
of my experience has been in analysis of many corrosion-related failures,
and I agree that the data presented in that article are representative of the
type and level of service failures.
To select the more representative case histories for this paper, records
from 1958 to the present were reviewed. This review not only recalled many
interesting, frustrating experiences but also revealed that the same types of
failures keep recurring. To express it in an old cliche, "history tends to
repeat itself." Or, as Dr. Mars Fontana of Ohio State University bluntly
1
Principal engineer, Knolls Atomic Power Laboratory, General Electric Company,
Schenectady, N. Y. 12301.
2
"Corrosion and Wear," Iron Age, 21 Jan. 1974.
117

TABLE 1—Corrosion failure breakdown.
Form Percent
General 31.5
Cracking
stress corrosion 21.6 1 23.4
corrosion fatigue 1.8 I
Pitting 15.7
Intergranular 10.2
Erosion
corrosion 7.4)
cavitation 1.1 9.0
fretting 0.5)
Crevice 1.8
De(metal)ification 1.1
Two metal 0.0
NOTE—High temperature, 2.3 percent; weld corrosion, 2.3 percent; cold wall, 1.8 percent;
end grain, 1.1 percent; hot wall, 0.5 percent; and hydrogen embittlement, 0.5 percent.
Source: DuPont Company.
states, "Virtually all premature corrosion failures occur for reasons well
known—and can be prevented."
Case histories and many other equivalent papers are being presented and
published continually. Each contains the pertinent data and the means by
which equivalent and other types of failures can be prevented or minimized.
Yet premature corrosion failures keep recurring at much too high a level.
These failures can be attributed to several possibilities: (a) available data
are overlooked; {b) available data may not reach those persons who could
benefit most; (c) potential use of the available data in minimizing future
corrosion problems was not recognized; and (d) uncertainty in relating
the available data from one failure to stop possible corrosion attack for
other applications.
Case histories of service failures that are related to localized corrosion
attack (exclusive of stress and intergranular corrosion) are reviewed in
this paper. In this effort, I shall explain the means used and the basis for
establishing the factors that contributed to these failures, and I shall review
some recommended actions to stop or minimize the specific forms of
attack. A program that 1 suggest as essential to reduce the extent of similar
premature corrosion failures will conclude this paper.
Case History 1
Through Perforation of Carbon Steel Tubes of a Heat Exchanger

The carbon steel tubes of a heat exchanger, based on studies and avail-
able data, had more than adequate corrosion resistance to the environment
both through the tubes and on the shell side. The tube resistance on the
suss ON LOCALIZED CORROSION ATTACK ON CARBON STEEL 119
shell side (outside diameter) required that specific instructions, listed as

follows, be followed during operations and shutdown periods.
1. During any shutdown period, the shell side shall either remain com-
pletely filled with the solution or completely drained.
2. The chromate levels during operations shall be maintained at 10 to 20
ppm; during periods of stagnancy (inactivity), at 1000 to 2000 ppm.
3. Final instructions covered chemical analyses procedures and the
frequency of such analyses.
After about a year in service, perforations developed in the carbon steel
tubes (Fig. 1) that affected the usefulness of the heat exchanger. A subse-
quent investigation and analysis provided the following information.
1. Operators did not follow instructions. The unit was allowed to remain
partially filled (note water line in Fig. 2 after the tube bundle was removed)
with solution, possibly during shutdown or maintenance periods.
2. Deposits formed on the tube surface because the wrong compound'
was used to develop the required chromate level. The compound was used
at a level equivalent to its maximum solubility, thereby forming a saturated
solution. At such concentration levels, chemicals can readily precipitate
out locally (Figs. 3 and 4) as a result of actions during heat transfer and
drain downs and at water lines.
3. The records indicated that the required number of analyses was con-
ducted and that the chromate levels were maintained within the specified
limits.
The end results of the actions, Items 1 and 2, were water-line attack and
under-deposit corrosion, both of which are forms of concentration cell
corrosion.
This failure, together with the consequences of another similar failure
and lack of manpower to ensure maintenance of the required controls for
the continued use of carbon steel, was reviewed and resulted in the recom-
mendation that the tubes of the replacement bundle be 90 to 10 or 70 to 30
cupro-nickel. Inspections of similar units in service at that time indicated
that the cupro-nickel alloy tubes were resistant to both general and
pitting attack in the absence of inhibitors and were not as sensitive to water-
line attack. The replacement bundle has been in service for more than
eight years with no reported problems.
Case History 2
Leak in Carbon Steel High-Pressure Steam Condensate Bypass Test Line—
Corrosion-Fatigue Attack
After five years of service, crack-like indications were observed in the
subject pipe (Fig. 5) during radiographic inspection of an adjacent repaired
' Proprietary inhibitor compound which consisted of about 30 percent chromate, zinc,
and polyphosphates. The basis for use of this compound could not be established.
FIG. 1—Pitting attack carbon steel heat exchanger tube, area of through performation, XIO.
weld. To establish the adequacy of the pipe, the assembly was hydro-
statically tested. A pinhole leak necessitated replacement of the pipe section.
After the failed pipe was longitudinally sectioned, similar pits or crack-
like indications were evident 4 to 6 in. from each end, in only the three and
nine o'clock positions (Figs. 6 and 7). The attack in the nine o'clock
position is shown in Fig. 6. The remainder of the pipe indicated no sig-
nificant evidence of any corrosion attack.
suss ON LOCALIZED CORROSION AHACK ON CARBON STEEL 1 21
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suss ON LOCALIZED CORROSION ATTACK ON CARBON STEEL 1 23
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FIG. 5—High pressure carbon steel steam by-pass line; attack, radiograph inspection.
A Study of the system and a review of the test unit in operation revealed
the following indications.
1. The chemistry and temperature of the condensate entering and
leaving the pipe were the same. Therefore, the attack could not be attrib-
uted directly to the environment.
2. The subject pipe was a by-pass line attached to a larger diameter main
pipeline of the test system. With each change (eight to ten times a day)
in the test conditions, as required by the program, the main line moved
vertically. This movement subjected the by-pass line to a bending moment
with peak tensile stresses equivalent to the yield strength of the material.
This case history is the only example in my experience where the com-
bined actions of corrosion and low-frequency cyclic loading promoted
accelerated pitting attack rather than the usual loss in the material's
fatigue strength (corrosion-fatigue).
To prevent the recurrence of a similar failure, the test unit would have
required a major redesign. The changes were not initiated, since the
assembly was required for the same test program for an additional six to
nine months. The replacement pipe of the same design was considered
more than adequate for the desired service period.
Case History 3
Localized Perforation of a Carbon Steel Waste Line

During a routine inspection, a perforation was observed in the twelve
o'clock position of a 3-in.-diameter interior coated carbon steel pipe
(0.215-in. wall) after about six years in service. The removed pipe section
with the failed area was submitted for failure analysis.
A 4-ft length of the pipe was sectioned longitudinally. Most of the inside
surface was covered with rust-colored corrosion products. After descaling,
the following were observed.
1. Only one area of significant attack, that of the perforation (Fig. 8),
was noted.
I
I
a
d
Through PerforaLioa
li^nd Section
'U Pi;;!i - Snaj.jow i-o NegliîblL' i'izi-iiii-l

L'i'tions
FIG. 7—High pressure carbon steel steam by-pass line, pitting attack.
2. In an adjacent area, where a large section of coating had failed,

relatively "uniform" metal attack was noted. The typical metal loss was
10 to 20 mils with one locahzed area reduced by 30 to 40 mils (Fig. 8).
3. The coating protected most of the interior surface, but some areas
evidenced the initiation of localized pitting attack (Fig. 9).
The perforation (shown in Fig. 8) is typical of the end result of corrosion
attack in areas of localized failure of the protective layers or of holidays
(voids) in the coating.
Coatings are a useful means for corrosion protection but require con-
tinual inspection to detect damage or deterioration. Since such require-
ments are not practical for inside walls of a pipe, an uncoated pipe would
have been the preferred condition.
suss ON LOCALIZED CORROSION AHACK ON CARBON STEEL 1 27
I
I
o
1 28 GALVANIC AND PiniNG CORROSION
suss ON LOCALIZED CORROSION AHACK ON CARBON STEEL 129
Although larger volumes of metal will be lost, with uncoated pipes, the
pipe would still be functional. Also, the possibility of a localized perfora-
tion developing before detection would be lessened. Routine spot checking
by nondestructive techniques could detect wall thinning that approaches
unsafe limits. To detect areas with localized attack before perforation
occurs would require either 100 percent inspection of the surface or re-
peated hydrostatic testing.
The use of improperly maintained protection systems can create more
concerns than if protective systems were omitted.
Case History 4
Localized Pitting Attack in Steam Generator Carbon Steel Blow-Down Lines

Based on experience and laboratory tests, carbon steel possesses more
than adequate corrosion resistance for service as blow-down lines during
periods of stagnancy. Yet, in one unit, severe pitting attack was detected
in some horizontal lines after less than four years in service.
After the pitted pipe was removed and sectioned, it was evident that the
attack was restricted to the bottom section, five to seven o'clock (Fig. 10).
Available data revealed that carbon steel pipe can exhibit pitting attack in
the environment when allowed to remain only partially filled with the
solution with air in the vapor phase. A subsequent analysis of the blow-
down system indicated that the pitting attack was restricted to specific
horizontal lines. In each instance, these lines remained partially filled with
the solution during periods of stagnancy because of the valve closing
sequence used.
Oxygen, the corrosion accelerant, is continually available in the vapor
phase of most partially filled systems. In a completely filled system, the
low dissolved levels of oxygen dissipate relatively rapidly, resulting in a
solution that remains nonaggressive. To avoid attack in the replacement
pipes, the valve closing sequence was therefore modified to ensure that all
lines would be, and remain, filled completely during periods of inactivity.
Corrosion Prevention Programs
In reviewing the report issued by the government-sponsored National

Committee on Materials Policy (NCMP),^ I quote the following paragraph:
One of the most obvious opportunities for materials economy is control of corrosion.
It has been estimated that the Nation's annual corrosion cost is $15 biUion. One
third of this cost can be saved by applying techniques presently developed and avail-
able. Engineers and designers can make more extensive use of anticorrosion tech-
niques. To this end, pertinent information must be widely disseminated. Research and
development can provide additional means of controlling corrosion.
^ Staehle, R. W., Corrosion, Vol. 31, No. 2, 1970, p. 41.
I
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With the increasing equipment complexity, the consequences of pre-

mature failures, and the data from corrosion failure analyses, a major
effort was initiated within my division several years ago to develop pro-
grams for corrosion prevention and to adopt the best available means for
their implementation. In planning the study, it was recognized that one of
the more important approaches was similar to the recommendation
prescribed in the foregoing quotation: dissemination of pertinent informa-
tion to all engineering disciplines including an understanding of all forms
of premature corrosion attack and available anticorrosion methods.
Following this study, a company-sponsored engineering-oriented cor-
rosion course was developed and presented. Data and experience from
prior failure analyses are an important part of the course content, and, as a
result of this program, interest among all engineers has increased. With
the consequences of this greater understanding, there has been a marked
increase in the means for prevention of corrosion failures. With this back-
ground of tangible results, management is now requesting that new courses
be developed and offered and is encouraging an increase in the level of
attendance.
The importance of engineering-oriented corrosion courses cannot be
overemphasized. If such efforts are not expanded throughout industry,
then other corrosion engineers will report similar case histories, express
concerns relative to their recurrence, or will report that many failures did
occur for reasons that were known but that could have been prevented.
J. W. Spence1 and F. H. Haynie1
Pitting of Galvanized Steel in Controlled

Clean Air Environments
REFERENCE: Spence, J. W. and Haynie, F. H., "Pitting of Galvanized Steel in

Controlled Clean Air Environments," Galvanic and Pitting Corrosion—Field and
Laboratory Studies, ASTM STP 576, American Society for Testing and Materials,
1976, pp. 132-146.
ABSTRACT: Specimens of galvanized steel sheet were exposed to polluted and
clean air in controlled environmental chambers having the capability to simulate
diurnal conditions. Corrosion of the zinc films was essentially a linear function
of time for each exposure condition. The range of weight losses for the polluted and
clean air environments were unexpected approximately the same. However,
uniform corrosion of the zinc occurred in the polluted exposures whereas pitting
corrosion of the zinc was observed in the clean air exposures.
Scanning electron microscopy/microprobe analysis of the galvanized zinc
surface was used to study the mechanism of initiation and propagation of pitting
corrosion. Corrosion products were observed to localize and form a barrier that
could accentuate an acidic condition within the pit. Pitting corrosion is thus accele-
rated by the difference in pH within and outside the pit. During the pollutant
exposures pitting corrosion is prevented because the drastic difference in pH
within and outside the pit. During the pollutant exposures pitting corrosion is
prevented because the drastic difference in pH did not occur.
KEY WORDS: corrosion, metals, galvanized steel, exposure chamber, clean air,
sulfur dioxide, statistical analysis
For the past several years the Environmental Protection Agency (EPA)
has been conducting field and laboratory investigations to assess the
detrimental effects of air pollution on materials [/-5]. 2 The ultimate
objective of these studies has been to develop predictive dose-response
relationships for various classes of materials. This information is needed
to serve as input for cost-benefit studies and as criteria for developing
secondary air quality standards.
Accelerated degradation of materials by pollutants is generally measured
by conducting controlled environment laboratory exposures with and
1
Research chemist and chief, Materials Section, respectively, National Environmental
Research Center, Environmental Protection Agency, Research Triangle Park, N. C. 27711.
2
132

SPENCE AND HAYNIE ON PIHING OF GALVANIZED STEEL 1 33
without pollutants and comparing the observed effects. Thus, a statistically

designed study involving the exposure of economically significant ma-
terials to controlled environments containing pollutants (sulfur dioxide,
nitrogen dioxide, and ozone) as well as clean air was performed. The
results of the polluted and clean air exposures for similar environmental
conditions were compared in order to assess material damage. Over
20 000 h of exposure time, which includes 4000 h of clean exposure, were
accumulated.
This exposure study was conducted in five environmental chambers that
were designed to operate continuously with each chamber having inde-
pendent control of temperature, humidity, lighting intensity, and concen-
tration of pollutant gases [6]. Before initiating this study, differences in
chamber lighting and pollutant distribution, as well as the control capa-
bility of the environmental variables within the five chambers, were adjusted
to be below 10 percent variation for 95 percent of the measurements.
The environmental chambers (Fig. 1) are equipped with a cap that houses
a xenon arc lamp for simulating sunlight. Each chamber also contains a
chill rack (Fig. 2) upon which the material specimens are mounted to
FIG. 1—Environmental chambers.
FIG. 2—Specimen chill rack.
enhance dew formation. Diurnal conditions are simulated as each chamber

features a controllable dew/light cycle. This mode of exposure allows the
surfaces of test materials to absorb and concentrate gaseous pollutants as
they do in real world environments.
Temperature-time profiles (Fig. 3) were obtained by monitoring specimen
temperatures during the dew/light cycles for each set of chamber condi-
tions (temperature and relative humidity). The temperature and relative
humidity of the air flowing into the chambers were maintained at desired
levels. However, the temperature of the specimens continually varied
during the dew/light cycle, thus changing the local relative humidity.
Moisture condensed on the specimens when the temperature was below the
dew point. Since the moisture content of the air is constant (set by feed air
conditions), the relative humidities at the specimens as a function of time
were calculated using the cycling temperature data. Visual detection of
condensation on the specimens occurred at or above a calculated relative
humidity of approximately 85 percent. Thus, at corresponding temperatures
(Fig. 3) the specimens were considered to be wet.
Time of wetness per cycle and geometric mean specimen temperatures
when wet were calculated from the data and are given in Table 1. Previous
studies have shown that the corrosion of metallic materials occurs only
SPENCE AND HAYNIE ON PiniNG OF GALVANIZED STEEL 1 35
40 0
CYCLE TIME-MINUTES
FIG. 3—Temperature-time profiles.
TABLE 1—Cycle time of wetness and geometric mean specimen temperature when wet.
Input Input Relative Humidity

Temperature
of Feed Air 90% 50%
35°C 24.5 min 20.7 min

302.4 K 293.4 K
13°C 22.0 min 7.0 min
283.2 K 277.6 K
NOTE—Geometric mean specimen temperatures were reported in degrees Kelvin (K) for
use in Arrhenius relationship.
when the specimens are wet [7,8]. Therefore, exposure data obtained from
this study should be analyzed in terms of the expected times of wetness.
Commercial 18-gage galvanized steel with an approximate 25 ;um zinc
coating was one of several economically important materials selected for
simultaneous exposure in these experiments. The sheet was cut into 7.6 by
12.7-cm exposure panels. The panels were scrubbed in a warm detergent
solution, rinsed in distilled water, and degreased in acetone. Initial panel
weights were measured on an analytical balance.
For each exposure condition, six galvanized panels were randomly
mounted on the chill racks with thermally conducting silicone paste which
also served to protect the contact surface from corrosion. After exposure
periods of 250, 500, and 1000 h, two panels were removed randomly from
1 36 GALVANIC AND PITTING CORROSION
the environmental chambers. The siUcone paste was removed mechanically.

The corrosion products were dissolved by immersing the panels for approxi-
mately 10 min in a 10 percent aqueous ammonium chloride solution
maintained at 72 to 80°C, followed by scrubbing and rinsing in water and
a final rinse in acetone. The galvanized steel panels were then reweighed
and corrected for the estimated amount of zinc metal lost during cleaning.
The weight loss measurements expressed as grams per panel were con-
verted to zinc film thickness loss in micrometres (yum) using the multipli-
cation factor of 14.98. Units of film thickness are normally used in esti-
mating and comparing product life.
Results
As was theoretically expected, corrosion of the zinc film was essentially

a linear function of time for each of the environmental exposure condi-
tions. Thus a least square fit of the following relationship was obtained
for each set of exposure conditions
CORK = bt
where
CORR = zinc lost in micrometers (/xm),
t = exposure time in years, and
b = coefficient representing the corrosion rate.
For the polluted exposures, the corrosion rates ranged from a low of
3.18 jum/year and to a high of 33.27 /^m/year. Based on analysis of variance
and regression analysis, the corrosion rate with pollutants present was
primarily a function of sulfur-dioxide concentration and input relative
humidity.
Clean air corrosion rates ranged from a low of 1.14 /^m/year to a high of
37.17 yum/year for the respective extremes of input relative humidity and
temperature. Thus, unlike other materials exposed in this study, calculated
galvanized steel corrosion rates for both polluted and clean air exposure
conditions showed the same approximate range.
The surfaces of panels exposed to both polluted and nonpoUuted condi-
tions were examined after removal of the corrosion products. Panels
exposed to polluted environments (Fig. 4) showed no pitting, thus indicat-
ing uniform corrosion; the entire surface of each panel developed a dull
appearance. For the clean air exposures the panels developed pitting
(Fig. 5); however, much of the surface area of each panel retained its
original shiny metallic appearance.
FIG. 4—Cleaned galvanized steel panel exposed to polluted air (X9.4).
The pitting corrosion, expressed as a uniform thickness loss, fits the

relationship
16,020"
CORK = tê 30.53 -
RTM
where
CORR = amount of pitting corrosion (MIH),
ty, = time of wetness, years, and
TM = geometric mean specimen temperature when wet, K.
At 25°C, the corrosion rate is equivalent to a current density of 2.2 ;uA/cm^

over the total specimen surface. Measured pit depths were approximately
25 jum for the most severe conditions (1000 h, high temperature, and high
relative humidity). This rate of corrosion is equivalent to approximately
22 /iA/cm^ Therefore, the estimated cathode to anode area ratio is 10.
Apparently, different corrosion mechanisms take place during the clean
air and pollution exposures. Electron microscopy/microprobe analysis was
used to investigate the corrosion mechanisms of the zinc film.
FIG. 5—Clean galvanized steel panel exposed to clean air (X9.4).
Discussion
Clean Air Exposure

The mechanism of pitting involves both initiation and propagation.
Conditions must exist for both phases to occur. These conditions may be
associated with the metal, the environment, or both.
Pitting corrosion of zinc has been reported [9-10] to occur when oxygen
was not replenished or freely available. A critical oxygen level was pro-
posed to exist below which pitting is initiated and propagated by the
formation of concentration cells on the zinc surface. These investigations
suggest that not only the rate of zinc corrosion but also the type of corro-
sion, uniform versus pitting, is controlled by the supply and diffusion of
oxygen through the corrosion products.
In our exposure study no attempt was made to remove the oxygen or
carbon dioxide gases. During the dew cycle, a thin layer of moisture con-
densed on panel surfaces; oxygen and carbon dioxide, therefore, were
readily available to react with the zinc film in both the clean air and pol-
luted exposures. Therefore, the critical oxygen level mechanism for pit
initiation was not likely.
Initiation of pits probably occurred around some inclusion or defect on

zinc surfaces. Scanning electron photomicrographs (Fig. 6) of unexposed
galvanized steel panels revealed minor inclusions that were identified by
microprobe scans (Fig. 7) as metallic lead. Inclusions that could definitely
serve as active sites (such as iron-aluminum intermetallics) were not found.
The lead inclusions, although not normally expected to be a problem,
possibly could have served as pitting-initiation sites when exposed to this
unique clean air environment.
An environmental factor that may have contributed to the initiation of
pits was the relatively short dry-wet cycle. Some moisture nucleation sites
on the galvanized surface may have stayed wet longer than the remaining
surface area. Possibly such sites may have never dried completely or may
have had a very short dry period compared with the remainder of the
surface. Under such conditions, a protective zinc carbonate film may not
have had time to form. As a result, a large cathode-to-anode area ratio
would have occurred, thereby producing a very high localized current
density at these active sites and subsequent formation of pits. Chemically,
zinc goes into solution as ions around the sites while hydroxide ions form
on the passive cathode surface. During migration the zinc ions react with
FIG. 6—Scanning electron microscopy of unexposed galvanized steel panel (X5000).
FIG. 7—Microprobe scan of unexposed galvanized steel panel (X5000).
water to form zinc hydroxide. This process produces hydrogen ions which
migrate toward the cathode and become neutraUzed. During the neutrali-
zation process, the corrosion products tend to precipitate about the active
site and produce a barrier that enhances pit formation.
Scanning electron photomicrographs (Figs. 8 and 9) of the corrosion
products formed during the clean air exposures revealed a locahzed,
circular buildup of an amorphous substance on the zinc surface. This
pattern of corrosion products is characteristic of pitting corrosion. X-ray
diffraction identified the corrosion products as primarily zinc oxide with a
secondary phase of zinc carbonate. Zinc hydroxide, although not identified
as a corrosion product, was formed during the dew cycle. However, since
the pH of the dew on an inert surface was acidic (4.5) because of dissolved
carbon dioxide, the zinc hydroxide probably reacted to produce zinc
carbonate. Also, zinc hydroxide probably decomposed to zinc oxide [11]
as the panel dried during the light cycle. The pH of the dew formed on the
corroding panels during the exposure was 7.5. This level of pH suggests
that the corrosion rate was near minimum [12] and a passive protective
film had formed on most of the surface; nevertheless, pitting corrosion
occurred.
SPENCE AND HAYNIE ON PITTING OF GALVANIZED STEEL 141
FIG. 8—Scanning electron microscopy of galvanized steel corrosion products from clean
air exposure (X50).
Other scanning electron photomicrographs (Figs. 10 and 11) show a

cross-sectional view of the exposed panels. Corrosion products, which
completely surround and cover the pits, apparently serve as a barrier that
hinders diffusion and causes highly acidic conditions to develop in the pits
by enhancing the concentration of hydrogen ions. This process is auto-
catalytic in that as more localized corrosion occurs, conditions become
more favorable for pitting corrosion.
Pollution Exposures
Uniform corrosion of the zinc film was observed (see Fig. 12) for the
exposures containing the three gaseous pollutants at various concentra-
tions. Scanning electron photomicrographs of the corrosion products
(Fig. 13) revealed primarily crystalline materials uniformly dispersed over
the zinc surfaces. X-ray diffraction patterns were very complex and indi-
cated one or more unidentifiable hydrated corrosion products. However,
microprobe scans revealed sulfur atoms, probably in the form of sulfate,
to be uniformly distributed over the zinc surface.
In the polluted exposure experiments, dew collected on an inert substrate
measured quite acidic with a pH of 3.2; collected on the galvanized panels
FIG. 9—Scanning electron microscopy of galvanized steel corrosion products from clean
air exposure (XJOOO).
the dew remained acidic but with a pH of 5.6. Apparently, the acidic
medium prevents the formation of a highly passive protective film, as well
as localized cells at possible pitting initiation sites. The acidic dew dissolves
and reacts with the corrosion products, resulting in the uniform distribu-
tion of these products across the galvanized surface. This process occurred
during each cycle of dew and light.
The conditions of corrosion, immunity, and passivation of zinc (Fig. 14)
as a function of pH and electrical potential have been reported [13]. This
figure shows the influence of pH on the corrosion of zinc in aqueous solu-
tions containing carbon dioxide. The dotted line represents the stability
limit of water.
The influence of pH on the potential of zinc galvanized steel panels with
two different aqueous media on the surface of each panel has been added
to Fig. 14. These measurements were recorded using a calomel reference
electrode with liquid junction (readings adjusted to hydrogen (H2) electrode
potential) and a glass miniature pH electrode. The deionized water used to
prepare this solution was not boiled and, therefore, contained dissolved
oxygen and carbon dioxide. With deionized water containing sulfur
dioxide, a potential of —0.763 V at a pH of 4.2 was initially recorded. Over
SPENCE AND HAYNIE ON PrTTING OF GALVANIZED STEEL 143
FIG. 10—Scanning electron microscopy of cross section of galvanized steel panel from
clean air exposure (X2000).
a period of 24 h the pH moved into the passivation region (8.2) of the

diagram (Fig. 14) and the potential leveled off at —0.799 V. The solution
on the panel remained clear; however, the panel had a dull stained appear-
ance over its entire surface. These panels resembled the galvanized panels
exposed to the polluted environmental conditions. For the other condition
with deionized water containing carbon dioxide, a potential of —0.823 V
was initially recorded at a pH of 4.2. After 24 h the pH moved into the
passivation region (8.0 in Fig. 14); however, the potential shifted to
— 0.690 V. This shift in potential was due to the formation of a passive film
over most of the surface. The appearance of a milky color solution gave
evidence that corrosion products had developed. Removal of the liquid and
products from the panel revealed localized pitting corrosion similar to that
observed for the clean air environmental exposures.
Conclusion
Galvanized steel revealed two different mechanisms of corrosion depend-
ing on whether the metal was exposed to clean air or polluted environments.
During exposure to the clean air environments programmed with short
FIG. 11—Scanning electron microscopy of cross section ofgalvanized steel pane from clean
air exposure (X5000).
FIG. 12—Scanning electron microscopy of galvanized steel corrosion products from

polluted air {X50).
SPENCE AND HAYNIE ON PITTING OF GALVANIZED STEEL 145
FIG. 13—Scanning electron microscopy of galvanized steel corrosion products from

polluted air (XIOOO).
- -0.1 1 —
>.
a -0.2
=" —
t
-0.3
—
-;
^ -0.4 — CORROSION
FIG. 14—Potential-pH behavior of galvanized steel compared with thermodynamic rela-

tionships for the zinc-water-carbon dioxide system.
wet-dry cycles, moisture nucleation sites on the zinc surface remained active
and initiated pitting corrosion. Propagation of pits occurred with the forma-
tion of diffusion barriers over active sites. Pitting corrosion resulted because
the pH (7.5) of the dew on the surface of panels minimized corrosion prod-
uct solubility while the pH within the pits was more acidic and conducive to
corrosion product solubility. For the polluted exposures, the surface dew
was acidic and prevented the formation of a highly passive corrosion film
as well as the formation of local active sites. Therefore, the corrosive effects
of polluted environments on galvanized steel are not additive to the cor-
rosive effects of these unique clean conditions and thus should not be
compared. The effects of different levels of pollutants, however, are com-
parable and meaningful. Galvanized steel that becomes only partially dry
during exposure to clean air environments in the real world could develop
the type of pitting that was observed in this study.
References
[/] Campbell, G. G., Schurr, G. G., Slawikowski, D. E., and Spence, J. W., Journal of
Paint Technology, Vol. 46, No. 593, June 1974, pp. 59-71.
[2] Beloin, N. J., Textile Chemist and Colorist, Vol. 4, No. 3, March 1972, pp. 77-82.
[3] Beloin, N. J., Textile Chemist and Colorist, Vol. 5, No. 7, July 1973, pp. 128-133.
[4] Haynie, F. H. and Upham, J. B., Materials Protection and Performance, Vol. 9, N o . 8,
Aug. 1970, pp. 35-40.
[5] Haynie, F. H, and Upham, J. B., Materials Protection and Performance, Vol. 10,
Nov. 1971, pp. 18-21.
[6] Spence, J. W. and Haynie, F. H. in Corrosion in Natural Environments, ASTP STP 558,
[7] Guttman, H. and Sereda, P. J. in Metal Corrosion in the Atmosphere, ASTM STP 435,
[S] Guttman, H. in Metal Corrosion in the Atmosphere, ASTM STP 435, American
Society for Testing and Materials, 1968, pp. 223-239.
[9] Bengough, G. D., Stuart, J. J., and Lee, A. R., Transactions, American Society of
Mining, Metallurgical, and Petroleum Engineers, Vol. 83, 1929, pp. 29-46.
[/O] Evans, U. R. and Davies, D. E., Corrosion, Vol. 8, 1952, p. 165-170.
[//] Gilbert, P. T., Journal of the Electrochemical Society, Vol. 99, N o . 1, 1952, pp. 16-21.
[12] Roetheli, B. E., Cox, G. L., and Littreal, W. B., Metals and Alloys, Vol. 3, 1932, p.
73-76.
[13\ Pourbaix, M. in Establishment and Interpretation of Potential-pH Equilibrium Diagrams,
Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamon, Oxford, England,
1966, p. 406.
L. C. Covington1
Pitting Corrosion of Titanium Tubes in Hot

Concentrated Brine Solutions
REFERENCE: Covington, L. C , "Pitting Corrosion of Titanium Tubes in Hot

Concentrated Brine Solutions," Galvanic and Pitting Corrosion—Field and Labora-
tory Studies, ASTM STP 576, American Society for Testing and Materials, 1976,
pp. 147-154.
ABSTRACT: Pitting problems have been encountered in titanium tubes in heat
exchangers handling hot saturated brines. These pits appear to be of two types. One
type results in symmetrical holes about one-fourth inch diameter. These are as-
sociated with scratches in which iron is found to have been smeared into the
titanium surface. The second type results in large irregular shaped holes. These
are believed to be associated with salt plugs. This second type of pitting is believed
to be initiated by the galvanic couple between the titanium tubes and the Monel
tube sheets. Use of titanium tube sheets might eliminate the pitting problem but
could introduce a crevice corrosion problem unless the tubes are welded into the
tube sheet. An alternate solution is the use of titanium alloy tubing that is resis-
tant to pitting attack.
KEY WORDS: titanium, pitting, corrosion, brines, heat exchangers
The salt industry has been troubled by pitting failures of titanium tubes
in salt evaporators. These salt evaporators are a tube and shell heat ex-
changer consisting of titanium tubes roller expanded into Monel tube
sheets. A saturated brine flowing through the tubes is heated to 268°F by
steam on the shell side at 276°F. The brine carries solid salt particles,
including flakes, that are large enough to plug a tube if they get turned
just right. This happens frequently enough that every few months the
units must be opened and the plugged tubes washed out. Occasionally,
following a cleaning operation, it will be noted that some of the tubes are
leaking. An examination of the tube will usually reveal the presence of one
or two pits that have perforated the tube. Sometimes these leaks develop
after the tube has been in service for five or six years, and sometimes the
tubes fail within a few weeks after installation.
1
Senior research engineer, Titanium Metals Corporation of America, Henderson, Nev.
89015.
147
Copyright" 1976 by ASTM International www.astm.org

University of Washington (University of Washington) pursuant to Lice
fjlffpifl
FIG. 1—Small sharply defined pits.
This paper describes an investigation that was made of this pitting

problem and the conclusions that were reached regarding the probable
causes.
Experimental
Samples of the pitted tubes were obtained. Photographs were made of

the pitted areas, and electron probe analyses of the pitted areas were
conducted.
Autoclave tests were conducted with specimens of titanium tubing in
saturated brine solutions in an attempt to reproduce the pitting observed
in the salt evaporators. These tests were conducted at 300°F for 500 h.
Results and Discussion
The pitting corrosion of titanium has been studied extensively. The

observations and conclusions reported here are consistent with the known
characteristics of pitting corrosion as reported by various investigators
[1-4].'^ Figures 1 and 2 show views of some of the pits. These failures
appear to be of two types. Pits of the type shown in Fig. 1 are usually
located within 4 in. of the tube end and are associated with scratches.
Pits of the type depicted in Fig. 2 may appear anywhere along the length of
a tube, and scratches have not been associated with this type of pit.
COVINGTON ON PiniNG CORROSION OF TITANIUM TUBES 149
HR-
m Ppif
FIG. 2—Large irregular shaped pits.
It should be pointed out that titanium is operating in a borderline condi-

tion as far as pitting is concerned in these salt evaporators. Figure 3 shows
the temperature and chloride concentration ranges in which titanium has
been observed to pit.' This chart is derived from industrial experience as
well as experimental data. At the temperature and brine concentration
present in a salt evaporator, titanium would be in the pitting possible zone
of this chart. Under these conditions tight crevices or scratches could be
expected to initiate pitting. Pitting is not observed in the tube to tube sheet
crevice, however, because of the presence of nickel and copper ions from
the tube sheet which passivate the titanium [5]. Galvanic corrosion is also
reduced in the crevice area by the presence of the nickel and copper ions
because these ions act as cathodic depolarizers and tend to shift the po-
tential of the titanium in the positive direction, thus, reducing the potential
difference between the Monel tube sheet and the titanium tubes.
Mechanism of Pitting Attack

Figures 4 and 5 are examples of pits resulting from scratches. Electron
probe analysis revealed traces of iron in the scratches. This suggests the
scratches were made by a piece of iron.
Temperature wise, 268°F is believed to be a borderline condition for
pitting to initiate in unalloyed titanium exposed to a saturated brine. At
' This chart was prepared by N. G. Feige and T. J. Murphy, Titanium Metals Corpora-
tion of America, West Caldwell, N. Y. 07006.
100 200 300 400

TEMPERATURE, "F
FIG. 3 - -Immunity of titanium from pitting in neutral chloride brine (ASTM Grade 2
materiats).
this temperature any defect in tiie protective oxide film can serve as the
nucleating site for a pit. The titanium-dioxide (Ti02) film is very resistant
to attack by chloride ions; however, a small fragment of iron abraded into
the surface by contact with a steel implement might rupture the film. The
presence of the iron particle would prevent the Ti02 film from healing.
Since iron is readily attacked by chloride ions, the iron particle would
provide a site for corrosion to initiate [6].
Once chloride ions have penetrated to the titanium metal surface, an
electromechanical cell is established in which the metal in the pit becomes
anodic to the surrounding oxide covered surface. According to Uhlig [2],
"The anodic sites do not spread along the metal surface because the
resulting high galvanic currents cathodically protect the immediate metal
surrounding the anode and prevent additional pits from initiating."
The titanium chlorides formed would tend to hydrolyze [J] on contact
with the solution, generating hydrogen ions and forming insoluble Ti02.
The Ti02 would form a slightly porous cap over the pit which would limit
the diffusion of the brine into the pit. Because of hydrogen ion generation,
the solution in the pit would become highly acidic, greatly accelerating the
attack on the metal.
Because of the effect of the galvanic current, the attack on the metal
would be limited to the area directly under the cap of corrosion product.
The result would be a corrosion pit filled with Ti02 that would continue
to propagate until the pit perforated the metal.
COVINGTON ON PiniNG CORROSION OF TITANIUM TUBES 151
FIG, 4—Inside diameter of lube showing two pits connected by scratch.
FIG. 5—Hole resulting from perforation of the tube by a pit associated with a scratch.
The small symmetrical pits associated with scratches as shown in Figs. 4

and 5 seem to be fully explained by the foregoing mechanism. In Fig. 4, we
even have an example of a pit still tightly plugged with a corrosion product.
When this plug was scraped away, a hole very similar in size and shape to
the one on the left was revealed. This would explain why tubes containing
pits of this type are not found to leak until after a cleaning operation. Indeed
it appears that unless the plug is dislodged the tube may operate for con-
siderable time without leaking.
The second type of large irregular pit is shown in Fig. 3. This type is
believed to be associated with salt plugs that develop during the operation
of the evaporators. The effect would be to produce a tight crevice in which
the stagnant brine would rise to a temperature equal to that of the steam
on the outside of the tube. In the stagnant crevice, acidic conditions
would develop [7] until a pH is reached at which the protective oxide film
is no longer stable. Pits would then develop and perforate the tube wall
underneath, the salt plug.
Attempts were made unsuccessfully to reproduce pitting attack in the
laboratory. Specimens of unalloyed titanium tubing (ASTM Grade 2) were
exposed to a saturated brine at 300°F for 500 h. The tube was packed in
solid salt to simulate a salt plug, but pits did not develop. In reviewing the
exposure conditions in a salt evaporator, it was noted that the titanium
tubes are expanded into a Monel tube sheet so that a galvanic couple
exists with titanium being the cathodic member of the couple. The potential
difference between Monel and titanium at 300°F in saturated brine was
measured and found to be 210 mV. This would result in accelerated attack
on the Monel with hydrogen being generated on the titanium. The potential
difference is not considered to be large enough to cause a serious galvanic
corrosion problem. However, it was decided that the test should be repeated
again, this time with Monel coupled to the titanium tubes to duplicate the
galvanic conditions.
This time pitting was observed as can be seen in Figs. 6 and 7. The metal
strips crimped to the edges of the tube are Monel. No corrosion occurred
under the Monel clips, but a very definite crevice corrosion type of attack
has occurred at other areas on the tube as shown in Fig. 6. Note the
similarity between this attack and the pits shown in Fig. 2. Figure 7 shows
two pits that have perforated the tube although they are still filled with a
plug of a corrosion product. These are examples of pits of the first type
resulting from iron contamination. The tube was cut off with a hacksaw,
and two scratch marks were made by the saw while getting the cut started.
Pits initiated in both marks.
In order to be certain that the galvanic couple triggered the pitting
reaction, the experiments were repeated with the same results. No pitting
was observed without the galvanic couple. With the galvanic couple,
severe pitting was obtained.
COVINGTON ON PIHING CORROSION OF TITANIUM TUBES 1 53
l|ij!|l|IH|ljm|l|-#|l|l|illt^|i|tji|J)l|l
FIG. 6—Pitting test with Monel coupled to titanium tube.
Apparently the galvanic couple between the titanium and the Monel
is involved in the pit initiation under salt plugs. Since the galvanic couple
would result in small amounts of hydrogen being generated on the titanium
surface it may be that patches of hydride would form. Titanium hydride
is not as stable a compound as Ti02 and in the stagnant confined areas
covered by the salt plug, this film would decompose allowing the chloride
ions to react with the underlying titanium metal. A corrosion cell would
then be set up in which highly acidic conditions would develop and an
accelerated attack on the metal in the pit would occur.
The question arises as to why pits associated with scratches are nearly
perfectly round, while salt-plug pits are irregularly shaped. This is probably
due to the fact that the pits associated with scratches initiate at a small
particle of iron embedded in the titanium and are, therefore, highly localized
in nature. The pits that are associated with salt plugs, on the other hand,
initiate as a crevice corrosion attack and involve a much greater area.
Turbulence near the tube sheet is not believed to be a factor in the shape of
the pits. It is generally agreed that corrosion occurs because of the develop-
ment of acidic conditions in the pit. This is promoted by stagnant condi-
tions. The fact that the round pits are nearly always found in the area
adjacent to the tube sheet is probably due to the fact that this area is most
likely to be scratched during installation of the tubes.
It appears the Monel tube sheet may trigger the reaction that causes
these tube failures. Use of titanium tube sheets may eliminate this problem,
but it would require that the tubes be welded into the tube sheet to eliminate
any crevices. Under the conditions involved in this application, severe
crevice corrosion could be expected if any crevices existed. This is not a
FIG. 7—Pits resulting from Monet couple.
problem with the Monel tube sheet because the nickel and copper ions from
the tube sheet inhibit crevice corrosion [5].
The ahernate to replacing the tube sheet may be to use tubes of a ti-
tanium alloy resistant to attack under these conditions.
References
[/] Posey, F. A. and Bohlmann, E. G., "Pitting of Titanium Alloys in Saline Waters,"
paper presented at the Second European Symposium on Fresh Water from the Sea,
Athens, Greece, 9-12 May 1967.
[2] Uhlig, H. H. Materials Protection and Performance, Feb. 1973, pp. 42-44.
[i] Brown, B. F., Corrosion-NACE, Vol. 26, No. 8, 1970, pp. 249-250.
[4] Greene, N. D. and Judd, G., Corrosion-NACE, Vol. 21, Jan. 1965, pp. 15-18.
[5] Covington, L. C. in Titanium Science and Technology, Vol. 4, R. I. Jaffee and H. M.
Burte, Eds., Plenum, New York, 1973, p. 2395.
[6] Cotton, J. B., Chemical Engineering Progress, Vol. 66, No. 10, Oct. 1970, pp. 57-62.
[7] Griess, J. C , Corrosion-NACE, Vol. 24, April 1968, pp. 96-109.
F. J. Cornwell,1 G. Wildsmith,2 and P. T. Gilbert2
Pitting Corrosion in Copper Tubes in Cold

W a t e r Service
REFERENCE: Cornwell, F. J., Wildsmith, G., and Gilbert, P. T., "Pitting

Corrosion in Copper Tubes in Cold Water Service," Galvanic and Pitting Corro-
sion—Field and Laboratory Studies, ASTM STP 576, American Society for Testing
and Materials, 1976, pp. 155-179.
ABSTRACT: The occurrence of pitting corrosion in copper tubes carrying cold
supply waters has been investigated in relation to (a) carbon residues in the bore
of the tube from the bright annealing operation, (b) the hardness and composition
of the metal, and (c) water composition. The electrode potential of tubes in several
supply waters has been used to assess their susceptibility to pitting corrosion. It is
concluded that pitting occurs only in certain types of water with a low level of
organic matter in tubes containing more than a critical amount of carbon residue
in the bore. Hardness of the metal appears to have little effect on susceptibility to
pitting corrosion, but the addition of about 1 percent tin to the copper substan-
tially reduces the rate of pitting for a given level of carbon contamination in the
bore. The significance of these findings is reviewed in the light of service experience
with copper water tubes in the United Kingdom.
KEY WORDS: corrosion, pitting, copper, tubes, domestic supply waters, carbon
residues
Copper tubes (usually phosphorus deoxidized, for example, copper 122)

are widely used in water distribution systems where they generally give
reliable performance and have a very long life [1-6].3 Not unexpected for a
material in widespread use in a variety of environmental conditions,
corrosion problems occasionally arise. In many countries the most trouble-
some problem occurs in cold waters originating from deep wells or bore-
holes in the presence of carbon residues on the tube surfaces. This type
of localized corrosion was first described by Campbell [7] and has since
been identified in tubes in service in Belgium, Germany, Holland, New
Zealand, the United Kingdom, and the United States [3,8-10]. Failures are
1
Technical manager, Yorkshire Imperial Metals Limited, Kirkby, Liverpool, England.
2
Manager, Metallurgical Services and Research, and technical director, respectively,
Yorkshire Imperial Metals Limited, Leeds LSI 1RD, England.
3
155

often comparatively rapid, many occurring within the first year or two of
service.
Investigations by a number of organizations during recent years have
indicated that several factors affect the incidence of this type of attack.
These can be briefly summarized as follows.
1. The presence of carbon residues on the tube surfaces produced during

manufacture aifect attack. If the amount of carbon residue is sufficiently
low, pitting does not occur.
2. The nature of the water is another factor. In surface-derived waters,
attack does not normally occur, even in tubes containing carbon films.
Campbell [7] attributed this to the presence of a naturally occurring
organic corrosion inhibitor. However, if such waters are treated to remove
organic matter (for example, by alum flocculation treatment) they may be
capable of supporting pitting in tubes containing carbon. Lucey [11,12] has
suggested that several inorganic constituents (Cl~, NOs", S04^~, Na+, O2)
are important in determining the pitting propensity of a water and that pH
is also a major factor, the pitting propensity increasing with decreasing pH
in the range 9.4 to 7.0. His analysis of the situation does not take any direct
account of the presence of organic substances, but there may be inter-
related effects since organic matter can stabilize the pH value at a higher
figure than would otherwise occur.
3. Another factor is the temper of the copper tube. It has been reported
[13] that other things being equal (including carbon contamination), hard
tubes (though not entirely immune to failure) are more resistant than
half-hard tubes, which are, in turn, more resistant than annealed tubes.
The reasons for these differences have not been elucidated.
4. The composition of the copper can influence attack. Modifications
to the composition of the copper can improve the resistance to pitting in
the presence of carbon residues. Small additions of aluminum and tin are
claimed to be beneficial [13].
5. The effect of tube wall thickness is another factor. Devroey and
Depommier [13] have reported that the rate of penetration falls off with
time in Brussels water, and they concluded that there was a limiting wall
thickness above which perforation of the tube would not occur however
high the carbon contamination.
The authors have investigated most of these factors during the past five
years, together with other factors, such as the use of different types of
tube-drawing lubricants, the use of various final cleaning processes, and
the application of protective treatments. This paper gives some of the
results obtained, particularly those relating to the effects of carbon residues,
water composition, and the temper and composition of the copper. Ref-
erence is made to laboratory investigations, field trials, and service ex-
perience in the United Kingdom.
CORNWELL ET AL ON PiniNG CORROSION IN COPPER TUBES 1 57
Experimental
Copper and copper alloy tubes were exposed to supply waters in test
rigs situated at two pumping stations, one in Yorkshire (Bramham) and
one in Lincolnshire (Barrow Park), and in the company's Leeds laboratory.
The test site at Bramham is supplied with both hard (untreated) borehole
water and base-exchange softened borehole water (public supply). Pre-
liminary trials established that both the untreated and softened supplies
were capable of supporting pitting corrosion of copper in the presence of
carbon residues, but the results presented in this paper are for copper tubes
exposed only to the softened supply. The test facility at Barrow Park is
supplied with hard, untreated, borehole water. Both sites are in areas
where pitting corrosion is experienced in service. The Leeds water is
mainly derived from surface sources and pitting failures do not occur in
this area.
It has been established that the electrode potential of the copper tubes
during exposure shows a significant correlation with pitting behavior, and
potential/time curves were plotted for tubes exposed at Bramham and in
the laboratory. Progress of pitting was followed using an eddy current
technique, and the time taken for tubes to be perforated was recorded at
each site.
Preparation of Tube Specimens

Half-Hard Temper Tubes—Half-hard copper tubes were manufactured to
British Standard Specification for Light Gauge Copper Tubes (light drawn)
(B.S. 659:1967), J^ in. Table A (now British Standard Specification for
Copper and Copper Alloys Tubes, Part 1, Copper Tubes for Water, Gas,
and Sanitation (B.S. 2871: Part 1: 1971), 15 mm Table X), from extruded
shells. In the course of manufacture the tubes are cold drawn to the penul-
timate size and then bright annealed. A final sinking pass increases the
hardness to the "half-hard" temper (80 to 100 VHN5 kg load). At final
size, the bore of the tube may be more or less contaminated with carbon
residues arising from: (a) graphite in the extrusion lubricant, {b) breakdown
of lubricant during drawing, or (c) decomposition of residual bore lubricant
during the bright annealing operation.
In the course of normal production within the authors' company, J/^-in.
or 15-mm half-hard copper tubes (the most commonly used size) are given
a final abrasive cleaning treatment using air-borne alumina or iron grit.
The exposure trials have included both cleaned and uncleaned tubes.
Copper alloy tubes have been manufactured for trial purposes by
basically similar procedures. Such tubes are somewhat more difficult to
produce than copper, but could be of interest if resistant to pitting corrosion
in the uncleaned condition. If cleaning were necessary they would probably
have no advantage over ordinary copper. Therefore the alloys were tested
in the uncleaned condition.
Hard-Temper Tubes—Hard-drawn copper tubes were manufactured to

British Standard Specification for Hard-Drawn Thin Wall Copper Tubes
(B.S. 3931: 1965), H in. (now B.S. 2871: Part 1: 1971, 15 mm Table Z)
from extruded shells. These tubes are not annealed at penultimate size and
the level of carbon residues in them is usually low. Occasional failures
occur in service when, for one reason or another, an abnormally high
amount of carbon residue is present in the bore.
Carbon Determination
Before installation in the test rigs the level of carbon contamination was
assessed using the carbon black (CB) test devised by Devroey and
Depommier and described by Campbell [74]. Briefly this test entails
taking a tube specimen (internal surface area 20 cm^), the outside surface
of which is filed clean. This is immersed in nitric acid and boiled for about
3 min. The specimen is then removed and washed with distilled water.
The solution (including washings) containing the carbon residues from the
tube bore is filtered under suction through a standard micropore filter
paper, 20 mm in diameter. The residue on the filter paper is washed with
distilled water and methylated spirit, allowed to dry, and compared with a
set of standard disks to establish the CB number. An increase of one in the
CB number corresponds to a doubling of the amount of carbon. A limita-
tion of the test is that it gives an average value for the level of contamination
and it gives no information about local variations over the 20 cm^ of
surface tested.
The CB number of an uncleaned half-hard tube can vary considerably
along its length, a typical range being CB 2 to 5.'' Normal abrasive cleaning
reduces the contamination to the range CB 1 to 2. However, if the tube is
initially abnormally heavily contaminated or if the abrasive cleaning
process is not operated efi"ectively or both, the CB numbers for the" cleaned"
tube will be higher, and there will then be a significant risk of failure if the
tube enters service in a water capable of supporting pitting attack.
The one-half inch size of hard-drawn tubing normally has CB numbers
in the range 1 to 2, though occasionally higher figures are encountered.
The general degree of contamination is not high enough to make it neces-
sary to apply the abrasive cleaning process to this product.
Description of Test Rigs

Site Test Rigs—The corrosion rigs at the Bramham and Barrow Park
sites have been described in detail elsewhere [15]. A general view of the
' These figures refer to standards established for Yorkshire Imperial Metals Limited.
Others, though using similar methods for carrying out the test, do not necessarily obtain
identical results, possibly because of variations in the standards used. Therefore, the CB
numbers quoted here are not necessarily directly comparable with those obtained in other
laboratories.
CORNWELL ET AL ON PITTING CORROSION IN COPPER TUBES 1 59
corrosion rig at Bramham is shown in Fig. 1. The tubes (about 5 m long)

were tested in sets of four in parallel (a bank) with common water inlet and
outlet pipes. Water flowed in a particular bank when a time switch opened
a solenoid valve positioned in the outlet pipe.
At both Bramham and Barrow Park, the time sequence was set to allow
water to flow for 35 s once an hour, every hour for 12 h, to change the
water in the tubes completely every hour. The water flowed to waste after
passing through the tubes. During the remaining 12 h, the water remained
stagnant in the tubes. This flow/stagnation sequence was used to simulate
the day/night conditions in domestic water systems.
Corrosion Rigs in the Laboratory—Two laboratory corrosion rigs, each
containing four tubes, were constructed. One rig was supplied with labora-
tory tap water (which does not support pitting), the other with water
brought regularly from Bramham. In both rigs, water from a large header
tank flowed into a smaller tank fitted with an automatic siphon, which
operated when the water in the small tank reached a critical level. The
feed from the header tank was adjusted so that the siphon operated once
every hour and the header tank contained sufficient water for the siphon to
operate for 12 h. Water (and some air bubbles) flowed from the siphon
FIG. 1—Corrosion rig at the Bramham site.
tank into another small tank situated immediately below it. This tank
allowed the air bubbles to be expelled before the water flowed through the
test tubes. Water was maintained in the tubes during the periods of water
flow by a 15-cm head at the outlet. The rig had the same flow/stagnation
sequence as the Bramham and Barrow Park rigs.
Previous work [15-17] has shown that pitting of copper occurs when the
electrode potential of the copper exceeds a critical value of about 100 to
170 mV (all potentials will be given on the saturated calomel scale).
The electrode potential of the tubes was measured periodically through-
out the exposure periods using a silver/silver chloride reference electrode.
The tube to be examined was completely removed from the test rig, and
the reading was taken before the tube had time to dry out. The reference
electrode was held in the center of the tube bore by plastic couplings which
also included an inlet for the supply water. The water flowed over the
reference electrode and along the bore of the tube, Which was inclined so
that the water had to flow up a slight incline thereby ensuring that the tube
was filled with water. The experimental technique adopted ensured that
the measurements were taken in the dark since both Lucey [18] and
Pourbaix [16,17] have demonstrated that the potential is aifected by
illumination of the specimen. The reference electrodes were calibrated
against a saturated calomel electrode before use, and the experimental
results have been converted to the saturated calomel scale.
Eddy-Current Examination
In order to follow the development of pitting, the tubes were eddy-
current tested periodically during exposure. An external coil, energized
with alternating current, was pulled slowly along the axis of the tube;
changes in electromagnetic response caused by the presence of pits pro-
duced electrical signals which were amplified to actuate a recorder. The
instrument was calibrated by passing the coil over standard defects ma-
chined into a tube of the same size and composition as those on test.
The sensitivity was adjusted so that the output obtained from the standard
defects produced specific sizes of deflections on the eddy-current recorder.
Composition of Supply Waters

Typical analyses for Bramham, Barrow Park, and laboratory (Leeds)
waters are given in Table 1. To assess the relative amounts of organic
matter present, a technique based on that described by Campbell [19] was
used, in which a sample of water is illuminated with ultraviolet light and
the degree of fluorescence compared with a standard sample illuminated
at the same time. The Leeds laboratory tap water has been adopted as
standard as this gives reasonably constant fluorescence, although slight
CORNWELL ET AL ON PITTING CORROSION IN COPPER TUBES 161
TABLE 1—Typical water analyses (results in ppm where appropriate).
Water Supply
Bramham Laboratory
(Public Supply) Barrow Park (Leeds)
pH 7.4 7.5 8.5

Total dissolved solids dried at 180°C 553 506 198
Total dissolved solids ignited at 600°C 490 433 178
Carbonate (temporary)
hardness CaCOa 174 219 30
Noncarbonate (permanent)
hardness CaCOs Nil 147 40
Total hardness CaCOs 174 367 70
Total alkalinity CaCOs 298 219 30
Calcium Ca 37 140 22
Magnesium Mg 20 3.7 4.0
Sodium Na 150 18 38
Iron Fe 0.22 0.06 0.08
Aluminum Al 0.36 0.03 <0.02
Copper Cu <0.025 <0.025 <0.025
Lead Pb <0.10 <0.10 <0.10
Manganese Mn <0.005 <0.005 <0.005
Chloride CI 48.5 41.8 29.0
Sulfate SO4 103 98 75
Ammoniacal nitrogen N <0.02 <0.02 0.04
Nitrate nitrogen N 7.2 6.4 1.9
Nitrite nitrogen N <0.02 <0.02 <0.02
Silica SiOj 4 3 4
Free carbon dioxide CO2 15.8 13.2 <0.01
Free chlorine CI <0.01 <0.01 0.05
Dissolved oxygen 0 8.2 12.6 9.5
Fluorescence fraction of laboratory
supply water 1/8 1/4 1
variations do occur. The laboratory water is diluted with deionized water

(zerofluorescence)in order to reduce its level of fluorescence to that of the
supply water under test. The intensity of fluorescence of this water is then
expressed as a fraction of that of the standard water.
Experimental Results
The results of early trials suggested that pits are initiated more readily
when water is left stagnant in the tubes for a period before switching to the
regular flow/stagnation sequence. Subsequent trials have not entirely
supported this conclusion, but the majority of the trials described in this
paper have included an initial period of one month during which water
was left stagnant in the tubes. No potential measurements were taken
during this period.
Effect of Carbon Residues on the Incidence of Pitting

Trials at Bramham—Exposure trials were carried out at Bramham with
12 uncleaned half-hard tubes (CB numbers in the range 2 to 6), 12 tubes
abrasively cleaned with iron grit for 0.5 s (CB numbers in the range 1 to 5),
and 23 tubes abrasively cleaned with either iron or alumina grit for 5 to 30 s.
Ten of these 23 tubes were manufactured using excessive amounts of lubri-
cant during drawing in order to deliberately produce a tube heavily con-
taminated with carbon in the bore before abrasive cleaning. These tubes
were abrasively cleaned with iron grit for 5 s. The remaining 13 tubes were
manufactured using normal lubrication procedures and abrasively cleaned
for a minimum of 7 s. The CB numbers of all 23 abrasively cleaned tubes
were in the range 1 to 3, although, in general, the CB number of those
manufactured with excessive lubricant was higher within this range than
that of tubes produced using normal lubrication.
The initial potential of the 12 uncleaned tubes was approximately
— 40 mV. After the initial stagnation period the potentials increased
steadily into the range 270 to 350 mV. Potential/time curves typical of
those obtained with uncleaned tubes are shown in Fig. 2. Rapid pitting
occurred and all the tubes were perforated within five months.
The 12 tubes abrasively cleaned for 0.5 s had potential/time curves
similar to those of the uncleaned tubes except that the peak potential
attained was generally somewhat lower. Typical curves are shown in Fig. 3.
Eight of these tubes were perforated within 4 to 16 months. Eddy-current
400
350 -
\K^ X indicates
300 - A/V failure
250 _
Lij
O
c2 200
f1 severe pitting
E 170
S 150 / some pitting
1 possible
"- 100 - fiit I no pitting
50 -)7
incubation y
period /
0
-50 1 1 1 1 1 1 1 1
2 3 4 5 6 8 10 20 30 40 60 100
50 80
Exposure (weeks)
FIG. 2—Potential/lime curves obtained with uncleaned copper tubes exposed to a water
that supports pitting.
University of Washington (University of Washington) pursuant to License Agreement. No further reproduc
CORNWELL ET AL ON PiniNG CORROSION IN COPPER TUBES 1 63
-50
2 3 4 5 6 810 20 3040 60 100 200
I ^ , 50 80
Exposure (weeks)
FIG. 3—Potential/time curves obtained with inadequately cleaned copper tubes exposed
to a water that supports pitting.
inspection of the remaining four tubes indicated that all were severely
pitted, but no failures had occurred in 42 months. The potentials of these
four tubes fell after approximately 18 months from the range 188 to 274 mV
to the range 33 to 140 mV. The potentials were relatively low, in some cases
for about 18 months before increasing again to higher potentials. Curves A
and B in Fig. 3 show this fall and rise in potential for two of the tubes.
The ten tubes manufactured with excessive carbon residues and abrasively
cleaned with iron grit for 5 s also exhibited this cyclic effect in their po-
tential/time curves, as shown in Fig. 4. For the first 6 months' exposure
the potentials of all ten tubes remained low. After 7 to 12 months the
maximum potentials observed were in the range 40 to 154 mV. The tubes
with potentials above 100 mV continued to have potentials > 100 mV for a
further 12 months, after which time they fell below 100 mV. The potentials
of all ten tubes remained below 100 mV for a further 8 to 16 months before
increasing during the next 12 months to peak values in the range 108 to
205 mV. The tube that attained a potential of 205 mV failed after 36
months' exposure.
Tubes manufactured by the normal production methods and abrasively
cleaned for a minimum of 7 s gave potential/time curves as shown in Fig. 5.
The potentials remained low (less than 100 mV) throughout the whole of
the exposure period and no pitting occurred.
Trials at Barrow Park—Similar trials were carried out at Barrow Park
with 16 uncleaned and 24 abrasively-cleaned tubes. Potential measure-
ments here were taken only at irregular intervals during the 38 months'
400
350
300 •
•
d
>200
severe pitting
S 170
S150 some pitting
possible
100 no pitting 7 ~ 1 ~ \~ ~ T ^ / l / ~
50 - incubation A* . /
period —Tj-^v A j
-50 1 I 1 J 1 1 1 1 I 1 1 1 I
2 3456810 20 3040 60 XX)
50 80
Exposurefweeks)
FIG. 4—Potential/lime curves obtained with abrasively-cleaned copper tubes manu-

factured with excessive carbon residues when exposed to water that supports pitting.
exposure period. All 16 uncleaned tubes had potentials in excess of 170 mV

but the highest value measured (270 mV) was somewhat lower than the
maximum value occurring at Bramham. Severe pitting of all the tubes was
detected by the eddy-current inspection, and nine failed within 6 to 31
months.
The potentials of the 24 abrasively-cleaned tubes never rose above
100 mV, and no pitting occurred during the 38 months' exposure.
Effect of Water Composition on the Incidence of Pitting

The results of exposure trials at Bramham and Barrow Park suggest that
there is a correlation between the pitting behavior and the organic content
of the supply water (as shown by fluorescence under ultraviolet light), as
well as the degree of carbon contamination of the bore. For example, the
most rapid failures in uncleaned half-hard copper tubes exposed at Barrow
Park (one-fourth fluorescence of laboratory supply) occurred in about
9 months, whereas similar tubes exposed at Bramham (one-eighth fluores-
cence of laboratory supply) failed in 3 months. Furthermore, it has been
found that Bramham water will induce pitting in tubes with CB number 3
(for example, tubes abrasively cleaned for only 0.5 s) whereas this level of
contamination is insufficient to cause pitting at Barrow Park. As men-
tioned earher, pits do not develop at Bramham if abrasive cleaning has
reduced the CB number to 2 or less.
The use of water treatments to remove organic matter is increasing, and,
if such treatments reduce the level of corrosion inhibitor in a water, an
University of Washington (University of Washington) pursuant to License Agreement. No further repro
CORNWELL ET AL ON PIHING CORROSION IN COPPER TUBES 1 65
400 -
350 -
300
->250 -
(J
(/>
>200
e severe pitting
•g 170
1 150 some pitting
possible
100
no pitting
50 / \ /vx^ /
incubation / ^
0
period ~^^^— " ^ ^ ^ ^ ^
-50 1 J 1 1 1 1 1 1
2 3456810 20 3040 60 100

50 80
Exposure (weeks)
FIG. 5—Potential/time curves obtained with copper tubes manufactured by normal

production methods.
increased pitting propensity may result. It is therefore of interest to deter-

mine the behavior of carbon-contaminated tubes, originally supplied with
water that does not support pitting when the water is changed to one that
does support this type of corrosion. It is also of interest to determine
whether a change to a water containing inhibitor is able to cause stifling
of pits that were previously developing actively. The following trials were
carried out to investigate these aspects.
Uncleaned Tubes Exposed Initially to a Water That Supports Pitting,
Then to One That Does Not—'Yht potential of four uncleaned tubes with
CB numbers in the range 3 to 5 exposed at Bramham increased steadily
to >350 mV (Fig. 6). An eddy-current examination indicated that after
2.5 months, severe pitting was occurring in all four tubes. Each tube was
cut into two equal lengths and one half brought to the laboratory without
being allowed to dry out. Two of the halves were installed in the laboratory
rig supplied with Bramham softened water and two in the laboratory rig
supplied with laboratory tap water. The results were as follows.
Tubes left at Bramham—Three out of four half-tubes left at Bramham
failed within a few days of the transfer. The fourth tube was perforated
after a further two weeks' exposure (giving a total exposure of 3 months).
Tubes transferred to the laboratory rig supplied with Bramham water—
Before transfer to the laboratory rig, the tubes had potentials > 350 mV.
Although the potentials fell shghtly after transfer (Fig. 7), the two half-
tubes failed after one and four weeks in the laboratory rig.
400 -
350 -
f/ / X indicates failure
300 j
u
/J
>200
E severe pitting
a 170
1 150 some pitting
1 possible
100
no pitting
50 - incubation
period
-50
2
1 1 J I
3 4 5 6 8 10
1
2 0 3 0 4 0 6 0 100
1
50 80
Exposure (weel^s)
FIG. 6—Potential/time curves for uncleaned copper tubes exposed at Bramham to water
that supports pitting.
Tubes transferred to the laboratory rig supplied with laboratory water—

Before transfer, these tubes also had potentials > 350 mV. Within one week
of being supplied with laboratory water the potentials of the two half-
tubes had fallen to less than 20 mV (Fig. 8). The tubes were exposed to the
laboratory supply for nine months without failure, and no further sig-
nificant changes in potential occurred.
Uncleaned Tubes Exposed Initially to a Water That Does Not Support
Pitting and Then to One That Does—Two uncleaned copper tubes, with
CB number 4, were exposed in the laboratory rig suppHed with laboratory
tap water. After five months' exposure the potential had never exceeded
54 mV. The tubes were transferred to the Bramham rig without being
allowed to dry out, and their potentials then increased steadily to > 300 mV
(Fig. 9). The tubes were perforated after 4 and 4.5 months' exposure at
Bramham.
These experiments demonstrated that with carbon-contaminated tubes
changes in water composition can promote pitting when it was not pre-
viously occurring, or stifle it when it was. Furthermore, the potential taken
up by the tubes is determined by the character of the water.
In a previous section it was stated that the potential of abrasively-cleaned
tubes with marginal levels of contamination exhibited periodic variations
in corrosion potential on prolonged exposure to Bramham water. It is
considered that this type of variation in potential probably results from
CORNWELL CT AL O N PITTING CORROSION IN COPPER TUBES 1 67
400 -
350 -
300
X indicates
/( 1
failure
-250 -
O / '
CO
>200
ra 170 1/ 1 severe pitting

| 1 5 0 ' incubation i ^ 1 some pitting
period 1 possible
100
no pitting
exposure- 1 -exposure in
50 - at 1 laboratory
Bramham ' Bramtiam
water
0
'
-50 1 1 I I I I I 1 1 1 1 1 1 1
2 3456810 20 3040 60 100
50 80
Exposure (weeks)
FIG. 7—Effect of transferring uncleaned copper tubes undergoing pitting at Bramham

to Bramham water in the laboratory.
relatively slight variations in water composition. There is evidence that

pits become stifled when the tubes have a potential < 100 mV, but continue
developing when the potential rises significantly above 100 mV.
Ejfect of Temper on the Incidence of Pitting
Hard-drawn tubes have been found to behave well generally in field
trials, and this is in accordance with practical experience, which is that
failures in such tubes are rare. As previously indicated, this type of tubing
is not normally abrasively cleaned. After the final plug-drawing pass,
residual lubricant remains in the bore, and this may not be completely
removed even when steam-cleaning or detergent-washing processes are
applied. It is possible that residual (uncarbonized) drawing lubricant may
give some protection against the development of pitting in service in some
circumstances, though, in general, the CB numbers for hard-drawn tubes
are so low that pitting would not be expected to develop anyway.
In field trials with six relatively clean (CB numbers 1 to 2) hard-drawn
tubes at the Bramham site and six rather less clean (CB numbers 1.5 to 5)
hard-drawn tubes at the Barrow Park site, no pitting developed and all the
tubes had low potentials throughout the exposure periods (14 months at
Bramham and 9 months at Barrow Park).
To eliminate any complications due to possible presence of residual
uncarbonized drawing lubricant in hard-drawn tubes, the effect of varying
the temper of the copper was investigated by exposing sheet specimens.
400
:1
350
300
250 -
200
severe pitting
1 170
s
^
I
150
100
incubatbn
i1/ 1
some pitting
possible
no pitting
50 _ period ' j
exposure 1 exposure in laboratory
at BramharTTl r^daboratory, water)
-50 1 1 1 1 1 1 r 1 f J 1 1 1 1
2 3 4 56 8 10 20 3 0 4 0 60 100
Exposure (weeks)
FIG. 8—Effect of transferring uncleaned copper tubes undergoing pitting at Bramham

to the laboratory (Leeds water).
These were prepared by the British Non-Ferrous Metals Research Associa-

tion (BNFMRA now the BNF Metals Technology Centre) as part of a
larger program carried out under International Copper Research Associa-
tion sponsorship. Phosphorus-deoxidized copper plate 34 in. thick was
cold-rolled to 0.1 in. thick and then bright annealed to give a hardness of
40 VHN5. Varying amounts of further cold-rolling were carried out to
give specimens with hardnesses of about 60, 80, 100, or 125 VHN5. All the
material was chemically cleaned in a nitric acid/acetic acid mixture, and on
certain specimens carbon was deposited from the vapor phase to give two
levels of surface contamination (a) lightly contaminated corresponding
approximately to CB number 1.5 and (b) fairly heavily contaminated
corresponding approximately to CB number 4.
Specimens in all tempers, with and without carbon deposits, were
exposed at the Bramham site. Figure 10 shows the experimental arrange-
ment.
Figure 11 shows the potential/time curve obtained with three specimens
having a hardness of 80 VHN5 and with CB numbers 0, 1.5, and 4. The
plots are typical of those obtained for these levels of contamination and
similar graphs are obtained irrespective of specimen temper. Figure 12
shows the peak potentials attained by the individual sheet specimens during
the exposure period. Only the most highly contaminated specimens reached
potentials greater than 100 mV, and there was no systematic variation of
CORNWELL ET Al O N PITTING CORROSION IN COPPER TUBES 1 69
400
350
X indicates failure
300
•^250
>200
,S 170
I 150
1 1
100
exposure in - 1 jU- exposure at
laboratory 1 / J Bramham
(laboratory \(
water) / ^ l
V 1
-50 1 1 1 1 1 1 1 1 1 1 1 1 1 1
2 3 4 56 810 20 3040 6 0 100
50 80
Exposure (weeks)
FIG. 9—Effect of transferring undeaned copper tubes from the laboratory {Leeds water)
to Bramham.
peak potential with hardness. The results obtained with these artificially
contaminated sheet specimens indicate, therefore, that hardness in itself
does not affect the pitting behavior of copper.
Ejfect of Alloying on the Incidence of Pitting

In an attempt to find a copper alloy with an increased resistance to
pitting in the presence of carbon residues, a number of special tubes, in the
half-hard condition, uncleaned, with CB numbers generally in the range
4 to 5, were tested at the Bramham and Barrow Park sites. The following
eight materials were evaluated: (a) special coppers: Cu-lSn, Cu-lAl,
Cu-0.7Al-0.4As, Cu-0.25Fe, Cu-0.5Fe; and (b) special brasses: Cu-15Zn,
Cu-lOZn-l.OAl, Cu-10Zn-0.5Sn. Their performance was compared with
that of uncleaned (CB numbers 3 to 4) half-hard copper tubes, which, as
already indicated, usually attain high potentials (300 to 350 mV) at Bram-
ham and are generally perforated in 3 to 12 months. Similar tubes tested at
Barrow Park do not attain such high potentials, the maximum being about
270 mV and the most rapid failures occurring in about 9 months.
With the iron-bearing alloys and the Cu-0.7Al-0.4As alloy at the Bram-
ham site, the electrode potentials increased rapidly and attained similar
values to those for uncleaned copper. Failures occurred in the iron-bearing
alloys within 7 months, and in the Cu-0.7Al-0.4As alloy tubes within 15
months. No failures occurred after 18 months' exposure in the Cu-lAl
FIG. 10—Experimental arrangement for exposure of sheet specimens.
alloy tubes at Bramham, but deep pits (up to 50 percent through the wall)
had developed.
No failures occurred in the Cu-lSn alloy tubing exposed at Bramham or
Barrow Park for 39 and 25 months, respectively. Peak potentials were about
150 mV and examination of tubes after trial showed that only relatively
shallow pitting had occurred.
Most of the Cu-15Zn and Cu-10Zn-0.5Sn tubes failed within 16 months
when exposed at Barrow Park. Although none of the Cu-lOZn-lAl tubes
CORNWELL ET AL ON PITTING CORROSION IN COPPER TUBES 171
400
350 -
300 -
250 -
iD
0200 severe pitting
ft 170
•S ISO • someprtthg /\
possible J \
1
J 100
nopitting /
50
A r—^
0 period 3 / ^ ^^ \^/C \
-50 ^
2 3 4 5 6 8 10 2030 5080 200
Exposure (weeks) "^ ™ ^°°
FIG. 11—PotentialI time curves obtained with three sheet specimens having a hardness of
80 VHN5 and CB numbers 0, 1.5 and 4.
failed at this site after 25 months, extensive deep pitting occurred in all
the specimens exposed.
On the basis of these trials, therefore, alloying the copper can give some
improvement in resistance to pitting in the presence of carbon residues.
The best addition was ISn, the other materials being less good, with
several of them no better than ordinary copper (for equal CB numbers).
Even the best material showed some attack, however, and it is doubtful
whether it would be wise to supply it for general service in the uncleaned
condition. Bearing in mind also the increased processing costs in manu-
facture, the use of alloys instead of phosphorus-deoxidized copper for
seamless water tubing does not appear to be an attractive proposition.
Service Experience in the United Kingdom

Pitting corrosion of copper became a serious problem in the United
Kingdom in the 1950's, when the practice of bright annealing was becoming
increasingly used in preference to an oxidizing anneal followed by a pickling
operation. Once it had been demonstrated that pitting corrosion was
associated with carbon films, British manufacturers began to introduce
cleaning operations designed to remove the deleterious films from the
bores of copper tubes. Abrasive cleaning using water-borne alumina and
cleaning using a variety of air-borne abrasives were processes that became
widely used. Campbell [5] analyzed the failures received by the BNFMRA
and by two large British tube manufacturers involving tubing installed
m150
O
lioo
t * .
• 1 1 ' 1 * » ' i *,
(J 0
O - 1
CD CO ai
a o a o o o S u a
40HV5 60HV5 80HV5 UI U O cj
125 HV5
FIG. 12—PeaA: potentials attained by individual sheet specimens during exposure at

Bramham.
between 1956 and 1962. The analysis led to the conclusion that a practical
solution to the problem had been found in abrasive cleaning.
Variation in the annual rate at which failures have been received by the
authors' company for investigation, for the years between 1958 to 1973,
is shown schematically in Fig. 13. Most of these failures involved half-hard
temper tubing in the one-half inch nominal size. Following the introduction
of cleaning with water-borne alumina in Nov. 1959, the number of failures
investigated fell to acceptable levels in 1964 and remained almost constant
for the next two years. This is in line with Campbell's analysis of the
situation in 1962.
In 1966, however, the British Standard Specification for Light Gauge
Copper Tubes for Water, Gas, and Sanitation (B.S. 659: 1963) was amended
introduction of
improved cleaning
procedures
introduction of
cleaned tubes
introduction of
thinner tutaes
1958 1960 1962 1964 1966 1968 1970 1972
FIG. 13—Variation in the annual rate at which failures have been received for investigation.
CORNWELL ET AL ON PIHING CORROSION IN COPPER TUBES 173
and tubing with a reduced wall thickness was introduced; in 1967 a sub-
stantial increase in the number of service failures was observed. The service
failures increased dramatically during the next three years (Fig. 13), and
it transpired that the abrasive-cleaning procedures that had hitherto been
satisfactory were no longer adequate. In the middle of 1969, more efficient
air-borne abrasive-cleaning treatments and tighter quality control pro-
cedures were introduced, and as a result the number of service failures
started to decrease (Fig. 13).
Figure 14 shows the cumulative number of pitting failures per million
metres for Yi in. (or 15 mm) half-hard tubing manufactured in 1967, 1969,
and 1971. These graphs confirm that the situation has improved con-
siderably since the introduction of abrasive-cleaning practices that are
more effective in removing carbon residues than the earlier treatments.
Summary
The results presented in this paper show that in certain water supplies
the presence of carbon residues in the bores of copper tubes causes the
potential of the surface to increase above a critical value and that rapid
pitting of the copper then occurs. Abrasive cleaning is one means of
reducing the level of carbon contamination to such an extent that the
potential does not rise above the critical value and pitting does not occur.
The results of service experience in the United Kingdom show that the
numbers of failures in bright-annealed half-hard tubing have been greatly
reduced by the use of effective abrasive cleaning techniques.
In surface supply waters that are believed to contain organic corrosion
inhibitors, carbon residues do not give rise to high potentials and pitting
does not occur. However, if the water in a carbon-contaminated tube is
changed from one that does not support pitting to one that does, pits will
develop. Conversely, active pits can be stifled by changing from an
aggressive water to one in which pits cannot be initiated.
FIG. 14—Cumulative number of pitting failures per million metres for 1/2-in. (15-mm)
half-hard tubing manufactured in 1967, 1969, and 1971.
Experience with hard-drawn tubing is that it normally gives good service

performance and pitting failures are rarely encountered. This is due to the
fact that such a tube normally contains only small amounts of carbo-
naceous residues; in addition, thin films of residual drawing lubricant may
give a degree of protection in some circumstances.
Copper containing about I percent of tin or aluminum (particularly the
former) are more resistant than ordinary coppers to pitting in the presence
of carbon residues. It appears, however, that these materials do not give
an economic answer to the problem of eliminating pitting in cold, organi-
cally pure supply waters.
Acknowledgments
The authors wish to thank the directors of Yorkshire Imperial Metals
Limited for permission to publish this paper. Thanks are also due to the
Claro and North Lindsey Water Boards (now part of the Yorkshire and
East Anglia Water Authorities, respectively) for providing sites for the
corrosion test rigs, without which the work would not have been possible.
The preparation of the sheet specimens by the BNF Metals Technology
Centre is also gratefully acknowledged.
References
[/] Campbell, H. S., Chemistry and Industry, 1955, p. 692.
[2] Hatch, G. B., Journal of the American Water Works Association, Vol. 53, 1961, p. 1417.
[i] Schafer, G. J., New Zealand Plumbing Review, Sept. 1964, p. 5
[4] Gerth, D., Sanitar-installaiion, Btechberarbeitung, Zentralheizungsbau, Lufttechnik,
Vol. 20, No. 19, 1965, p. 350.
[5] Rambow, C. A. and Holmgren, R. S., Jr., Journal of the American Water Works
Association, Vol. 58, 1966, p. 347.
[6] Gilbert, P. T. and Cairns, J. H. in The Technology of Heavy Non-Ferrous Metals and
Alloys, Newnes, London, 1967, p. 144.
[7] Campbell, H. S., Journal of the Institute of Metals, Vol. 77, 1950, p. 345.
[8] Campbell, H. S., Proceedings, Second International Congress on Metallurgical Cor-
rosion, National Association of Corrosion Engineers, 1963, p. 237.
[P] Schafer, G. J., Australian Corrosion Engineering, Vol. 6, 1962, p. 5.
[10] von Franque, O., Werkstoffe und Korrosion, Vol. 19, No. 5, 1968, p. 377.
[//] Lucey, V. F., "Pitting Corrosion of Copper in Supply Waters—The Eflfect of Water
Composition, First Report," Research Report No. A 1692, British Non-Ferrous Metals
Research Association, June 1968.
[12] Lucey, V. F., "Pitting Corrosion of Copper in Supply Waters—The Effect of Water
Composition, Second Report," Research Report No. A 1723, British Non-Ferrous
Metals Research Association, April 1969.
[13] Devroey, P. and Depommier, C , unpublished work.
[14] Campbell, H. S., "The Resistance of Hard Drawn Copper Tubes to Pitting Corrosion,"
Technical Memorandum 209, British Non-Ferrous Metals Research Association,
May 1966.
[75] Cornwell, F. J., Wildsmith, G., and Gilbert, P. T., British Corrosion Journal, Vol. 8,
1973, p. 202
[16] Pourbaix, M., Corrosion, Vol. 25, 1969, p. 267.
[17] Pourbaix, M., Corrosion Science, Vol. 12, 1972, p. 183.
[18] Lucey, V. F., British Corrosion Journal, Vol. 2, 1967, p. 175.
[19] Campbell, H. S., Journal of Applied Chemistry, Vol. 4, 1954, p. 633.
DISCUSSION OF PITTING CORROSION IN COPPER TUBES 175
DISCUSSION
Arthur Cohen^—The authors have prepared a detailed report on a prob-

lem that has been underway on a semicontinuous basis for the past 25
years in both Britain and the United States. This study originated in the
late 1940's during Britain's massive reconstruction of war-damaged
housing when a serious epidemic of pitting corrosion in England was
circumstantially associated with the presence of heavy films of carbon
inside copper water tube. The paper by Hector Campbell of the British
Non-Ferrous Metals Research Association publicized this circumstantial
evidence and as a result of Campbell's investigation, production practices
were adopted by British brass mills that were intended to produce tubes
"free from . . . deleterious films in the bore".
While it is scientifically sound to associate the presence of carbon films
in the bores of copper water tube with the occurrence of pitting corrosion,
we are convinced that carbon films have never been demonstrated to be the
cause of pitting corrosion in copper water tube. More important, neither
has it been demonstrated that special procedures to produce tubes free of
carbon films solve the problem of pitting by aggressive water because it can
and has been demonstrated that an aggressive water can cause pitting of
copper in the absence of such films.
But most important, we are certain that pitting of copper water tube
cannot occur without exposing the tube to an aggressive water in the
first place, irrespective of surface condition or degree of cleanness.
It is surely true that if there were carbon present on the inside surface of
a tube it would, in theory, provide the electrochemical conditions that
would favor pitting. However, we maintain that no direct evidence has
ever been established showing a direct cause and effect relationship be-
tween carbon films and pitting corrosion. Nor has it been shown that
complete absence eliminates the problem. For example, in laboratory
experiments conducted at a Belgian brass mill, hard drawn tube with
appreciable amounts of carbon on the inside surface were found to resist
pitting corrosion, while annealed tube with the same amounts of carbon
present suff'ered failures.
This experience has been verified in both the United States and Britain
where pitting corrosion by an aggressive water has occurred even in the
absence of carbon films as, for example, in hard drawn tube. Even though
the British tube producers have introduced aqua- or dry-blasting cleaning
techniques, they still experience pitting corrosion.
' Standards engineering manager, Copper Development Association, New York, New
York.
A recent paper by Cruz and Pomeroy^ also confirms the fruitlessness of

work to try to establish that carbon films cause pitting. Their data also
clearly show that pitting corrosion has occurred in carbon-free tubes.
Also supporting the position that the presence of carbon films is un-
necessary for pitting corrosion to occur is the report of the British N on-
Ferrous Metals Research Association.' It illustrates that copper hot water
cyHnders or combination tanks fabricated from carbon-film-free copper
sheet have given completely trouble-free service except for a few districts
which are supplied with aggressive hard or moderately hard deep well
waters. The pitting that has been experienced has occurred in the cold
water section of these tanks.
A paper by Lyman and Cohen^ rejected the British position of carbon
film as being responsible for pitting corrosion and established how it is the
chemistry of water that determines whether or not pitting will occur. The
paper also pointed out how tube production methods differ in the United
States and Britain. Regrettably, this paper has not been referenced despite
its familiarity to the authors. Also regrettably omitted by the British
authors is any reference to the work of Rambow and Holmgren which
demonstrated how water chemistry controls whether or not pitting occurs
and how pitting can be eliminated by simply treating an aggressive water
to increase the pH and drive out the free carbon dioxide.^ The British
authors cite Rambow and Holmgren (Ref 5 of paper) but only in passing
in the first sentence of their paper and for the purpose of establishing that
"copper tubes are widely used . . . and have very long life."
Information received from a number of U.S. water companies have
confirmed that the solution to overcome pitting corrosion has been and
continues to be to treat the aggressive water. This is accomplished by the
addition of either lime or caustic soda.
In the United States, treatment of well waters to control their corrosivity
to plumbing materials is a common practice. We are convinced that this
is the route to follow rather than to follow the suggestion of the British
and introduce another operation in the tube manufacturing process, an
operation whose quality control cannot be reproduced (and for which no
standards exist) despite repeated efforts by numerous laboratories on both
sides of the Atlantic.
Attempts at controlling the operation by measuring the level of carbon
contamination in a carbon black (CB) test devised by Devroey and
^ Cruz, H. and Pomeroy, R. D., "Corrosion of Copper Pipe, Journal of the American
Water Works Association, Aug. 1974.
' "Copper Cylinders and Combination Tanks for Long Service," British Non-Ferrous
Metals Research Association.
* Lyman, W. S. and Cohen, A., "Service Experience with Copper Water Tube," Materials
Protection and Performance, Feb. 1972.
' Rambow, C. A. and Holmgren, R. S., Journal of American Water Works Association,
Vol. 58, 1966, p. 347.
Depommier in Belgium, have been fruitless. In one study with which we

are familiar, seven independent laboratories conducted several round-robin
tests to determine whether it was possible to achieve uniformity of labora-
tory results in the determination of the CB numbers. The data were com-
pletely nonreproducible and, in fact, so were the colors which ranged from
black to gray to brown despite rigorous adherence to the prescribed
procedure.
The one significant contribution of the authors' paper is the tests where
tubes were exposed to an aggressive pitting water at Bramham and then
moved to Leeds where they were exposed to a nonaggressive water, and
vice versa. The tubes which were exposed to the nonpitting water initially
and then to a pitting water, experienced no failure in the first water and
then failed in four to four and one-half months after transfer to the pitting
water. Similarly, those tubes which were exposed first to a pitting water
and then to a nonpitting water experienced failure in the first water but no
further failures after transfer to the nonaggressive water because the
pitting progression through the tube wall became stifled.
The British authors seem to be offering us a solution to pitting which
their own and other data show to be unreliable. We would propose to them
a simple solution that has been demonstrated to work everytime; treat the
water to render it nonaggressive. Since the British promote water treatment
to control dezincification of the brasses they choose to use in their water
systems, it is strange indeed that they do not take the same approach to
pitting problems.
F. J. Cornwell, G. Wildsmith, and P. T. Gilbert {authors' closure)—
In reply to Cohen's contribution the authors wish to make the following
points.
1. It is agreed that pitting of copper occurs only in certain waters that
support this form of attack.
2. The relationship between pitting corrosion and presence of carbon
residues on tubes as installed, in waters that support this form of attack,
has been demonstrated both by direct experiment and by analysis of
overall operating experience in the United Kingdom.
Clean (well-abraded) copper tubes suff"ered no pitting at the Bramham
test site and had consistently low potentials (see Fig. 5 of paper), whereas
tubes containing carbon residues assumed high potentials (see Fig. 2 of
paper) and failed rapidly by pitting when tested in the same water at the
same time.
Analysis of service failures in the United Kingdom over many years and
correlation with production control data recorded by the authors' company
has shown that over a period of some years about 1 percent of the tubes
manufactured had rather higher levels of carbon residues than normal,
and these gave rise to over 90 percent of the failures occurring. Effective
removal of carbon residues by dry abrasive cleaning with iron grit has
practically eliminated the failures previously occurring. Almost all the
failures still experienced are in tubes made prior to the introduction of
this process (see Fig. 14 of paper).
3. Hard-drawn (unannealed) tubes can contain carbon residues as there
are other possible sources of carbon besides decomposition of residual
drawing lubricant during bright annealing (such as use of graphitic lubri-
cants during extrusion and decomposition of lubricant during drawing).
In general, however, hard-drawn tubes have low levels of carbon residues
as produced, and work, in United Kingdom and in Belgium, has shown
that this is the main reason why such tubes behave relatively well, any effect
of temper as such being secondary. No doubt the widespread use of hard
temper tubes in the United States is one reason why pitting corrosion has
been a less severe problem than in the United Kingdom where most of the
tubing used is of half-hard temper.
4. The CB test is certainly far from ideal. However, when used under
strictly standardized conditions by a single organization it has proved a
most useful aid to quality control. On the basis of this control the authors'
company has reduced the incidence of pitting failures in half-hard tubes to
a few percent of those previously occurring.
5. After a period of service carbon residues become incorporated in the
general corrosion product films on the tube surfaces and can then be
readily removed by treatment with dilute citric acid solution. This cleaning
process has been applied to several large-scale installations in which
pitting corrosion was occurring. In each case trouble then ceased, showing
that the removal of carbon was an effective remedy; there was no change
in the nature of the supply water at any stage.
6. The role of carbon in promoting pitting corrosion in certain types of
water has been recognized and accepted, to the authors' knowledge, by
authorities in Belgium, France, Germany, Holland, New Zealand, South
Africa, and Sweden as well as the United Kingdom, and no doubt in
other countries as well.
7. There are many factors that influence the development of pitting of
copper under nodules of corrosion product in cold supply waters, including
the nature of the supply water, the condition of the metal surface, and the
geometrical features that affect disposition of copper corrosion products.
This last factor can explain why copper cylinders can suffer corrosion in
certain waters whereas clean copper tubes do not.
8. In the paper by Cruse and Pomeroy it is interesting to note that the
three specimens containing least carbon (Specimens 24, 40, and 41) suffered
no pitting. All the other specimens for which a carbon figure is given
contained enough to account for the observed attack. The paper by Lyman
and Cohen, though valuable in other respects, has only limited information
on pitting corrosion. It deals with only a few cases and gives no informa-
tion on carbon contamination.
9. It is encouraging that in the United States pitting has been successfully
overcome by treating the water. The authors look forward with interest to
hearing of further evidence from the United States of the successful appli-
cation of this technique.
Florian Mansfeld1
Pitting Caused by Chlorides or Sulfates in

Organic Media
REFERENCE: Mansfeld, Florian, "Pitting Caused by Chlorides or Sulfates in

Organic Media," Galvanic and Pitting Corrosion—Field and Laboratory Studies,
ASTM STP 576, American Society for Testing and Materials, 1976, pp. 180-202.
ABSTRACT: The pitting behavior of titanium and titanium alloys, pure nickel,
aluminum 6061, ana stainless steel Type 304 has been studied using electrochemical
techniques in methanol in the presence of sulfates or chlorides. An important fac-
tor is the water content of these solutions. In anhydrous solutions of methanol and
hydrochloric acid (HC1), passivation cannot occur for titanium and high corro-
sion rates are observed. Addition of water at a concentration as low as 0.6 percent
leads to passivation. The passive region is limited to noble potentials by the pitting
potential which, up to 2.5 percent water, increases linearly with water content
and is more or less independent of water content for higher concentrations.
Similar observations are made for methanol containing sulfuric acid (H 2 S0 4 ).
Aluminum 6061 suffers from severe pitting when polarized anodically in methanol
with 0.1 or 1.0 N H 2 S0 4 . Pitting was observed also for nickel after anodic polariza-
tion experiments in 2 TV H 2 S0 4 in methyl alcohol (CH3OH). Iron, on the other
hand, could not be passivated and pitting, therefore, did not occur. Pitting occurred
for stainless steel Type 304 in 0.1 N H2SO, in CH3OH at rather noble potentials
in the transpassive region. These results indicate that the solvent can have a large
influence on the pitting susceptibility of metals. Titanium is very resistant in
aqueous media, but shows pitting behavior similar to aluminum in organic media.
It is also found that sulfates which do not cause pitting in aqueous media, where
they even might be used as inhibitors, cause severe pitting in organic media for cer-
tain materials. Perchlorates have also been fpund to induce pitting in methanol.
Phosphates lead to passivation by formation of a film of high electronic resistance.
While pitting occurs on titanium in methanol containing 0.1 N H 2 S0 4 , no localized
attack was observed under the same conditions in ethanol, ethylene glycol, or
isoprbpanol.
KEY WORDS: corrosion, chlorides, sulfates, pitting, passivation, perchlorates,

phosphates, methanol
Most studies of localized corrosion in the form of pitting have been

carried out in aqueous media and have led to the conclusion that the halide
ions, especially the chloride ion, are very dangerous in promoting failure
1
Member of technical staff, Science Center, Rockwell International, Thousand Oaks,
Calif. 91360.
180

MANSFELD ON PITTING CAUSED BY CHLORIDES OR SULFATES 181
of a wide variety of materials. Other types of anions, such as sulfates,

nitrates, perchlorates, and chromates, seem to inhibit pitting when present
in solutions containing halides as shown by Uhlig et al for iron [1],^
18Cr-8Ni stainless steel [2], and aluminum [3].
The susceptibility of metals and alloys to localized corrosion in non-
aqueous solutions is of interest since Mori et al [4] have shown that stress
corrosion cracking (SCC) of titanium occurs in methanol containing
hydrochloric acid (HCl) or sulfuric acid (HjSOO, while zirconium cracked
in methanol containing HCl or H2SO4 and in ethanol containing HCl.
Small additions of water were shown to inhibit SCC of zirconium or
titanium.
In order to obtain further information concerning locaUzed corrosion in
nonaqueous media, the author has recently studied the effect of water on
passivity and pitting of titanium in solutions of methyl alcohol (CH3OH)
and HCl [5] and the passivation and pitting behavior of titanium, alumi-
num, nickel, stainless steel, and other materials in CH3OH containing
H2SO4 [6]. More recent studies [7] include the corrosion behavior of ti-
tanium in CH3OH containing perchloric acid (HCIO4), nitric acid (HNO3),
and phosphoric acid (H3PO4) and comparison of polarization behavior in
methanol, ethanol, ethylene glycol, and isopropanol containing sulfuric
acid.
Experimental Procedures
Anhydrous solutions of CH3OH-HCI were prepared by saturating methyl
alcohol (nanograde, Mallinckrodt) with HCl gas. These solutions were
then diluted by adding more methyl alcohol to give a certain concentration
of HCl which was measured by titration. Aqueous solutions ofCH30H +
HCl were prepared by adding water to anhydrous solutions of CH3OH -f
HCl or by adding certain amounts of concentrated hydrochloric acid to
pure methanol. Due to the water content of concentrated HCl, a solution
of I N HCl in CH3OH contains about 6.3 percent water (H2O).
Unlike the case of methanolic solutions containing HCl, anhydrous
solutions of CH3OH + H2SO4 cannot be prepared. The solution of 0.1 N
H2SO4 in CH3OH used for most tests contains, however, only 0.04 percent
H2O, while a solution of 1.0 A'^ H2SO4 in CH3OH contains 0.4 percent H2O
as determined by Karl Fischer titration. Pure titanium (iodide), com-
mercially pure titanium (Ti-75A containing about 4000-ppm total inter-
stitial impurities), or Ti-6A1-4V were machined to cylindrical electrodes
(about 2 cm^ geometric surface) and connected to a holder so that only the
electrode. Teflon, and glass were in contact with the solution. The electrode
was degreased in boiling benzene at 80°C for 5 min, then etched in a
solution of 30 percent HNO3-2O percent hydrofluoric acid (HF)-20 percent
+u. / 1 1 1 1 1 ini| 1 I r l 1 TTTT T I I TTin^ r i I ITTI] T I n IITT
+0.5 - -
+0.3 - -
® X = 1.0
(2) X = 0.1
+0.1 ( D X = O.OI
> 0
ID
'
> U
-0.1
;;
-0.3
-0.5
1 1 1 III J 1 1 J-Llllll 1 ] 1 1 mil 1 1 1 1 1 ml 11 1 1 I m l . 1 1 1 Mil
-1
10 10 10 10-^ 10 10^
i (/J.A/cm )
FIG. 1—Potentiostatic anodic polarization curves for titanium 75A in solutions of

CHzOH + xN HCl anhydrous (x = 1.0, 0.1, or 0.01).
H2SO4-H2O for 30 s, washed thoroughly in pure methanol, and then

immediately immersed in the test solution, which was either air saturated
(but unstirred) or deaerated and stirred with argon. The reference electrode
was an aqueous saturated calomel electrode (SCE).
All potentials refer to SCE. After the rest potential had become constant,
the potential was changed in steps of 10 mV/min using a potentiostat. In
most experiments, a cathodic polarization curve was recorded first, the
potential was then made more positive, and an anodic curve was recorded.
At higher potentials when no pitting was observed, the rate of potential
change was 50 mV/5 min. Since methanol solutions of hydrogen chloride
of H2SO4 have high electrical conductivity due to the anomalously high
mobility of the methoxonium ion CH3OH2+, no major experimental
problems concerning ohmic drops were encountered.
Results
Titanium in CH3OH + HCl
Figure 1 shows potentiostatic polarization curves for Ti-75A in anhy-
drous CH3OH + xN HCl for X = 1.0, 0.1, or 0.01.' The effect of HCl con-
centration is clearly seen. The curves are shifted parallel in the noble
direction with decreasing HCl concentration, and no active-to-passive
transition is observed up to the highest currents studied. For comparison,
'Due to the water content of pure methanol (=a0.02 percent) these "anhydrous solu-
tions" contain a small amount of water.
MANSFELD ON PiniNG CAUSED BY CHLORIDES OR SULFATES 1 83
Fig. 2 shows polarization curves in methanol to which sufficient concen-

trated HCl was added to give aqueous solutions of CH3OH + xN HCl for
X = 1.0, 0.1, or 0.01. Again, the rest potential has the most noble value for
the lowest HCl concentration, but surprisingly, passivity is observed in the
solution with the highest HCl concentration (1.0 N, 6.3 percent H2O) but
not for the solution with the lowest HCl concentration (0.01 N, 0.06 percent
H2O). For the solution which contains 0.1 A^' HCl, the region of passivity
is small due to pitting, the occurrence of which was confirmed by micro-
scopical observation. In these aqueous HCI-CH3OH solutions, the H2O
content increases with increase of the HCl content, because of the water
content of concentrated HCl (37 percent HCl).
+\.B I t III 1 r- -1 1—I I I r I
+ 1.6
/
+ 1.ii
+ 1.2
+ 1.0
+0.8 -
e +0.6
+0.'f
+0.2
x=0.01
-0.2 -
-O.i)
-0.6 I 1—u-
10 1.0 10 10^
i ( liA/cm )

CH3OH + xN HCl aqueous (x = 1.0, 0.1, or 0.01).
+0.9 1 ; 1 I I 1
- CH OH + IN HCl aq.j ^^4.4%
+0.7 - (6.3% H2O) j y ^ /3.2% -
1 1 /
+0.5 - y 1 . 9%
+0.3 - 1.3%-
'+0.1
0 - -
-0.1
0.6%
-
-0.3- 0-
-
-0.5 — " " i r 1 1
10 10 10 10^ IC
i ifiA/cm)

CHzOH + 1^ HCl anhydrous + HtO.
In the experiments of Fig. 3, increasing amounts of H2O were added to a

solution of anhydrous 1 N HCI-CH3OH. In the absence of H2O no active-
passive transition is observed; the addition of 0.63 percent H2O shifts the
polarization curve in the noble direction, and a small region of passivity is
observed limited by breakdown of passitivity through pitting. With an
increase in H2O content, the region of passivity is extended, the passive
current density being about 1.3 /iA/cm^ The passive region is limited by
the critical potential for pitting V^' which becomes more noble as the H2O
content increases. After each run the specimen was investigated under a
microscope to make sure that pitting had indeed occurred. At higher
water contents, establishment of VJ from polarization curves was very
difficult. In aqueous 1 A'^ HCI-CH3OH (about 6.3 percent H2O), no precise
value of Vc' could be established. For this reason, the following two
different experiments were carried out to determine more precisely the
steady-state value, ¥„ of the critical pitting potential.'' In the first experi-
ment, a constant current density of about 50 ^lA/cm^ was applied to the
test electrode and the potential-time curve recorded. This technique has
been recently used by Tsinman et al [8]. Figure 4 shows the results for
CH3OH -h 1 N HCl -\- AA percent H2O. After application of the constant
* The notation by Leckie and Uhlig [9] is used here to distinguish between short time
(KcO and steady state (Ve) critical pitting potentials.
MANSFELD ON PIHING CAUSED BY CHLORIDES OR SULFATES 1 85
-T r 1 r- -1 1 1 T" -1 1 1 r-
+ 1.0
J = +100uA
-1.0
1 1
10 15
t[min]
FIG. 4—Changes of potential at a constant anodic current of 100 nA in CHzOH + 7 N

HCl anhydrous + 4.4 percent HiO.
current density, the potential increased slowly to more noble values.

When the maximum value was reached, small fluctuations of the potential,
which were probably due to formation of the first pits, were observed.
The potential then decayed fast to a constant value, which has been called
the activation potential by Tsinman [5]. Microscopic observation of the
electrode after the test showed occurrence of a number of pits. In the next
experiment this constant potential was applied to a fresh electrode imme-
diately after immersion into a fresh solution and the current-time curve
recorded. If the potentiostatically applied potential was below the critical
pitting potential V„ the current decayed continuously due to passivation
of the surface and no pits were observed (Curve A, Fig. 5). The potential
was then increased by 15 or 25 mV. If Vc was exceeded, the current increased
after an initial decrease and pitting was observed (Curve B). Critical pitting
potentials estimated from polarization curves {Vc) and measured more
precisely at a constant potential {V^ are plotted in Fig. 6. While VJ seems
to increase linearly with water content, values for Vc seem to level off after
a H2O content of 2.5 percent H2O. Values of Vc in solutions of CH3OH +
3.15 percent H2O + xN HCl {x = 0.01, 0.1, 1.0) are shown in Fig. 7,
which shows an increase of about 0.3 V when [HCl] is decreased by a
factor of 10.
30 r~—r r 1 r ^ 1 1 1 1 p
25
^ '5
V = +0 mV (A)
• •! I I I I —t • • '
10 20
t/100[secl
FIG. 5—Changes of current at constant potential in CH3OH + 7 N HCl anhydrous +

4.4 percent H1O.
Various Materials in CHzOH + H^SOi

Titanium and Titanium Alloys—Polarization curves were obtained for
pure titanium (iodide), Ti-75A, and Ti-6A1-4V. No significant differences
in the polarization behavior were observed for different alloy compositions.
Figure 8 shows polarization curves for pure titanium in 0.1 A'^ H2SO4 in
CH3OH. In the absence of water starting from the corrosion potential, a
cathodic polarization curve has been obtained with a Tafel slope of be ^
0.09 V. This cathodic polarization apparently resulted in reduction of the
surface oxide and a lowering of the hydrogen overvoltage as can be seen
from the cathodic curve obtained on shifting the potential in the more
noble direction. This effect might also result from formation of titanium
hydrides which are assumed to have a hydrogen overvoltage lower than
oxide covered titanium [70]. On the anodic branch of the curve, a short
region of passivity can be detected, at about — 0.24 V versus SCE, a sharp
increase of the current occurs. Examination of the electrode after the
experiment showed that localized attack in the form of pitting had occurred
(Fig. 9).
When 1 percent of water was added to the test solution, the titanium
electrode apparently was in the passive state. The anodic current remained
MANSFELD ON PITTING CAUSED BY CHLORIDES OR SULFATES 187
+o.'ii 1 r
+0.3 -
+0.2
+0.1 -
-0.1 -
FIG. 6—Dependence of pitting potential on water content of CH%OH + 7 N HCl anhy-

drous + X percent HiP.
small and constant up to about +0.7 V (Fig. 8). At higher potentials the
current increased steadily, but not as sharply as in water-free solutions.
Nickel—Figure 10 shows the effect of water on the polarization behavior
of pure nickel (99.9 percent) in 0.1 A^ H2SO4 in CH3OH. The cathodic
branches and the anodic branches of the polarization curves were identical
up to +0.2 V for solutions with 1 percent H2O and without added H2O.
A decrease of the current was observed upon further anodic polarization
indicating passivation in the solution containing added water, while only a
very small decrease of the current was observed at +0.35 V in solutions
where no water had been intentionally added. These results show that
+0.R
FIG. 7—Dependence of pitting potential on concentration of HCl anhydrous in solutions

ofCHiOH + 3.15 percent HiO + xN HCl (x = 1.0, 0.1, or 0.01).
water has no influence on the kinetics of the hydrogen evolution reaction

(HER) and on active dissolution. The water plays, however, a decisive role
in passivation. Figure 11 shows the effect of H2SO4 concentration in meth-
anol. While an increase in acid concentration leads to an increase in the
critical current density for passivation, it also leads to a decrease of the
passive current density. The latter effect most likely results from the higher
water content inherent in the solution of 2 A'^ H2SO4 in CH3OH. Pitting of
+1.6 1 1 1 r 1
111111
"1 1/ '1 1 ' 1
/ IODIDE Ti
+1.2 - / CHjOH + O.IN H^SO^
/ NO HÔ ADDED
+0.8-
+0.4 -
0 -
-0.4 =^
= 5
-0.8 -
——--~-^^\'^
-1.2 III 1 1 I I 1 1 1 1
10 10" 10-^ 10" 10
i (liA/OT )
FIG. 8—Potentiostatic polarization curves for pure titanium on 0.1 N HtSOi in CHiOH,
argon stirred.
the electrode was observed after the anodic polarization experiments in

2 A^ H2SO4 in CH3OH (Fig. 12).
Stainless Steel Type 304—Stainless steel Type 304 is readily passivated
at rather low potentials in 0.1 NnSOi{V\g. 13)or 1.0 A'^HjSOiin CH3OH.
The active to passive transition in Fig. 13 is only observed after cathodic
reduction of the surface film formed in air or in solution. At potentials
higher than +1.1 V versus SCE, a rapid increase of the current was ob-
served. Microscopic observation of the surface of the specimen showed
that pitting had occurred (Fig. \Ad). The area around the pits appears to
be attacked as shown in Fig. \Ab in a different pattern than observed for
titanium, aluminum, and nickel.
Aluminum 6061—^The corrosion rate of aluminum 6061 in 0.1 N H2SO4
in CH3OH was low (about 0.2 mg/dmVday (mdd)). The potentiostatic
polarization curve is shown in Fig. 15. When the specimen is polarized in
the cathodic direction, the current starts to increase continuously with time
at potentials more negative than — l.O V. This leads to the loop in the
cathodic polarization curve shown in Fig. 15. Upon anodic polarization,
the aluminum alloy is in the passive state up to about 0.0 V when the
current increases very sharply due to pitting. Gas evolution from the pits
is observed under these conditions. Very large pits are observed as shown
FIG. 9—Pits on surface of titanum after anodic polarization in 0.1 N HtSOi in CHzOH
without water addition, magnification approximately X180.
in Fig. 16. Similar results were obtained in 1.0 N H2SO4 in CH3OH. The
effect of water additions has not yet been studied.
Iron—For pure iron, no passivation occurred in 0.2 N H2SO4 or 2 A'^
H2SO4 in methanol up to a potential of +0.8 V versus SCE. The effect of
water addition is different than that in the case of titanium or nickel.
Additions of water up to 10 percent did not produce passivation upon
anodic polarization, but increased the rate of anodic dissolution reaction
(Fig. 17). The corrosion rate of iron in 0.1 N H2SO4 in CH3OH was very
high compared to that of titanium or nickel in the same medium. Using
polarization resistance measurements and extrapolation of potentiostatic
polarization curves to the corrosion potential, an average corrosion
current density of 0.32 mA/cm^ was measured for iron, which corresponds
to 800 mdd.
MANSFELD ON PIHING CAUSED BY CHLORIDES OR SULFATES 191
+1.6 -1—I—I I I 111| 1—I—I I I I ii| 1—I—I I I I I I I 1—1—r
+1.2
+0.8
+0.4
CH3OH + O.IN H2S0^

NO H2O ADDED
-0.4- n HÔ ADDED
-0.8 I I I 11II I I I I 11111 I I I I I I I I III 1 I I
10 10' 10-' 10" 10

i (MA/CIH'^)
FIG. 10—Potentiostatic polarization curves Jor nickel in 0.1 N H^SOt in CHsOH with
and without addition of I percent H%0, argon stirred.
+2.0 ] J 1 I I M II
+1.6
+1.2
5 +0.8
+0.4
-0.4 J-JJ I I i I I I -I— I I I I
10 10 10'' 10" 10
i (yA/cm )
FIG. 11—Potentiostatic polarization curves for nickel in 0.1, N HiSOi in CH3OH and
2 N H2SO^ in CH,OH.
FIG. 12—Pitting on nickel after test in 2 N HiSOi in CHzOH; magnification approxi-

mately XI80.
Copper—The anodic polarization curve for copper (Fig. 18) was similar
to that observed in aqueous H2SO4. No active-passive transition was
observed up to an applied potential of +2.0 V. The anodic current at
potentials more noble than about 0.0 V versus SCE increased when the
solution was stirred by argon, indicating that the anodic process is limited
by mass transport in this potential region.
Platinum—Experiments on platinum were carried out in order to investi-
gate the stability of the electrolyte. Figure 19 shows a polarization curve
which was started at —0.8 V versus SCE. Tafel behavior with a Tafel slope
of be = 45 mV is observed over 4 decades; the deviations at higher current
density are most likely due to uncompensated ohmic drop. The anodic
current remains low up to about +1.0 V from where it increases con-
tinuously. This is most likely due to oxidation of methanol as also ob-
+1.6 I 1—I I I I I ii| 1—I I I I I ii{ 1—I I I I 111| I I I I ll| 1 1—I M i l l
+1.2
+0.8
+0.4
-0.4
I I I I I I I 1 I I I I I III I—I—I I I III

-0.8
10 10' 10 10^ lO''
i (yA/cm )
FIG, 13.—Potentioslatic polarization curves for Type 304 stainless steel in 0.1 'N HiSOt
in CH3OH, argon stirred.
served by Stolica on platinum in lithium chloride (LiCO-CHsOH-HaO

solutions [77]. No oxygen evolution has been observed on platinum or any
other metals studied.
Titanium in CH3OH Containing Different Acids

In order to study further the effect of different anions on passivity and
pitting in methanol, potentiodynamic polarization curves have been
obtained in CH3OH containing HCIO4, HCl, H2SO4, HNO3, or H3PO4
with an anion concentration of one (Fig. 20). The different water content
of these solutions makes it difficult to obtain a quantitative evaluation of
anion effects. The occurience of pitting in solution containing HCIO4 is,
however, very surprising since the perchlorate ion in aqueous solutions
usually is much less damaging to passive films. It is remarkable, in addition,
that pitting is most pronounced in CH3OH + 1 A'^HC104 since this solution
has the highest water content. The absence of pitting in solutions containing
H2SO4 or HCl is expected due to the high water content (Figs. 3 and 8). A
film of very high resistance seems to form on the titanium surface in
CH3OH + H3PO4 as shown by alternating current impedance measure-
ments [7]. This film protects the surface in the passive region and slows
down the reduction reaction in the cathodic region. The rate of the reduc-
tion reaction is the highest in the presence of nitric acid, probably due to
reduction of the nitrate ion.
FIG. 14—Pitting on Type 304 stainless steel after anodic polarization in 0.1 N HiSOt in
CHuOHiFig. 13): (a) magnification approximately X45, and(b) magnification approximately
X180.
Titanium in Different Organic Solvents Containing H-iSOi

The effect of water on passivity and pitting of titanium in organic sol-
vents has been studied further for water contents between 0 and 100 percent
in methanol, ethanol, isopropanol, and ethylene glycol in the presence of
HCl or H2SO4 [7]. Figure 21 presents an example obtained for titanium 75A
in solvents containing 0.1 A'^ H2SO4 (0.04 percent H2O). Pitting as evidenced
by the sharp rise of the current at a characteristic potential in the passive
region is only observed in methanol, in which the corrosion potential has
the most active value. In ethanol, an increase of the current is observed at
the most noble potentials, while in ethylene glycol, the typical active-
passive passivation is observed in the polarization curve. In isopropanol
the most noble corrosion potential and passive behavior in the entire
potential region studied are observed.
FIG. 14—(Continued).
Discussion
Passivating Ejfect of Water
The results obtained in this investigation have shown clearly that passiva-
tion of titanium cannot occur in CH3OH-HCI in the absence of water. In
anhydrous solutions anodic dissolution occurs following Tafel behavior.
The polarization curves are shifted parallel in the noble direction as the
HCl concentration decreases. Addition of water to the anhydrous electro-
lyte leads to passivation at a concentration as low as 0.6 percent water
although the extent of the passive region is very small. This results from the
fact that the critical pitting potential Vc is only slightly noble to the corro-
sion potential. It has to be considered at this point that the surface concen-
tration of water might be diiferent from that in the bulk due to double-
layer effects and solvation of dissolved metal ions. The latter effect would
-1—I—[ I I I i i | 1—I—I I I 111| 1—I—I I 11 i i | -I—I I I I I III r
Al 6061
CH3OH + O.IN H^SO^
+0.4
-0.4
-0.8
-1.6 _i 1 • I I I I ll I 1 I L I ] ] I M ] _J I -J
10 lO' 10 10 10
i (pA/on')
FIG. 15—Poteniiostatic polarization curves for aluminum 6061 in O.I N HiSOi in CHzOH,
argon stirred.
decrease the amount of water available for passivation. No information is

available concerning double-layer effects in the solutions studied. Increasing
additions of water lead to a broader region of passivity in which the current
is independent of potential. At a certain potential (the critical pitting
potential) chloride ions are absorbed strongly enough to displace the
adsorbed water molecules and penetrate the passive film. As more water is
added to the electrolyte the passivating species (presumably the oxygen of
water) is more strongly absorbed and Vc is shifted to more positive values.
When a sufficient amount of water is added to produce a sufficient concen-
tration of the passivating species at the surface of the metal, the critical
pitting potential increases only very slightly. At a sufficiently high, constant
water content, the pitting potential becomes more noble as the chloride ion
concentration decreases, as observed for many metals in aqueous electrolyte.
These findings also explain the initially surprising results of Fig. 2, where
the electrode was polarized in the anodic direction in solutions prepared
from pure methanol and concentrated hydrochloric acid containing a
constant ratio of water to chloride ion. In the solution of CH3OH + 0.01 N
HCl the water content is too small to allow formation of a passive film.
In the solution containing 0.1 A'^ HCl, enough water is present in the bulk to
passivate the surface. However, the passive film is not very stable and
therefore penetrated by chloride ions at a relatively low potential. In
University of Washington (University of Washington) pursuant to License Agreement. No further repr
FIG. 16—Pitting on aluminum 6061 after anodic polarization in O.I ti HiSOt in CHzOH,
argon stirred; magnification approximately X45.
CH3OH + 1 N HCl, enough water is present to protect the surface from

pitting up to rather noble values. The film becomes more and more stable
when the electrode is polarized slowly in the noble direction.
Experiments on titanium in 0.1 iV H2SO4 in CH3OH (Fig. 8) show that
water also has a passivating effect in these solutions. It cannot be decided
unambiguously whether the small region of passivity observed in 0.1 N
H2SO4 in CH3OH containing about 0.04 percent H2O results from adsorp-
tion of the oxygen from the sulfate or from the water. By analogy with
the results obtained in HCI-CH3OH solutions and because of the large
efi"ect of the addition of 1 percent H2O on passivity, it seems logical that
the initial step in the passivation reaction on titanium is
Ti + H2O -^ Ti-Oad9 + 2H+ + 2e- (1)
where Ti-Oads represents oxygen absorbed on titanium.
+0.8 T| 1 1—I I I I ll| -I 1—I I I I III r- I I I i|| 1 1 I I I I II
Fe
CH3OH + O.IN HgSO^ + X% HjO
0.6 I I—J I Mini I — I — 1 — 1 i iiil I—I I I I I III LUlL _I L I I I I II
10 10 lo-" 10 10
i (yA/cm )
FIG. 17—Potentiostatic polarization curves for iron in solutions of 0.2 N H^SOt + x per-
cent H2O (x = 0,1, or 10) in CHiOH.
+1.0 "1 I I I I I Ml 1 1—I I I I I I I 1 1—I' I I I I I I T 1—I I IIII

I I II II 11 1 1—I I I I I I
Cu
+0.8
CH3OH + O.IN H2S0^
+0.4
-0.4 -J I I I I III I I I I I 11II I I I I M i l l ! I I I I I I III
10 „4 ,,5
10^ 10 10 10"
i(yA/cm^)
FIG. 18—Potentiostatic polarization curve for copper in 0.1 N H^SOi in CHzOH, deaer-
ated.
I I 1 1 1 1 1 1 111{ 1 1 1 1 1 M 1 1 1 1 1 M 1 l{ 1 I 1 1 1 f 11
+ Z.0 '
Pt
+1.6 CHjOH + O.IN H2S0^
+1.2 -
+0.8 - -
+0.4 - -
0 ^ —
- . b_= 0.045V -
-0.4 - ^^^^^
-
.n H 1 I 1 1 1111 1111 1 1 1 1 1 1 1 1 1 1 1 1 J 1 i l l 1 J 1 1 1 i 11
10 1.0 10 10 10 10
i(yA/cm^)
FIG. 19—Potentiostatic polarization curves for platinum in 0.1 N H^SOi in CH3OH,

argon stirred.
The results obtained for nickel (Figs. 10 and 11) support the assumption
that water is responsible for passivation. For stainless steel Type 304 it was
found in the present study (Fig. 13) that very small amounts of water
(about 0.04 percent) are sufficient for passivation. For iron, on the other
hand, no passivation could be observed even with water additions of up to
10 percent (Fig. 17). Additions of water in fact increased the anodic dis-
solution current in the potential range studied. A similar behavior was
found by Kiss et al [72] for iron in acetic acid containing 0.5 M sodium
acetate (HCaCOONa) or 0.5 M HCIO4. Additions of water in each case
accelerated the rate of active dissolution. The authors concluded that in
sodium acetate solutions passivation occurs only in the presence of water,
while in solutions containing perchloric acid passivation occurred only in
the absence of water. These results show that many factors determine the
ability of a metal to passivate. These may include the electronic structure
[13,14], the relative affinity to oxygen,^ and the characteristics of ion pairs
formed in solution [12].
When the results for nickel and iron are compared, it becomes evident
that water molecules also have a different effect on the region of active
dissolution of these metals. While the rate of the anodic dissolution re-
action is not affected by water in the case of nickel (Fig. 10), it increases
with increasing water content in the case of iron (Fig. 17). An increase in
' Evans, U. R., private communication.
FIG. 20—Potentiostatic polarization curves for tilanum 75A in CH3OH containing

HClOi, HCl, HiSOi HNO3, or HiPOt.
the acid concentration apparently increases the rate of anodic dissolution

of nickel and the critical current density for passivation (Fig. 11). In the
passive region, the passivating effect of the higher water concentration is
stronger than the activating effect of the higher acid concentration in
2 N H2SO4 in CH3OH.
Pitting Produced by Sulfate Ions—It has been observed in this investiga-
tion that all metals which undergo passivation also suffer from localized
attack in the form of pitting. This is a very surprising result since pitting is
usually observed only in the presence of halides, especially chloride ions.
Anions like sulfates, nitrates, perchlorates, and chromates have been
shown to inhibit pitting of iron [1], 18Cr-8Ni stainless steel [2], and alumi-
num [3] in aqueous solutions containing halides. Tousek [15] recently
pointed out, however, that there is no apparent reason why some of these
anions should not lead to pitting. It was shown [75], that under certain
conditions pitting can be produced by sulfates on iron and nickel in aqueous
acid solutions containing both sulfate and chloride ions. Tousek also
mentions briefly that "some sort of pitting corrosion" by sulfate ions
occurs in a solution of 2 A^ H2SO4 and 2 percent H2O in CH3OH resulting
in a polarization curve which is similar to that shown in Fig. 8.
MANSFELD ON PIHING CAUSED BY CHLORIDES OR SULFATES 201
o
z
I
J
^
^
t
1
^^)
Since pitting on nickel and stainless steel is observed at potentials where

methanol decomposition occurs (0 > 1.0 V) as shown on platinum (Fig.
19), it cannot be concluded solely from the increase of the anodic current
that localized attack has occurred. Microscopic observation (Figs. 12 and
14) has confirmed, however, that pitting occurred in both cases. The possi-
bility of reaction between oxidation products of methanol (HCHO,
HCOOH) and the passive film has not yet been studied.
It is quite remarkable that titanium, which is so resistant to pitting in
aqueous solutions containing halides, is more susceptible to pitting than
aluminum 6061, nickel, and stainless steel in H2SO4-CH3OH. The degree
of susceptibility of titanium is similar in H2SO4-CH3OH and HCI-CH3OH.
Although this author does not believe that SCC results from a pitting-type
attack, there is a striking resemblance in the susceptibility of titanium to
pitting and SCC in these solvent systems. This behavior suggests that the
nature of the passive film and its rate of formation is diff'erent in aqueous
solutions (sodium chloride) (NaCl) and methanolic solutions containing
small amounts of water. Recent results by Smith and Mansfeld [16] have
shown however, no differences of film properties in the two media as
measured by ellipsometry.
Acknowledgments
The author thanks D. H. Hern and J. V. Kenkel for help in carrying
out many of the experiments.
References
[/] Matsuda, S. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 111, 1964,
p. 156.
[2] Uhlig, H. H. and Oilman, J. R., Zeilschrift furPhysilcalische Chemie, Vol. 226, 1964,
p. 127.
[3] Bohni, H. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 116, 1969,
p. 906.
[4] Mori, K., Takamura, A., and Shimose, T., Corrosion, Vol. 22, 1969, p. 29.
[5] Mansfeld, F., Journal of the Electrochemical Society, Vol. 118, 1971, p. 1412.
[6] Mansfeld, F., Journal of the Electrochemical Society, Vol. 120, 1973, p. 188.
[7] Mansfeld, F. and Kenkel, J. V., to be published.
[8] Tsinman, A. I., Kuzub, V. S., and Katrevich, A. N., Soviet Electrochemistry, Vol. 2,
1966, p. 513.
[9] Leckie, H. P. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 113, 1966,
p. 1262.
[10] Armstrong, R. D., Harrison, J. A., Thirsk, H. R., and Whitfield, R., Journal of the
Electrochemical Society, Vol. 117, 1970, p. 1003.
[77] Stolica, N. D., Proceedings, 5th International Congress on Metallic Corrosion, Tokyo,
May 1972, p. 318.
[72] Kiss, L., DoNgoc, L., and Varsanyi, M. L., Collection of Czechoslovak Chemical
Communications, Vol. 36, 1971, p. 914.
[13] Uhlig, H. H., Zeitschrift fiir Elektrochemie, Vol. 62, 1958, p. 626.
[14] Mansfeld, F. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 117, 1970,
p. 427.
[IS] Tou5ek, T., Corrosion Science, Vol. 12, 1972, p. 15.
[76] Smith, T. and Mansfeld, F., Journal of the Electrochemical Society, Vol. 119, 1972,
p. 663.
L. C. Rowe1
Measurement and Evaluation of Pitting

Corrosion
REFERENCE: Rowe, L. C , "Measurement and Evaluation of Pitting Corrosion,"

Galvanic and Pitting Corrosion—Field and Laboratory Studies, ASTM STP 576,
ABSTRACT: Pitting is a destructive form of localized corrosion that requires
careful analysis and evaluation. Metal surfaces are examined first to identify and
determine the extent of pitting, which may be described in terms of standard
charts. Nondestructive tests may be used, but they have limitations. Pit depths
provide more meaningful information and can be determined by microscopic
measurement, depth gages, and other techniques. Statistical methods can be used
to show the probability of pitting to estimate maximum pit depths or to show the
relationship with time. The change in mechanical properties may also provide
useful information.
KEY WORDS: pits, pitting, corrosion, pitting evaluation, pit depth measure-
ment, microscopic pit-depth measurement, nondestructive tests, pitting proba-
bility, statistics
Pitting is a form of localized corrosion that affects only small portions

of a metal surface but causes a rapid change in metal thickness at these
areas because of the accelerated corrosion rate within the cavities that are
formed. Pits can produce early service failure because they may provide
sites for crack initiation, may decrease the mechanical strength of a
material, or may penetrate the metal wall and allow leakage of a contained
gas or liquid. Thus, it is important to be able to determine the extent of
pitting, either in a service application where it is necessary to predict the
remaining life in a metal structure or in laboratory test programs that are
used to select the most pitting resistant materials for service.
A number of different techniques have been used to measure and evaluate
pitting corrosion. A recommended practice on this subject was prepared
by a task group under ASTM Subcommittee GO 1.05 on Laboratory
Corrosion Tests and was the basis for this review. (Much of the supple-
1
Supervisory research chemist, Physical Chemistry Department, General Motors
Research Laboratories, Warren, Mich. 48090.
203

University of Washington (University of Washington) pursuant to Lice
mentary information from this review was used in a subsequent revision

of the recommended practice to improve and to expand its content.)
Identification and Examination of Pits

Visual Methods
The initial examination of a corroded metal surface can provide useful
information and should receive careful attention. The surface is examined
visually under ordinary Hght, with or without the use of a low power
magnifying glass. It is often advisable to photograph the corroded surface
so that it may be compared with the clean surface after removal of corrosion
products. If there is some doubt about the cause of pitting or the environ-
mental exposure conditions, the corrosion products should be removed
carefully following a recommended procedure, such as the National
Association of Corrosion Engineers (NACE) Recommended Practice on
Collection and Identification of Corrosion Products (RP-01-73). In some
cases an analysis of pit sites before cleaning can be helpful in identifying
the cause of pitting. An example of this is shown in Fig. 1 where the electron
microprobe analysis of an aluminum surface shows a direct association
between a pit site and the presence of a high concentration of iron particles.
After the preliminary examination has been completed and sufficient
corrosion products have been reserved for analysis, the remaining corrosion
products should be removed by proper cleaning procedures, such as those
given in ASTM Recommended Practice for Preparing, Cleaning, and
Evaluating Corrosion Test Specimens (G 1-72).
i^*fe-i5-''«-
0.001"
FIG. 1—Electron microprobe analysis of a pit in aluminum. The high concentration of iron
at the pit site is shown by light areas in the photograph on the right.
ROWE ON MEASUREMENT AND EVALUATION 205
The approximate size and distribution of pits are determined by visual

examination, followed by a more critical and detailed examination through
a microscope to determine the exact size, shape, and density of pits. The
true shape and depth of a pit are not always evident from an examination
of the surface because the pit cavity may have enlarged in a lateral direction
beneath the surface (Fig. 2). If this should be the case, it is necessary to
make a cross section of the specimen through the pit to determine its true
shape and depth.
It is a tedious and time-consuming job to determine pit density, but the
use of a plastic grid will be of some help. The grid, containing 3 to 6-mm
(3/8 to M-in.) squares, is placed on the metal surface. By counting and
recording the pits in each square, one can readily determine a density. In
addition, eye strain is minimized when this procedure is used because the
eyes can be taken from the field of view without fear of relocating the area
of interest.
If the relationship between pitting and microstructure is of interest, a
portion of the specimen must be mounted metallographically and etched
according to recommended procedures, such as those provided in ASTM
Preparation of Metallographic Specimens (E 3-62). The etched specimen is
FIG. 2—Cross section of a pit in aluminum showing the undercutting beneath the metal
surface. The size and depth of the pit would not be evident from the surface, X 200.
examined through the microscope to show the relationship between pits

and microstructure.
Nondestructive Methods
There are a number of techniques that have been developed to assist in
the detection of cracks or cavities in a metal surface without destroying the
product [7]. 2 These nondestructive methods are less useful than the visual
methods previously discussed for the identification and evaluation of pits,
but they merit attention because they can often be used in situ.
Radiographic—Radiation, such as X-rays, are passed through the object.
The intensity of the emergent rays varies with the thickness of the material.
Imperfections may be detected if they cause a change in the absorption of
X-rays. Detectors or films are used to provide an image of interior imper-
fections. The technique is used for both ferrous and nonferrous castings.
The metal thickness that can be inspected is dependent on the available
energy output. Pores or pits must be at least as large as one-half percent
of the metal thickness to be detected. The technique has only slight appli-
cation to pitting evaluation, but it might be a useful means to compare
specimens before and after corrosion to determine whether pitting has
occurred and whether it is associated with previous porosity.
Electromagnetic—Eddy currents can be used to detect defects or irregu-
larities in the structure of electrically conducting materials. When a speci-
men is exposed to a varying magnetic field, produced by connecting an
alternating current to a coil, eddy currents are induced in the specimen;
and they, in turn, produce a magnetic field of their own. Materials with
defects will produce a magnetic field that is different from that of a ref-
erence material without defects; differences can be determined by the
use of an appropriate detection instrument.
Another approach is the induction of a magnetic field in ferromagnetic
materials. Discontinuities that are transverse to the direction of the mag-
netic field cause a leakage field to form above the surface of the part.
Ferromagnetic particles are placed on the surface to detect the leakage
field and to outline the size and shape of the discontinuities. Rather small
imperfections can be detected in these materials by this method. However,
the method has some limitations: the required directionality of defects to
the magnetic field, the possible need for demagnitization of the material,
and the limited shape of parts that can be examined.
Sonics—One approach is based on the use of ultrasonics. Pulses of sound
energy are transmitted through a couplant, such as oil or water, onto the
metal surface where waves are generated. The reflected echoes are con-
verted to electrical signals that can be interpreted to show the location of
flaws or pits. Both contact and immersion methods are used. The test has
* The italic numbers in brackets refer to the hst of references appended to this paper.
good sensitivity and provides instantaneous information about the size

and location of flaws. However, reference standards are required for
comparison, and training is needed to properly interpret results.
In another method, acoustic emissions are used to detect flaws in metals.
Imperfections, such as pits, generate high-frequency emissions under
thermal or mechanical stress. The frequency of emission and the number
of occurrences per unit time determine the presence of defects.
Penetrants—Defects opening to the surface can be detected by the appli-
cation of a penetrating liquid that subsequently exudes from the surface
after the excess penetrant has been removed. Defects are located by spray-
ing the surface with a developer that reacts with a dye in the penetrant, or
the penetrant may contain a fluorescent material that is viewed under black
light. The size of the defect is shown by the intensity of the color and the
rate of bleedout. This technique provides only an approximation of the
depth and size of pits.
None of these nondestructive tests provide satisfactory detailed informa-
tion about pitting. They may locate pits and ofi"er some information about
their size. But they generally are not able to distinguish small pits, and
there can be confusion between the identification of pits and other surface
blemishes. When more detailed information is required, it is necessary to
use other methods of measurement.
Determination of the Extent of Pitting
Weight Loss
Metal weight loss is not very satisfactory as a measure of the extent of
pitting unless the overall corrosion is small, and even in this case it provides
no information about variations in depth of pitting. When uniform corro-
sion is significant, the contribution from pitting to the total weight loss is
too small to provide meaningful information. However, there are several
other methods that can be used to provide more precise pitting measure-
ments, and weight loss data may aid in assessing the results from these
measurements.
Pit Depth Measurements

Metallographic—The specimen is sectioned vertically through a pre-
selected pit, and the cut surface is mounted metallographically and polished.
The depth of the pit is measured by the use of a microscope with a cali-
brated eyepiece. A typical pit is shown in Fig. 3, and the depth can be seen
to be 0.006 in. (0.152) mm). This method has several disadvantages:
(a) it is time consuming, {b) it offers no assurance that the deepest pit has
been selected, and (c) it is difliicult to section the pit at the deepest point of
penetration.
FIG. 3-—Cross section of a pit showing how a microscope with a micrometer reticle may
be used to measure pit depth; one scale division = 0.0005 in. (IS fim), XIOO.
Machining—This method requires a specimen that is somewhat regular

in shape, and it involves the destruction of the specimen [2,3]. An un-
affected portion of the metal is selected to measure the original thickness.
One side of the specimen is machined with a lathe until the last trace of a
pit has disappeared. The thickness between the machined surface and an
unaffected portion on the opposite side is measured and subtracted from
the original thickness to give the depth of the deepest pit. The procedure is
repeated on the unmachined side.
This procedure can also be used to determine the number of pits that
reach specific depths. The surface is machined away in measured stages,
and the visible pits are counted at each stage. The difference between the
number of pits at any stage and the number at the previous stage gives the
number of pits at each depth of cut.
Micrometer or Depth Gage—A pointed needle is attached to a micrometer
or calibrated depth gage. The instrument is zeroed in on an unaffected area
at the lip of the pit. The needle is inserted in the pit until it reaches the
base where a new measurement is taken. The distance traveled by the
needle is the depth of the pit. It is best to use a spring tension instrument to
avoid excessive penetration of the metal by the needle. This method is only
applicable to pits that are wide enough to allow the needle to penetrate the
pit without obstruction.
In a variation of this method, the probe is attached to a spherometer and
connected through a micrometer and battery to the specimen [3,4]. When
the probe touches the bottom of the pit, the circuit is completed, and the
depth of probe movement is a measure of pit depth. This method is Hmited
to very regularly shaped pits because any contact with the side of the pit
would give a false reading.
Microscopic—This method is valuable when pit openings are too narrow
to allow penetration with a probe. However, it can only be used when the
microscope can be focused on the base of the pit; this eliminates pits where
undercutting has occurred.
A microscope with a magnification range in the order of 50 to 500 and a
calibrated fine focusing knob (for example, 1 division = 0.001 mm) is
required for this method. The pit is centered under the objective lens at low
magnification, which is increased until the pit area, including the lip, fills
most of the field of vision. The microscope is focused first on the lip of the
pit and then on the base of the pit. The difference in the two recorded read-
ings from the fine focusing knob is the depth of the pit. Repeatability of
measurements improves with increasing magnification, as shown in Table 1.
The method is limited to the depth of pits that are within the range of
movement of the fine focusing knob on the microscope. This method is
time consuming and fatiguing, particularly if many pits have to be meas-
ured. If specific pits are to be measured, it is often necessary to mark them
with a stain before attempting to locate them under the microscope.
In a variation of this technique, the interference microscope is used [5].
In this method a beam of light is split so that one portion of the light is
projected on the specimen and the other on a reference mirror surface.
When the reflected light from the two surfaces is recombined, interference
fringes are formed that provide a topographical map of the specimen
surface. The fringes provide a measure of the vertical deviations on the
metal surface.
Evaluation of Pitting Corrosion
Standard Charts
Some procedure is often needed to quantitatively describe or classify the
extent of pitting. One such procedure is to rate the pits in terms of their
density, size, and depth on the basis of standard charts, such as those used
by Champion [3] and shown in a modified form in Fig. 4. Columns A and B
relate to the extent of pitting at the surface of the metal (that is. Column A
is a means for rating the number of sites per unit area, and Column B is a
means for showing the average size of these sites). Column C rates the
intensity or average depth of attack. A typical rating might be A-3, B-2,
TABLE 1—Microscopic pit depth measurement of pit in Fig. 3.
Pit
Magnification Depth, mm
65 0.183
0.159
0.179
0.174avg
132 0.159
0.160
0.155
0.159
0.159 avg
200 0.149
0.157
0.150
0.153
0.152 avg
370 0.151
0.151
0.151
0.152
0.151 avg
C-3, representing a density of 500 pits/dm^ an average pit opening of

2.0 mm^, and an average pit depth of 1.6 mm. This system offers a means
of communication between those who are famiUar with the standard
charts, and it is a simple method for storing data for comparison with
other test results. However, it does not show the full impact of pitting be-
cause it is concerned with averages. The determination of the average pit
depth is not highly recommended because of the time involved in making
measurements and the difficulty associated with measuring the depths of
all pits.
Metal Penetration
The depths of the deepest pits are usually more significant than the
average depth of all pits, particularly if a hole through the wall of a metal
enclosure for a gas or liquid could lead to a loss of fluid. Therefore, metal
penetration is often expressed in terms of the maximum pit depth or the
average depth of several of the deepest pits. It is often advisable to use both
methods because the maximum pit depth may indicate a greater severity of
pitting than that shown by other pitting.
ROWE ON MEASUREMENT AND EVALUATION 21 1
A B C
DENSITY SIZE DEPTH
25/dm
2.0 mm 0 . 8 mrr
SOO/dm^
lOOO/dm^
5000/dm2 24.5mm' 6.4mm
FIG. 4—Charts for rating pits according to their density, size, and depth.
Metal penetration may also be expressed in terms of a pitting factor. This

is the ratio of the deepest metal penetration to -the average metal penetra-
tion, determined from weight loss, as shown in the following relationship.
deepest metal penetration
pitting factor =
average metal penetration
A pitting factor of one represents uniform corrosion; the larger the number,
the greater is the depth of penetration.
Statistical
Pitting is usually divided into two stages, initiation and propagation.
Many pits are stifled after initiation and fail to propagate, while others
continue to propagate to varying depths. A pitting probability test can be
conducted to determine the susceptibility of metals to pitting, but it will
not provide information about the rate at which pits propagate. The
pitting probability {P) after the exposure of a number of specimens to a
particular set of conditions can be expressed in percent as follows (taken

from Ref 6)
p = 4 r X 100
N
where
Np = number of specimens that pit, and
N = total number of specimens.
The pitting probability for a metal will vary with conditions of exposure,
such as the corrosivity of the environment, the specimen area, and the
length of exposure.
Aziz and Godard [7] demonstrated the importance of specimen area on
the determination of aluminum pitting probability. In their experiment,
large aluminum specimens were subdivided with wax into various rectangu-
lar areas. A drop of test solution was placed in each subdivision, which was
kept wet by exposure to 100 percent relative humidity. The subdivisions
showing any evidence of pitting were counted at the end of the test. The
results showed that the probability of pitting increased with the area of
metal exposed, and the probability of finding only one pit per subdivision
was a maximum for an area of one square centimetre.
Several methods have been developed to show the relationship between
pit depth and area or time of exposure. For example, Scott and others
[8-10] found the following relationship between the maximum pit depth (d)
and area (A) of a pipeline exposed to soil.
d = bA"
In the equation a and b are constants that are obtained from the slope and
the y-intercept of a straight line curve obtained by plotting the logarithms
of the mean pit depths for successively increasing areas against the loga-
rithms of the corresponding areas.
Godard [6,11] found that the maximum pit depth of aluminum exposed
to various waters was a function of the tube root of time as expressed by
the following relationship
d = Kt'"
where
d = maximum pit depth,
t = time, and
A" = a constant that is a function of the composition of the water and
alloy.
It was found that this relationship applied to several aluminum alloys
exposed to different waters. One example is the pitting rate of 5052 alumi-
num alloy pipeline in Arvida, Quebec. When the maximum pit depths were
plotted against the cube root of time, Pathak [6] found a straight line rela-
tionship, as shown in Fig. 5.
Summerson et al [12] used a statistical approach to analyze pit depth
measurements on aluminum. By plotting the square root of the pit depth
against frequency, a reasonable normal distribution was obtained. From
these curves, the mean square root of the pit depth, the standard deviation,
and the probability error could be determined. This approach required the
measurement of many pits. But once it was established that a normal
frequency distribution was a function of the square root of the pit depth,
a sampling procedure could be developed that would allow the measure-
ment of a smaller number of randomly selected pits to give a predetermined
confidence level.
Extreme value probability statistics have been applied successfully to
maximum pit depth data to estimate the maximum pit depth of a large
area of material after examination of a small portion of that area [3,6,11].
Gumbel [13] is given credit for the original development of this method,
but Aziz [14] simplified its use by plotting data on extreme value proba-
bility paper.
The procedure is to measure maximum pit depths on several replicate
specimens that have pitted, and then arrange the pit depth values in order
of increasing rank. A plotting position for each order of ranking is neces-
sary, and this is obtained by substituting in the relationship
M/(n + 1)
where
M = order of ranking, and
« = total number of specimens or values.
I 4 8 12 1« 24 40 60
TIME,years (cube root)
FIG. 5—Pitting rate curve for 5052 aluminum alloy pipeline showing the relationship
between maximum pit depths and the cube root of time (taken from Ref6).
For example, the plotting position for the second value out of 10 would be
2/(10 + I) = 0.1818. These values are plotted on the ordinate of extreme
value probability paper versus their respective maximum pit depths. If a
straight line is obtained, it shows that extreme value statistics apply.
Extrapolation of the straight line can be used to determine the probability
that a specific depth will occur or the number of observations that must be
made to find a particular pit depth.
Figure 6 shows an example of how this approach was used by Pathak [6]
to estimate the maximum pit depth of a 610-m (2000-ft) pipeline by the
measurement of maximum pit depths on a segment of the line. The 13-year
data are based on the determination of maximum pit depths for an 18-m
(60-ft) length of pipe divided into 1-m (3-ft) sections. A smaller segment of
the same pipeline was used for the 22-year data. By extrapolation of the lines
to the point on the return period of the graph representing the entire length
of the pipeline [666 for (A) and 1000 for (fi)], the estimated maximum pit
depth was 90 mils after 13 years and 99 mils after 22 years.
Loss in Mechanical Properties

The mechanical properties of a material may change because of pitting
corrosion, and the amount of change may be used as a means for evaluating
the degree of pitting. Typical properties that are often considered for this
.Ml 99 1000
•
90/ A
SCO
.M8 400
• ••7- / / - aoo
.••S _ / aoo
.**» . 100
.•>0
/ O
J;.»M . . so O
3.»70 QC
V 7 lU
m.»So . •/ / _ 20 a.
<.»»0
".too , 10 Z
O
/ ; - s 3
0£ / / - « 1—
cL.toe
/ /* 4 LU
QC
.TOO
A - 3
.seo „
/• /
.100 ^ /*
/A
.100 A/ 1.1
• 050
.010
: /
- / . • 1.0
50
MAX. PIT DEPTH. mi Is
FIG. 6—Straight line curves obtained when maximum pit depths from 5052 alloy pipeline
are plotted on extreme probability paper. Curve A is based on data from the subdivision of
an 18-m (60-ft) section after 13 years; Curve B is based on a 6-m (20-ft) section after 22 years
(taken from Ref6).
University of Washington (University of Washington) pursuant to License Agreement. No further reproduct
ROWE ON MEASUREMENT AND EVALUATION 21 5
purpose are tensile strength, elongation, fatigue strength, impact resistance,

and burst pressure. The use of this method is often more suitable for other
forms of localized corrosion, and it has had particular application to
intergranular or stress corrosion. Summerson [72] found that the measure-
ment of changes in tensile strength and elongation were not satisfactory for
aluminum because the changes due to pitting were usually small. So this
must be considered if these techniques are to be used.
The precautions that must be taken in the use of these procedures are
well defined in most standard methods and need no further discussion here.
What must be stressed is the importance of using as nearly replicate speci-
mens as possible for both the exposed and unexposed specimens. This
means consideration should be given to edge effects, direction of rolling,
surface conditions, etc. Representative specimens of the metal are exposed
to the same conditions except the corrosive environments. The mechanical
property of the exposed and unexposed specimens is measured after the
exposure, and the difference between the two results is because of corrosion.
It may be difficult to separate the effects due to pitting and those from other
forms of localized corrosion, but this must be determined by the investigator.
Baboian [75] measured the burst pressure of metal tubes to determine
whether a subsurface layer of stainless steel would decrease the depth of
pitting through terne-coated steel. This was a reasonable approach because
burst strength is dependent on metal thickness, and a reduction in thickness
at even a small area will affect pressure retention. The change in burst
strength was determined with time on successive specimens exposed to salt
spray, and it was found that the stainless steel caused a reduction in the
depth of pitting.
Summary
1. Metal surfaces are examined visually and under low magnification to

identify pits and to determine their number.
2. Nondestructive methods can be used to locate pits, although other
metal defects may interfere. There is a limit to the size of pit that can be
detected.
3. Metal weight loss alone is not a satisfactory procedure for the deter-
mination of the extent of pitting.
4. Pit depths can be determined by the following techniques: (a) micro-
scopic measurement of a cross-sectioned pit that has been mounted metallo-
graphically, (b) determination of the difference in metal thickness before
and after machining a specimen to the bottom of a pit, and (c) measurement
of a pit depth by the use of a micrometer, pit depth gage, or a microscope
that has a graduated focusing knob.
5. Standard charts can be used to describe the degree of pitting in
terms of density, size, and depth of pits.
6. The measurement of the maximum pit depth or the average of a num-

ber of the deepest pits is often a more meaningful way to show the extent
of pitting.
7. Statistical methods can be used to show the probability of pitting
occurring, to show the relationship between pit depth and time of exposure,
and to estimate the maximum pit depth on the basis of an examination of
a portion of the exposed metal surface.
8. The change in a particular mechanical property of a metal can be used
to show the effect of pitting under some conditions, but this approach is
often more applicable to other forms of localized corrosion.
Acknowledgments
The author is indebted to R. L. Chance and M. S. Walker for their
helpful suggestions during the preparation of this paper.
References
[/] Mock, J. A., Materials Engineering, Vol. 69, June 1969, p. 60.
[2] Bengough, G. D. and Wormwell, F., Journal of the Iron and Steel Institute, Vol. 3,
1935, p. 168.
[i] Champion, F. A. in Corrosion Testing Procedures, 2nd ed., Wiley, New York, 1965.
p. 205.
[^] Thornhill, R. S., Journal of the Iron and Steel Institute, Vol. 146, 1942, p. 90P.
[5] Saur, R. L., Plating, Vol. 52, July 1965, p. 663.
[6] Pathak, B. R. in Handbook on Corrosion Testing and Evaluation, W. H. Ailor, Ed.,
Wiley, New York, 1971, p. 553.
[7] Aziz, P. M. and Godard, H. P., Journal of the Electrochemical Society, Vol. 102,
Oct. 1955, p. 577.
[8] Scott, G. N., Proceedings, American Petroleum Institute, Vol. 14, 1934, p. 204.
[9] Romanoff, M., "Underground Corrosion," Circular 579, National Bureau of Standards,
U. S. Government Printing Office, Washington, D. C , 1957, p. 71.
[/O] Denison, I. A. in Corrosion Handbook, H. H. Uhlig, Ed., Wiley, New York, 1948,
p. 1048.
[//] Godard, H. P., Canadian Journal of Chemical Engineering, Vol. 38, Oct. 1960, p. 1671.
{l2\ Summerson, T. J., Pryor, M. J., Keir, D. S., and Hogan, R. J. in Metals, ASTM STP
196, American Society for Testing and Materials, 1957, p. 157.
{13\ Gumbel, E. J., "Statistical Theory of Extreme Values and Some Practical Applica-
tions," Series 33, U. S. Department of Commerce Applied Mathematics, Washington,
D. C , 1954.
[14] Aziz, P. M., Corrosion, Vol. 12, Oct. 1956, p. 495t.
[is\ Baboian, R., "Corrosion-Resistant, High-Strength Clad Metal System for Hydraulic
Brake Line Tubing," Preprint 720290, Society of Automotive Engineers, Detroit,
Mich., 1972.
D. L. Crews1
Interpretation of Pitting Corrosion Data from

Statistical Prediction Interval Calculations
REFERENCE: Crews, D. L., "Interpretation of Pitting Corrosion Data from

Statistical Prediction Interval Calculations," Galvanic and Pitting Corrosion—Field
and Laboratory Studies, ASTM STP 576, American Society for Testing and
Materials, 1976, pp. 217-230.
ABSTRACT: The National Bureau of Standards data for pitting corrosion of

ductile iron and steel pipe in four soils and gray cast iron and 3-in. Bessemer steel
pipe in one soil have been treated by statistical methods to obtain the prediction
intervals of estimated pit depths as a function of time. In the nonaggressive soils
which are representative of most pipe installations, these ductile iron and gray
iron pipe exhibited less corrosion than the companion steel pipe.
Prediction interval calculations are useful for quantitative analysis of corrosion
data which has considerable inherent scatter and where service life is determined
by the failure at relatively few points.
KEY WORDS: corrosion, pitting, statistical analysis, nodular iron, gray iron,
steels
Corrosive attack on buried ferrous materials is characterized by pitting;

total attack, as measured by weight loss, may be moderate in specimens in
which severe pitting has developed.
In underground pipes conveying liquids or gases, the termination of
service life by corrosive attack is characterized by pits which have perforated
the pipe wall. At the time of failure, the overall decrease in bursting strength
or loss in weight may be minimal. It is obvious then that the evaluation of
corrosive attack or determination of service life under such circumstances
must be based on measurements of pit depth.
In representative conditions of actual service, corrosion proceeds quite
slowly; service life usually exceeds the professional life span of an indi-
vidual observer. Accelerated tests which utilize highly corrosive environ-
ments or aggressive soils are of questionable validity. Extrapolation of pit
depth measurements therefore becomes an essential part of an evaluation
1
Research consultant, Clow Corporation, Coshocton, Ohio 43812.
217

of pipe materials or environments or both which seeks to represent actual

service conditions.
The method of statistical treatment of the data should be carefully
ch\)sen to avoid errors in interpretation. A method which provides a calcu-
lation of the distribution of pit depths for extrapolated periods of ex-
posure, rather than an average pit depth, includes the element of proba-
bility.
The technique of measuring pitting attack consists of exhuming speci-
mens which have been buried in selected environments and measuring
the penetration of the pits into the metallic material. Since the products of
corrosion cannot escape, they accumulate on the exposed surface; hence,
it is necessary to completely clean the specimens before it is possible to
make measurements of pit depth. Obviously, a specimen which has been
measured cannot be returned to the environment for further exposure.
An adequate number of specimens must be buried initially, then a selected
number are exhumed at intervals of time.
It is a characteristic of underground pitting corrosion that a wide range
of pit depths exists at any moment in time. Any particular specimen of
practical size can contain only a small fraction of the total population of
all pits or even the deepest pits. It has been a practice in evaluating speci-
mens to measure only a selected number of the deepest pits, since such pits
eventually produce failure. This small sample size, compared to the popu-
lation, accounts for the observed result that the data from a series of pit
depth measurements over a period of time exhibit considerable dispersion
and apparent anomalies; some increments of time result in a decrease in
the measure pit depth.
Due to this statistical scatter, interpretation of pitting corrosion is
difficult. Most commonly, the position of different materials or environ-
ments are merely placed in rank; no quantitative interpretation of the data
is attempted, either as to relative attack at any point in time or a projection
of expected service life.
Data Treated
The most extensive tests of underground corrosion have been conducted

by the National Bureau of Standards (NBS).^ These tests were initiated in
1922; the most recently reported data are those of ductile iron pipe and
carbon steel pipe, which had completed 8 years exposure in 1966.^ The
maximum exposure in the earlier NBS tests is reported as 18 years. By
comparison, the service life of cast iron pipe is expected to be in excess of
2 See National Bureau of Standards Circulars 450 and 579.

' Romanoff, Melvin, Journal of the American Water Works Association, Vol. 60, 1968,
pp. 645-655.
CREWS ON INTERPRETATION OF PITTING CORROSION DATA 219
100 years. The recent tests provided data for four exposure periods (1, 2, 4,
and 8 years); the earlier data provided, typically, six exposure periods. The
data of the recent series consist of the average of the deepest pits measured
on four 12-in.-long specimens; only 5 of the 6 test sites survived for 8
years; two of these 5 exhibited instances of perforation of the pipe wall,
so that some bias exists in the data. All of the published data of the NBS
tests identify the data as "an average of the maximum pit depths of four
specimens." Table 1 reproduces the data reported for the recent series of
tests.
Calculation of the regressions relationship between pit depth and time
can be made from a series of test values using the accepted exponential
equation and utilizing the logarithms of the variables to obtain a straight
line. However, a regression value is merely an estimate of the central
tendency; half of the population values are expected to fall below the
regression value and half above.
More relevant is an estimate of the distribution of the pits in the popula-
tion. The scatter of the measured data about the regression is an expression
of the width of the distribution band; the greater the deviation of the data
values from the regression relationship, the wider is the distribution band
of the population values.
The distribution of the population is termed, in statistical inference,
the prediction interval; this is in distinction to the confidence limits. Of the
total prediction interval, the deepest pits are the ones which are relevant
to estimates of longevity.
Manual statistical calculations are particularly laborious, which may be
the reason that they have been used so infrequently in the analysis of
pitting corrosion data, despite the demonstrable need. That difficulty has
been removed by the development of computers and prepared computer
programs which can make the required calculations with a feasible invest-
ment of time and effort. Compared to the effort required to produce the
original tests data, the effort of the calculation becomes minimal.
Prediction Intervals
The statistical treatment in this paper utilizes a prepared computer
program which provides calculated values of both the regression and the
distribution, expressed as prediction intervals, of pit depths for times both
within the exposure period of the test and extrapolated exposure times.
Specifically, the values were calculated for times of 4, 7, 10, 20, 40, 70, 100,
and 400 years. The data were entered as the logarithms of the experimental
values. Since the computer program provided the normal distribution, the
resulting distribution is log-normal. The extreme-value distribution is
believed to provide the most accurate representation of pit depth but the
log-normal distribution is similarly skewed and is judged by the writer to
It
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approximate the extreme-value distribution of the interval used for this

interpretation of the data and the estimate of service life.
As an illustration of the proposed statistical procedure, the prediction
interval was calculated for the NBS data of ductile iron and steel pipe
exposed concurrently in four test sites representing a range of corrosivity
from very mild to extremely aggressive soils (300 to 30 000 n/cm resistivity);
the prediction intervals chosen were 50, 80, 90, 95, and 99 percent. The
results of the calculation are shown in graphical form in Figs. 1 through 8,
with the omission of the 99 percent interval and, in the case of Figs. 7 and 8,
the omission of the lower Hmits, which are redundant for estimates of
service life. The regression hne is marked "0".
The interpretation of the prediction interval is that the indicated fraction
of the population pit depths lies between the limits shown. For example,
90 percent of the deepest pits lie between the upper and lower 90 percent
lines and 5 percent lie above the upper 90 percent prediction line.
The wall thickness of the specimens is also shown in these figures. As a
practical index of service life, whose magnitude corresponds in general
to actual experience, the upper 90 percent line was chosen for purposes of
interpretation. Figures 9 through 12 show the upper 90 percent line of the
two materials, carbon steel and ductile iron, for four soil environments.
T I M .TO T^;
po'
_5Q:
-.s3Sc
^ 0 -
~95~
5 e 7 8 10 IS 20
J
30
L
4 0 SOeb so ISO 150 200 30Q 400
cxPosunF, TiMi:, Y E A R S
FIG. 1—Ductile iron pipe, Site A; prediction intervals ofpit depth versus exposure time.
5 £7810 ra 20 ;3b 40 sb 60 so 100 150 zoo 300 400

EXPOSURE TIME, YEARS
FIG. 2—Steel pipe. Site A; prediction intervals of pit depth versus exposure time.
5 6 7 8 10 rs 20 30 40 50 60 SO l6o 150 200 300 400

FIG. 3—Ductile iron pipe. Site B; prediction intervals of pit depth versus exposure time.
"1 3 4 5 6 7 8 1 0 (6 20 30 40 S060 SO 100 i50 200 36o W

FIG. 4—Steel pipe. Site B; prediction intervals of pit depth versus exposure time.
FIG. 5—Ductile iron pipe, Site D; prediction intervals ofpit depth versus exposure time.
8 10 15 2 0 30 4 0 5 0 6 0 «0 100 ISO ZOO 300 400

FIG. 6—Steel pipe. Site D; prediction intervals of pit depth versus exposure time.
Z 5 4 5 6 if 8 10 tS 2 0 3 0 4 0 50 60 80 100 ISO 200 » 0 400

FIG. 7—Ductile iron pipe. Site G, prediction intervals (upper limit only) of pit depth versus
time.
CREWS ON INTERPRETATION OF PiniNG CORROSION DATA 225
1000 1 1 1 11 1 1 •• 1 _
eoo ^ ' ^^
/ / '
600 -
500 : / /
^ /
400 —
300
leo ^tiM-l— .
/ • / •
IOC y
80 —
60 -
40 -
30 — J
-
(5
• 1 1 1 1 1 1 1 1 1 1 , 1 1 1 1 1 1
2 10 tS 20 30 4 0 5060 80 100 150 ZOO JOO AC
s 4 ;> 6 7 6
FIG. 8—Steel pipe. Site G; prediction intervals (upper limit only) of pit depth versus time.
lOOOr
"567810 rs 2 0 30 4 0 50 60 00 100 ISOMO 300 '400

FIG. 9—Five percent of the deepest pits (the upper 90 percent prediction interval line) of
ductile iron and steel pipe. Site A.
226 GALVANIC AND PiniNO CORROSION
1000 _ i • 1 1 MM I \ /\ 1 11 1 I I _
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/
600 / ^ —
500 •4.
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-^ —
400 /
/ —
300 / . x*^"
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1 1
15 *0
,.|,
30
1 , 1 1 1 1
4 0 50 6 0 80 100
1 1
150 ZOO TOO 40
EXPOSURE TIME, yEARS
FIG. 10—Five percent of the deepest pits (the upper 90 percent prediction interval line) of
ductile iron steel pipe. Site B.
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50 —
4C-
30-
20
/5
IC _L I I M J_ J30 4L0 9 0^610 I SO

J. I O,
! > 6 7 8 10 15 2 0 100 150 200 300 400
FIG. 11—Five percent of the deepest pits (the upper 90 percent prediction interval line)
of ductile iron and steel pipe. Site D.
1000 _ 1 1 \ / Mil 1 1 1
1 1 II
eoo / -
600 —
500\
AQO—
300 /y i>'^
-
01
A leo \y -
1 100
I 80 -
-
60
4C —
30 —
/5
1 1 1 1 1 r 1 1 1 1 1 1 1 1 1 1
z 3 i, i 6 7 8 !0 fS 2 3 30 •" rO 9960 80 100 ISO zoo 300 401
FIG. 12—Five percent of the deepest pits {the upper 90 percent prediction interval line)
of ductile iron and steel pipe. Site G.
Estimation of Service Life
From these upper 90 percent lines, estimates of service life and rates of
corrosion can be made which have the same magnitude as service experience.
Numerical values are shown in Table 2, in which service life is expressed in
years for 5 percent of the deepest pits to perforate the pipe wall. Pitting
corrosion rate provides a comparison which eliminates the effect of the
differences in wall thickness of the two materials, ductile iron and steel
(0.25 in. for ductile iron pipe and 0.145 for steel pipe) and can be expressed
as exposure in years for 5 percent of the measured pits to be equal to or
greater than some specified depth; for this tabulation 0.25 and 0.50 in. were
chosen.
The absolute values of longevity and corrosion rate in some of the NBS
tests, as they relate to service conditions generally, may be open to question;
soils of 300 or 400 fi/cm do not represent realistic service conditions (in
practice, pipe in such soils, which are infrequently encountered, would be
provided with some type of external protection, such as coating or wrap-
ping). However, relative longevity may be useful since the materials which
were tested concurrently have experienced the same environmental circum-
stances. Soils A and G are examples of highly aggressive soils which might
TABLE 2—Estimated service life and pitting corrosion rate of carbon steel, ductile iron, and
gray cast iron in different soils.
Service Life Pitting Corrosion Rate
Years to 5 % Years to 5 %
Years to 5 % at 0.25 in. at 0.50 in.
Site Material Perforation Depth Depth
A, Sagemoor loam ductile 14 14 43

400 O/cm, 8.8 pH steel 21 74
B, Hagerstown loam ductile 52 52 300
5 200 a/cm, 5.8 pH steel 6 21
D, Lakewood sand ductile 2 500 2 500 10 000
30 000 fi/cm, 7.3 pH steel 7 14 33
G, Tidal, marsh ductile" 2y2 2V2 6H
300iJ/cm, 7.1 pH steel" 1 1.9 3M
11, Hagerstown loam gray cast iron
metal mold 1 000 350 2000
11 OOOn/cm, 5.3 pH Bessemer steel
3-in. pipe 26 37 140
" Biased data
be employed to provide accelerated testing but which do not actually

yield estimates of representative service life.
In Soil B, which may be considered representative of soils encountered
in normal practice, the relative status of ductile iron versus carbon steel
in these tests falls within a range of about 5 to 15 for rate of corrosion and
about 8 for longevity, ductile iron pipe being the more resistant to corrosion.
A major deficiency in the recent NBS series is the omission of gray iron
pipe, which has been the principal underground piping material for several
centuries. A comparison of the expected service life of ductile iron with
gray cast iron is of major practical importance; no direct comparison is
possible from NBS data, since concurrent testing of these two materials
was not conducted.
The NBS reports data in Hagerstown loam for gray cast iron produced
in a metal mold and Bessemer steel pipe (see footnote 2). The prediction
intervals for these two materials are shown graphically in Figs. 13 and 14
and the upper lines alone in Fig. 15. The ratio of the rates of corrosion, as
shown in Table 2, fall within a range of about 10 to 15, gray cast iron being
the more resistant.
Summary
The statistical treatment of pitting corrosion data which calculates the
prediction intervals of pit depth for exposure periods greater than the test
CREWS ON INTERPRETATION OF PiniNG CORROSION DATA 229
S67810 »S 20 30 40 50 60 80 100 156 iOd 306 4da

FIG. 13—Bessemer steel pipe (3-in. pipe). Site 11, prediction intervals of pit depth versus
time.
1000 1 1 1 1 1 1 1 1 1 1 MM 1 1 _
eoo
600 —
500
-WALL
•400
300 ^
^ ^
^^
300
-.^
3 180 , .--
-^
1 too
Q
^"^1
.---'^ „ _ - — "
60
50
4C • ^^
•
30 •
-
ft
20
;5
IC I--' 1 1 1 1 t 1 1 ~^^~-,-ê • ^ I - - L t 1 1 ~'

2 3 4 .7 6 7 8 10 15 20 30 40 50 6 0 SO r<)6 \ta a)0 300 40
FIG. 14—Gray cast iron pipe (metal molds). Site 11, prediction intervals of pit depth
versus time.
lOOOr- TTTT T "1 r I I I I

600- xi.
600-
500 —
<oc-
300-
c,< <P^
200
i leo
,%^-
100 •*£&
' ^
80
60-
50-
40-
30-
20
/5-
fO Z
JS L 5 6I 7I 8M 10
4 rS 20 30 40 5060
I I ' I
80 100 150 ZOO 300 400
EXPOSURE TIME, YEAI1S
FIG. 15—Five percent of the deepest pits (the upper 90 percent prediction interval line)
of gray cast iron and 3-in. Bessemer steel pipe. Site 11
periods is proposed as a means for obtaining quantitative estimates of

service life or corrosion rate in normally encountered environments;
adequate statistical interpretation has been notably absent in the past.
The examples of longevity which are contained herein are relevant to
commercially important underground piping materials.
D. B. Anderson1
Statistical Aspects of Crevice Corrosion in

Seawater
REFERENCE: Anderson, D. B., "Statistical Aspects of Crevice Corrosion in

Seawater," Galvanic and Pining Corrosion—Field and Laboratory Studies, ASTM
STP 576, American Society for Testing and Materials, 1976, pp. 231-242.
ABSTRACT: The natural variability in incidence and severity of oxygen concen-
tration cell crevice corrosion in seawater systems has been shown to follow pre-
scribed statistical patterns. These considerations have been used to develop a viable
multiple crevice test method for assessing comparative alloy capabilities and for
isolating specific geometrical and environmental effects. Test data developed by
this method have also provided interesting insight into the corrosion mechanisms
involved.
KEY WORDS: corrosion, concentration cell corrosion, pitting, seawater
corrosion, corrosion tests, stainless steels, nickel alloys
Crevice corrosion is generally recognized as the limiting corrosion

phenomenon in seawater systems determining serviceability of stainless
steels and a variety of other commonly used marine materials which
exhibit marked susceptibility to localized corrosion induced by either oxy-
gen or metal-ion concentration cells. Crevices can be built in from gaskets,
O-rings, lap seams, etc. or can develop in service from sediments, fouling,
etc.
Unfortunately, the severity of attack often defies prediction ranging
from no apparent attack to superficial etching to catastrophic failure.
The inherent variability in both occurrence and intensity of attack, plus the
frequency with which seawater crevice corrosion test data reflect the
particulars of the evaluation method, compound the problem of trying to
accurately assess the merits and capabilities of candidate materials for a
specific application without resorting to unduly complex evaluations.
Consistent trends indicative of comparative alloy capabilities (for
example, Type 316 stainless steel is generally considered more resistant to
1
Project manager, The International Nickel Company, Incorporated, New York, N. Y.
10004.
231

crevice corrosion than Type 304) can be derived from critical comparisons
of data from a variety of sources and from tests involving extended ex-
posures of a reasonable number of specimens and specimen configurations.
However, comparisons based on limited data or data developed for diff-
ferent alloys using different test methods are all too often inconclusive or
misleading.
Development of Statistical Test Method
Attempts to introduce a "standard" crevice capable of providing con-

sistent and reproducible data for seawater corrosion studies have been
notably unsuccessful. The variability observed suggests the potential
usefulness of a cumbersome statistical approach involving exposures of
large numbers of specimens with varying exposure periods. The use of a
reduced number of specimens, each exposed with a large number of
duplicate crevices, has been evaluated as a reasonable alternative.
Several criteria were considered of primary importance in the develop-
ment of a viable test method using the multiple crevice approach.
1. The required test period must be reasonably short, both to salve
researcher anxiety and to reduce conflicting interactions due to fouHng
attachments, seasonal temperature variations, etc.
2. The test method must be capable of clearly demonstrating recognized
diffêrences in alloy capabilities (that is, properly rank Types 304 and 316
stainless steel).
3. The test method must be capable of providing a clear assessment of
the merits of highly corrosion-resistant alloys for use in critical applications
requiring corrosion immunity.
4. The test method must be adaptable to specimens of various thick-
nesses, shapes, and surface conditions and not entail modification or
destruction of "as-received" surfaces.
5. The test should not require electrochemical stimulation or chemical
alteration of the environment.
The basic test method which evolved exposes flat panel specimens with
multiple crevices formed by two grooved acetal resin washers as shown in
Fig. 1. A 4 by 6 in. (10 by 15 cm) specimen size was selected out of con-
venience. Subsequent tests, described as follows, showed important effects
which can be studied by introducing specimen size as a controlled variable.
A typical grooved washer is shown in Fig. 2. Each washer has 20 grooves
and plateaus, providing 40 crevices per specimen. Grooves are typically
0.020 in. (0.5 mm) deep and 0.040 in. (1.0 mm) wide, but these dimensions
are not critical variables except to provide a minimum creviced/exposed
surface area ratio of at least 1:10 to assure sufficient cathode area to
ANDERSON ON CREVICE CORROSION IN SEAWATER 233
3/16" DIA. SUPPORT ROD
4"X6"X .05 - . 2 5 " P4NEL

^ ' WITH 1/2" CENTER HOLE
I 1 I -f OELRIN NUT
^-jt^ < EXTERNALLV THREADED 1/2"

0,0. DELRIN SLEEVE
FIG. 1—Multiple crevice test assembly.
prevent interference between crevices. The selection of the washer ma-

terial was based on the attractive combination of mechanical properties
and dimensional stability in seawater. Other nonmetallics with similar
properties should be equally suitable.
Specimens are prepared by degreasing and pickling using pickling
solutions appropriate for the materials involved. Generally, three speci-
mens of each alloy are provided to produce a good statistical base of 120
crevices per alloy. Specimens are exposed vertically (to reduce silting) in a
wooden flume where gravity flow of fresh, well aerated seawater produces
a constant velocity of 2 ft/s. Exposure periods vary, depending upon the
relative corrosion resistance of the materials being evaluated. For most
stainless steel alloys, the optimum exposure period has generally been
found to be one to three months.
Analyses of the particular alloys used in these investigations are given
in Tables 1 and 2.
TABLE 1-—Alloy compositions.
%
Alloy Fe Ni Cr Mo Cu Other
Type 304 stainless steel 68 10 19

Type 316 stainless steel 65 12 17 2.5
6X 48 24 20 6.5
Incoloy alloy 825 30 42 22 3 2
Inconel alloy 625 3 61 22 9 Cb,Ta
Hastelloy alloy C 5 56 15 16 W,Co
65:35 Ni-Cu 1 67 32
70:30 Cu-Ni 0.5 30 69 Mn
Copper (electrolytic tough
pitch) 99.9
^ E g;
a.
1
6 5
fSCT\Ov -H o O
>n
A <
&^
^Jn!
§
1
I 6
c C3
<
o
o rt 8!
^
o
U 'S
tt,
a
-^ O O O O
^-^<r^ V) 14-1 tn
8 0\ 0\ 0\ '—I
I 00 oo <^ so
U
o
O ^:7^ 00 O O i-H
^
Ô ^ ^ OO O ^
O O O (N »0 fvi
&?
W
pa
CO P3
^ . O
H ca "
^< I •^ 2 °
FIG. 2—Grooved acetal resin washer.
Test Results
The creviced area on a typical cast stainless steel specimen is shown in
Fig. 3. Despite precautions to make the individual crevices as uniform as
possible, a random pattern persists. Four distinct degrees of corrosion are
evident: (1) no attack, (2) uniform shallow attack, (3) accelerated "pit-in-
crevice" resulting from buildup of acidic corrosion products, and (4)
catastrophic attack. Although the corrosion appears to follow a random
pattern, statistical evaluations reveal consistent trends. Probability plots
(ASTM Recommended Practice for Applying Statistics to Analysis of
Corrosion Data (G 16-71)) of tabulated depths of attack measured in each
crevice area on multiple specimens provide clear alloy comparisons. A
typical probability plot, comparing two cast stainless steel alloys is shown
in Fig. 4. These data indicate a 100 percent probability of corrosion
initiation (zero probability of no corrosion) for alloy CA-15 and a 50
percent probability of crevice corrosion penetrating greater than 30 mil.
The higher level of corrosion resistance to be expected for alloy CF-8M
is delineated by a 25 percent probability of corrosion initiation with only
a 2 percent change of corrosion penetration to > 3 0 mil. Thus the proba-
bility curve can be used to assess alloying effects on resistance to both cor-
rosion initiation and corrosion propagation.
The probability curves in Fig. 4 follow two distinct slopes for each
alloy, one associated with crevices where uniform corrosion occurred
(Type 2 in Fig. 3) and the second where accelerating pit-in-crevice attack
FIG. 3—Four stages of crevice corrosion observed on single cast stainless steel specimen
exposed with multiple crevices, 30-day exposure.
developed (Type 3). Where Type 4 or catastrophic corrosion occurs, a

third steeper slope is frequently observed. Only alloy CA-15 suffered any
pitting (that is, localized corrosion not associated with known crevices),
and typical for many of the tests, the maximum pit depth exceeded the
maximum depth of crevice attack.
2 FPS 32DAYS I5'C 75:1 RATIO
«PIT
-j 150
"
CA-15
/^
z
lu
Q. 50 •/^ CF-8M ,-''
95 90 80 70 60 50 10 30 20 10 5 2
PROBABILITY - X
FIG. 4—Probability of crevice corrosion for cast stainless steels; exposure conditions: 32
days, 59°F {15°C), 75:1 bold/shielded area ratio.
Table 2 summarizes data developed for a series of cast alloys. Alloying

appears to have equal effects on corrosion initiation and the various stages
of crevice corrosion. However, it is of interest to note that all of the alloys
containing <0.6Mo suffered distinct pitting while alloys containing
>2.6Mo did not, even though two of the three alloys in the latter category
did incur significant crevice corrosion. Only the development alloy IN-862,2
containing 5Mo, provided immunity to both pitting and crevice corrosion.
This is a clear indication of the different alloying requirements for control
of pitting and crevice corrosion in seawater.
Area Ratio Effects
Initial tests on wrought alloys have concentrated on three alloys: Types

304 and 316 stainless steel and Incoloy alloy 825, alloys which have been
recognized through field experience to provide three different levels of
inherent resistance to crevice corrosion in the seawater system.
Specimen size was introduced as a second variable in these studies to
assess the effects of creviced/exposed surface area ratio (that is, anode/
cathode area ratio), a factor previously shown to be important in determin-
ing severity of crevice corrosion in seawater.' Various area ratios were
created by varying both specimen size and by machining different sized
plateaus on the washers. Figure 5 shows creviced areas on typical specimens
from a one month exposure. The importance of area ratio is evident, both
in relation to the corrosion initiation and corrosion propagation stages.
Area ratio effects have been isolated for these two stages in Figs. 6 and 7.
Variability provides considerable overlap in both instances, but the con-
sistent differences in the relative merits of the three alloys are readily
apparent.
The highest area ratio used in these studies was 580:1. The marked
effect of increasing area ratio suggests that even higher ratios could be
used effectively to reduce the exposure period required to induce sig-
nificant attack.
Metal-Ion Versus Oxygen Concentration Cell Corrosion
Similar studies have been conducted with copper, copper-nickel, and

nickel-copper alloys to provide comparative data for metal-ion concentra-
tion cell corrosion to contrast the oxygen concentration cell corrosion
2 Forbes-Jones, R. M., AFS Transactions, American Foundrymen's Society, Vol. 81,
1973, pp. 349-352.
3 Ellis, O. B. and LaQue, F. L., Corrosion, Vol. 7, 1951, pp. 362-364.
Type 304 Stainlesf Stsel
Type 316 Stainless Steel
Incoloy Alloy 825
290:1
Bold Exposure: Creviced Area Ratio
FIG. 5—Area ratio effects on oxygen concentration celt corrosion in seawater, one month
exposure.
Studies described previously. Crevice areas from a three-month test are

shown in Fig. 8. Following the classic pattern for metal-ion cells, corrosion
developed adjacent to, rather than within, the creviced areas. The lack of
any apparent statistical pattern is also apparent. Neither copper nor copper-
nickel showed any sensitivity to area ratio effects (Fig. 9) reflecting reduced
cathodic control in metal-ion concentration cell corrosion. The nickel-
copper alloy exhibited an apparent mixed mode between oxygen and
metal-ion cell control.
Q ] T-304 Stainless Steel

g 50 ^T\ T-316 Stainless Steel
FTH Incolov Alloy 825
0
O 30
1/1 10/1 100/1
Bold/Creviced Area Ratio
FIG. 6—Probability of crevice corrosion initiation, one month exposure inflowing seawater.
60
I I T-304 Stainless Steel

50 ^ T-316 Stainless Steel
E|J Incoloy Alloy 825
40
I 30
20
10
0.1/1 10/1 100/1 1000/1
Bold/Creviced Area Ratio
FIG. 7—Probability of crevice corrosion penetration to 10 mil in one month
Copper
70/30 Cu-Ni Alio/
65/35 Ni-Cu Alloy
3:1 426:1
Bold Exposure: Creviced Area Ratio
FIG. 8—Area ratio effects on metal-ion concentration cell corrosion in seawater, three
month exposure.
/
t
T --304
304 '
Stainless Steel
<
r
(0
0
80
60
y
Q.
/
Q
^ 40 65/35 Ni-Cu -
£ /
> -
70/30
' Copper^ y Ni
" - ^
1/1 10/1 100/1
Bold/Sheltered Area Ratio
FIG. 9—Area ratio effects on depth of attack in tight crevices, three month exposures in
flowing seawater.
Evaluation of Highly Corrosion Resistant Alloys

The use of highly corrosion resistant alloys in critical applications re-
quires assurance of virtual corrosion immunity, that is, demonstration of
an exceptionally high probability of resistance to corrosion initiation, or
assuming extreme conditions permit some corrosion to initiate, resistance
to active corrosion penetration to any significant depth. Table 3 shows
typical data for one year (as contrasted to the one month exposures in
Table 2) for three highly corrosion resistant alloys which are finding
increasing acceptance for a variety of marine applications. Of the three
TABLE 3—Crevice corrosion of wrought corrosion resistant alloys.'^
Probability, %
Corrosion 1-mil 10-mil

Alloy Initiation Attack Attack Pitting
6X 0
Inconel alloy 625 23
Hastelloy alloy C 0
" One year tests, seawater temperature = 40 to 90°F (4 to 32°C), creviced/exposed

surface area ratio = 1:89.
alloys only alloy 625 incurred any visible corrosion in this particular test,
but it is important to consider the exceptional resistance to corrosion
penetration exhibited by this alloy as is evidenced by the 1 percent proba-
bility indicated for corrosion penetration deeper than one mil.
Summary
Statistical evaluation of data developed through the multiple crevice
approach provides a useful basis for isolating geometrical and environ-
mental factors affecting oxygen concentration cell crevice corrosion in
seawater. The method also provides a useful laboratory test for detailed
assessment of inherent capabilities of a variety of candidate alloys for
marine service.
C. W. Petersen1
Solution Chemistry of Pitting of Iron in

Artificial Sea water
REFERENCE: Petersen, C. W., "Solution Chemistry of Pitting of Iron in Artificial

Seawater," Galvanic and Pitting Corrosion—Field and Laboratory Studies, ASTM
ABSTRACT: The mechanism of pitting corrosion in carbon steel in a simulated
seawater environment was studied by obtaining data on the chemical changes
which occur with time in the pit and cathode solutions. Quantitative measure-
ments were made of pH; sodium, magnesium, calcium, iron, chlorine, sulfate
concentrations, and weight loss. The solutions used in the analysis were generated
by using a recently developed artificial pit which not only provided a sufficient
amount of solution but also made it possible to obtain specimens from specific
locations in the cell itself. The results show a depletion of magnesium, calcium,
chlorine, and sulfate in the cathode region while sodium and hydroxyl ion concen-
trations increased. Inside the pit the chlorine, iron, and hydrogen ion concentra-
tions rose while the calcium, magnesium, and sodium concentrations dropped.
Based on the results of these tests, it is shown that the decrease in pH in the pit is
greatly enhanced by the magnesium and calcium reactions occurring at the
cathode and by the formation of iron colloids (Fe(OH)4~ and Fe(OH)2+).
KEY WORDS: corrosion, corrosion tests, pitting tests, artificial pit, seawater
attack, solution chemistry, carbon steel pitting, evaluation, pitting mechanism
Many people have studied pitting corrosion [i-3] 2 and have compiled a
vast amount of data. Unfortunately, as stated by Parsons, Cudd, and
Lochte [4] in 1941, "while theories regarding the mechanism of . . . pitting
have been well developed . . . this has been done largely without the aid of
chemical analysis of the solutions enclosed within the pit." This point was
reiterated by Szklarska-Smialowska [3] in her 1970 review of pitting
corrosion research, "knowledge of the composition of the solution within
the pit, and it changes during pitting, would throw more light on the
mechanism of processes occurring in the pits. Unfortunately, there are
only a few quantitative references concerning that problem." For this
1
Senior engineer, Bettis Atomic Power Laboratory, Westinghouse Electric Corporation,
West Mifflin, Pa. 15122.
2
243

University of Washington (University of Washington) pursuant to Li
reason a study was conducted to determine the changes in the solution

chemistry of a pit during its growth.
Experimental
Test Apparatus
A macropit developed in an earlier study [5] was used to provide sufficient
pit solution for chemical analyses. Figure 1 shows the test cell and the
entire test apparatus. The test cell consisted of a ^ by 1^-in.-diameter
cylinder made of low carbon steel clamped between two plexiglass disks.
The interior portion of the cylinder was partially filled with the electrolyte.
A pressure vessel was used to house the cells during testing. Figure 2 shows
how the pit formed and denotes the cathode and anode areas as well as
the sampling areas.
Procedures
Each specimen was poHshed to a standard surface using 320 grit emery
paper. The polished specimen was dipped in hydrochloric acid, cleaned in
acetone, rinsed in alcohol, and dried. The specimen was weighed, clamped
between the plexiglass disks, and partially filled with a test electrolyte. The
complete test cell was then placed in the pressure vessel which was subse-
quently sealed and charged with oxygen. The oxygen pressure (500 psi)
was used to accelerate attack and to set up a concentration cell.
The progress of each run was monitored visually, and photographs were
taken or sketches were made of the test cell appearance during the test
and at the completion of each run. The vessel was then depressurized, the
cells removed, and the chemistry specimens taken. The solutions were
saved for chemical analysis and the specimen itself was reweighed to
determine weight loss.
The sampled solutions were analyzed using atomic absorption and wet
chemistry techniques. They were tested only for the major anions and
cations. In so doing, the composition of the solution was monitored both
as a function of time and as a function of location in the cell.
Results
There were many electrolytes used in the tests conducted for this study
[6], varying from 0.535 M sodium chloride to an ASTM sea salt (according
to ASTM Specifications for Substitute Ocean Water (D 1141-52)). Although
much valuable information was gained from all of these tests, only the
results of those tests which were designed to determine the roles of the ions
during pit formation in the artificial seawater will be discussed. The solution
used was prepared according to ASTM Method D 1141-52, Table 1,
Section 4, Formula A.
PETERSEN ON SOLUTION CHEMISTRY 245
TEST CELL
TEST APPARATUS
FIG. 1—Test cell apparatus.
FIG. 2—Cell formation and sampling locations.
Changes in the Solution Chemistry

The results reported in the following pages were obtained by analyzing
specimens from three locations in the cell: (a) along the cell wall near the
cathode, {b) in the middle of the top bulk solution, and (c) at the very
bottom of the cell near the anode (below the layer of corrosion products
which formed across the pit) (Fig.2). Each test was run in triplicate, and
the averages are plotted for each ion in Figs. 3 to 10 as a function of time
in the Hfe of the cell.
X-ray Results
A qualitative fluorescence analysis of the corrosion products revealed
the presence of iron, calcium, and manganese in the products. Elements
with an atomic number less than 20 could not be detected by the equipment
available. The lighter elements were, however, detected by emission
spectrographic analysis, and these results are shown in Table 1. X-ray
diffraction yielded amorphous patterns with no distinct peaks.
In Situ pH Measurements
The pH variations during pitting proved to be very important. On
selected time series experiments, in situ measurements were made prior to
sampling of the electrolyte by carefully lowering a micro-pH electrode
into the test cell at various locations. Readings were taken at the cathode
surface, on a vertical line through the center of the cell, and at the anode
surface. This allowed precise pH determinations at pinpoint locations
which would otherwise be missed in testing extracted specimens. The
results are presented graphically in Fig. 11. It should be noted that in the
early stages of the cell formation the pH was constantly decreasing from
top to bottom. After products began to form, however, there was a pH
inversion in the pit solution and the pH actually rose slightly as the elec-
trode approached the anode surface.
TABLE 1—Results of elemental analysis.
Cathode Material" Bridge Material Pit Material
X-ray fluorescence Fe Fe Fe
Ca Ca Mn
Mn Mn
Emission spectrography (bridge material only), %'
Na, 0.1 to 10 Cr 0.0001 to 0.001
Mg, 0.1 to 1 Mn, 0.01 t o o . 1
Al, 0.001 to 0.1 Fe, >10
Si, 0.0001 Cu, 0.0001 to 0.001
Ca, O.OltoO.l Zr, 0.001 toO.01
K, none detected
' Cathode material was scraped from cathode wall and combined with white floe obtained
by centrifuging the cathode solution.
'Results based on dried crushed samples; instrumentation = 3.4 m Ebert Mark IV
Spectrograph.
Discussion of Results
The quantitative results show the changes in ion concentrations within

the electrolyte. There are some general trends which seemed to affect all
ions. The changes were: {a) every ion in solution experienced a period of
instability during the first 6 h; (fc) the period from 6 to 41 h was a period of
transition, with large changes occurring; and (c) the period from 41 h
until the end of the test was a period of stabilization and solution equi-
librium.
Instability
The fluctuations in ion concentrations (Fig. 12) coincided with fluctua-
tions in the potential of the solution (see Appendix) and were due un-
doubtedly to the changes occurring on the cell surface itself. For the ions
initially in solution, the instability took the form of temporary depletions.
The cell has many anodes and cathodes spread over the whole surface, the
anodes generating iron ions and the cathodes generating hydroxyl ions.
This was evidenced by the rise in iron concentration in all areas. Initially
these sites are close together, and there is rapid interaction between the
iron and hydroxyl ions produced at these sites, causing the formation of
basic salts which remove ions from the solution. As the anodic and cathodic
regions grow, the iron and hydroxyl ions must migrate farther as a part of
the corrosion current before reacting, and there is less chance of a rapid
interaction trapping other anions and cations. Thus, as the metal surface
stabilized into localized anodes and cathodes, the behavior patterns of the
ions also stabilize.
15
Cathode Solution (#1)
jQu Jb
10 ~ ^ ® ^ TT
pH
I I J_>J L. J I 1 L
10 20 30 ifO 50 6o 70
Hours
15 r
Tbp Bulk Solution (jfe)
jQ
O
u o o
pH
5 -
. 1 . 1 • 1 . 1 1 1 1 1 ' -L.
10 20 30 Uo 50 6o 70
Hours
15
n t Solution (jfe)
10
pH
•e <^ o
J I L I I t J L
10 20 30 1*0 50 6o 70
Hours
FIG. 3—Hydrogen concentration as a function of time.
Transition
During the 6 to 41-h period there were a variety of changes in ion con-
centrations. The changes encountered in the top solution will be discussed
first since they play an important part in what occurs elsewhere in the cell.
Magnesium experienced a rapid depletion in the upper region. Calcula-
tions indicate that the solubility of magnesium hydroxide was exceeded at a
pH of approximately 9.5. Thus, the equilibrium between hydroxyl genera-
30 r
Cathode Solution (#l)
20
(CI)
•o o—e g o Q o—o—0
10
10 20 3© '*0 50 6o 70
Hours
30
Ibp Bulk Solution (#2)
20 <r
^©a-_o—a. -e e- "D" T)
(a)
ppt
10 -
10 20 30 ito 50 60 70
Hours
Pit Solution (#3)
(CI)
ppt
FIG. 4—Chloride concentration as a function of time {ppt = parts per thousand).
tion and magnesium depletion accounts for the first plateau in the pH curve.
The formation of magnesium hydroxide prevented some hydroxyl from
reaching the pit region. The actual precipitate which formed was white and
quite voluminous. Because of its nontenacious character, the product
accumulated at the interface between the pit and upper solution rather
than adhering to the walls. During this time the magnesium concentration
in the pit slowly decreased.
3
o^^ Cathode Solution (#l)
ppt
10 20 30 kO 50 60 70
Hours
3 r-
Ibp Bilk Solution (jfe)
O ^ cr
Jl.
ppt
20 30 1*0
X 60 70
10 50
Hours
2 Pit Solution (#3) o
-O.
ppt
I -L J.
10 20 30 kO 50 6o 70
Hours
FIG. 5—Sulfate concentration as a function of time.
Once the magnesium was depleted in the top solution, however, the
hydroxyl was able to enter the solution as free ions, and the pH increased.
This rise in pH in Areas 1 and 2 was accompanied by large changes in the
chemistry of the pit solution. After 24 h the slow decrease in magnesium
was altered, and there was a rapid drop in concentration. Since the mag-
nesium did not show up in either Area 1 or 2, it must have been removed
from solution either in the pit or at the interface between the pit and the
15
Cathode Solution (,#i.)
ppt
10
'V-^ jQ o O- -e o—o—o
• I I 1 I I I I I I 1 1 1 L
0 10 20 30 ko 50 6o 70
Hours
^5 r
^ p Bulk Solution (fe)
10 'Hs^^ g € O- ~a—O"
o o
(Ifa)
ppt
t i l l I I I I,. I I I 1 1 L
10 20 30 ko 50 60 70
Hours
15 r
Pit Solution {ii)
10
« _—Q
(Na) 0 o^
ppt
I • I I I \ \ I I L J L
10 20 30 ko 50 6o 70
Hours
FIG. 6—Sodium concentration as a function of time.
Upper solution. Also, since none of the solubilities of magnesium com-

pounds was exceeded in the pit, the magnesium removed from solution
must have been incorporated into the structure of other precipitates as an
impurity. The rise in pH in the pit at 24 h was accompanied by a rapid drop
in iron and chloride-ion concentrations as well as magnesium. Rapid pre-
cipitation of iron could have trapped the magnesium and chloride into the
1-5 ,
Cathode S o l u t i o n (#1)
1.0 h
(Mg)
ppt
0.5
I nN-O I... In ^. Al î—J^

0.0
10 ao 30 ko 50 6o 70
Hours
1-5 r
Top Bulk S o l u t i o n ()fe)
1.0
(Mg)
ppt
0.5
I 0|^ IM !•' S± ^£
0.0 10 20 30 UO 50 60 70
Ikmrs
1.5
r Pit S o l u t i o n (#3)
1.0
(Mg)
ppt
0.5
0.0
0 10 20 30 ItO 50 60 70
Ifours
FIG. 7—Magnesium concentration as a function of time.
products. It is interesting to note that emission spectrometry identified

magnesium as an element in the bridge. At this same period when iron,
magnesium, and chloride decreased, the first signs of a layer (bridge) of
corrosion products began to appear at the anode/cathode interface.
Unfortunately, no analysis was made of the pit products by emission
spectrometry. It is interesting to note that the weight loss increased sharply
0.6
Cathode Solution (#1)
o.k
(CSi)
ppt
0.2 -
0.0
0.6
O.U
0.2 -
0.0
0.6
n t Solution (#3)
O.k <-
Pz—«'—o—^
0.2
0.0 J L J L X70
0 10 20 30 ho 50 6o
Hours
FIG. 8—Calcium concentration as a function of lime.
between 32 and 41 h, as did the amount of iron in solution. These increases

could be explained by a depolarization of the anode due to the decrease of
iron in the pit solution between 24 and 32 h.
Calcium experienced a slower reduction in concentration in all areas than
did magnesium. Calculations show that the solubility of calcium hydroxide
was not exceeded; therefore, its formation is not a major factor in calcium
depletion. Calculations do show, however, that the solubility of calcium
0 3 r—
Cathode S o l u t i o n (#1)
0.2 -
(Fe)
ppt
0.1 -
OySsO I.-. • r)| .., Ift , P . ^ . ..j Q 40

10 20 30 Uo 50 6o 70
Hours
0.3 r-
Top Bulk S o l u t i o n (#2)
0.2
(Fe)
ppt
0.1
(f>oo IM . g | ... IP I p • g • fli Q lo

0,0
10 20 30 ho 50 6o 70
Hours
6 r-
Pit Solution (#3)
(Fe)
ppt
2 -
FIG. 9—Iron concentration as a function of time.
carbonate was exceeded and plays an integral part in the reduction of

calcium concentration in the cell. The calculations also show that at 32 h
when the pH was 10.9 all of the available bicarbonate would have been
completely depleted and the complexing of calcium would cease. This
accounts for the large change in calcium slope.
Calcium in the pit was less affected by the depletions in the upper region
and, except for the slight anomaly between 24 and 41 h, it underwent a
O.lU r-
0.12 -
0.10 —
0.08 -
5 o.o6
a
o.o4 -
0.02 -
0.00
Hours
FIG. 10—Weight loss as a function of time.
gradual depletion. The fact that this calcium did not reappear in the upper
solution indicates that, like magnesium, it was incorporated into the prod-
ucts of the iron precipitates. The results of the X-ray and emission spec-
trometry analyses show that calcium was present in the bridge and cathode
products but not in the pit products. The incorporation of calcium from the
pit, therefore, must have taken place at the interface between the pit and
upper solution.
Sodium was a very difficult ion for which to obtain consistent measure-
ments, and the values which were averaged were very sporadic. This was
due to the large dilution and low sensitivity required for the analysis of
the large concentration of sodium in seawater. As a result of the wide
range of values, the intervals of confidence are large.
After its initial fluctuations, sodium settled into a simple migration pat-
tern, and the concentrations in Areas I and 2 gradually rose while de-
creasing in the pit. This migration pattern supports a role of balancing
changes for sodium.
A mass balance calculation using the sodium concentrations in the top
and pit areas indicated that there was a loss of sodium. This depletion
a. After 24 Hours
b. After 35 Hours
FIG. n—pH profiles.
appears to be quite negligible, but this is deceiving since the concentration

of sodium is so large. Since sodium did not exceed any of its known solu-
bility limits, it must be assumed that the loss was due to incorporation of
sodium into the structure of some of the precipitates. The presence of a
large quantity of sodium in the bridge was confirmed by the emission
spectrometry results.
Iron in Areas 1 and 2 had stabilized at a low value within 4 h and re-
mained there for the duration of the test. Since iron hydroxide is extremely
insoluble in the pH range encountered in Areas 1 and 2, the iron in solution
was probably in equilibrium with the insoluble material. This governed the
final concentration of iron in the upper region. Many of the measured
values fell below the sensitivity of the atomic absorption unit so the actual
amount of iron in solution was extremely low. Even using the measured
value of approximately 10^* M, however, the measured and calculated
equiUbria values were within one order of magnitude (~10-^ to 10~^ M).
Area 1 Area 2 Area 3
(CI)
H 10 0
V*>e
10
'\y
10
Hours
(Fe)
, ^
10
rv* 10
kl 10
(Ca)
v 10
lA
10
(MB)
0
\
10
f\
0 10 0
^
10
FIG. 12—Concentration functions during instability period.
Iron, during this transition period, gradually increased in concentration

in the pit due to its generation at the anode. There was a slight anomaly
between 18 and 32 h, but this was explained by the sudden release of
hydroxyl from the cathode due to magnesium depletion.
Chloride was very similar to sodium, experiencing a drop in concentra-
tion in all areas during the first 4 h and then recovering to achieve a gradual
migration pattern. The anomaly in the pit between 18 and 32 h was ex-
plained earlier.
Sulfate exhibited a behavior that mirrored the pH changes. The concen-

tration leveled off at 6 h to form its first plateau, then dropped between 24
and 32 h. Solubility and stability data indicate that the sulfate would
complex all the cations by forming ion pairs, but it does not exceed any of
its known solubility limits. Therefore, the decrease in sulfate must be due
either to migration or coprecipitation as an impurity. While migration
does not seem to be the sulfate's depletion mechanism, there was no readily
apparent explanation for the plateaus observed for sulfate in Areas 1 and 2.
Inside the pit the sulfate did appear to be increasing in concentration.
Mass balance calculations indicated that there was a slight loss in overall
concentration; thus, some of the material from Areas 1 and 2 may have
been incorporated into the solid products.
Stabilization {41 to 72 hours)

The period from 41 h until the end of the test was a stabilization period
for many ions, apparently caused by the depletions which occurred earlier.
In Areas I and 2 the solution had essentially been reduced to a sodium
solution by the depletion of magnesium and calcium. The sodium concen-
tration was rising to satisfy charge neutrality but had virtually no effect on
the hydroxyl ion generated at the cathode. Thus, the hydroxyl was free to
migrate towards the pit essentially unimpeded.
The leveling off of the iron concentration in the pit as well as the plateau
in the pH curve in the upper solution are important. The leveling off of the
pH and iron could be due to the cessation of attack, but the weight loss was
still increasing during this period so attack was still occurring. The leveling
off could also be due to a steady state equilibrium between the hydroxyl
and the iron. The hydroxyl, which was now free to migrate from the
cathode to the pit, would react with the iron which had been building up
in the acidic pit area and a steady state could be reached. It should be
noted that during this time rapid bridge growth occurred, but there was no
apparent depletion of ions in solution. Besides iron and hydroxyl, the
other ions also stabilized.
Magnesium in the cathode region was unaffected and remained depleted.
In the pit region, it had risen slightly from the earlier drop in concentration
and stabilized into a slow decline. Again, the magnesium did not reappear
in Areas 1 or 2, so it must have become incorporated into the products.
Calcium and sulfate essentially leveled off in all areas during this period,
as did the iron and hydroxyl. The chloride and sodium still exhibited a
slight migration pattern. These reductions in slope would be expected
since the hydroxyl ions were providing most of the needed charge neu-
trality by complexing iron.
This series of events coincided with the period of rapid bridge building
and supports a theory of rapid agglomeration at the interface between the
high and low pH regions. It is also important to note that the amorphous
patterns obtained when X-raying fresh products confirms that these prod-
ucts were formed from colloids since the only way to obtain an amorphous
precipitate is by first forming colloids [7]. The aging of the products into
crystalline magnetite (Fe304) and hematite (Fe203), which is a known
phenomenon among colloids, also provides support for a mechanism
involving colloid formation and bridge building.
Conclusions
For many years the study of pitting corrosion has been hampered by a
lack of quantitative data about the solution chemistry related to the attack.
The data obtained in this study provide information concerning reactions
inside the pit as well as those occurring near the cathode. Based on these
results, roles and mechanisms were proposed for the major ions. The
principal results of the work are as follows.
1. The attack found in seawater was not solely a function of a single

anion-cation pair but rather a complex mixture which depended on:
(a) types of ions present, (b) individual ion concentrations, and (c) relative
ion concentrations (for example, magnesium/sulfate or magnesium/sodium
ratio).
2. The anions allowed an increase in hydroxyl concentration near the
cathode by forming ion pairs.
3. The initial pH buildup caused precipitation of magnesium hydroxide.
This complexing of hydroxyl ions stabilized the pH at a value of 9.5.
4. The complexing of hydroxyl ions at the cathode limited the ions
ability to migrate to the pit. Thus, the iron generated at the anode hydro-
lyzed water and the pH dropped due to free hydrogen ion generation. The
reduction in pH in the pit did not first require the formation of solid
products over the pit area.
5. Solution potential measurements, stability calculations, and solubility
data indicate that the major iron ion present in the pit is the ferrous ion.
6. The formation of amorphous products and visual observations indi-
cate the presence of colloids which appear to be quite important to the
cell formation.
7. X-ray and emission analyses have shown that all of the major cations
except potassium are incorporated into the bridge structure.
Acknowledgments
The author wishes to thank V. C. Rose, K. H. Mairs, and T. J. Rockett,
University of Rhode Island, who have contributed greatly to the general
development of the project and helped to stimulate its progress.
APPENDIX
Solution Potential
Electrode potential (E°) is a common term in corrosion studies, whereas solution
potential [8] is not as common. A brief explanation of solution potential (Eh) and
how it is used in corrosion studies is presented to clarify the term.
If we consider the general half cell reaction
oxidation + ne~ ;^ reduction, then log K = log Aêd —
log Ao^ + «pE, and pE = pE° + «-> log (A„JA,,i)
where pE° = /i~' log K, and pE is a pure number, which is similar to pH. The
value pE corresponds to the oxidizing power of the equilibrium system. The
quantity pE is related to the more general redox potential (Eh) by the relationship
pE = - l o g (e-)
2.3 R T / ° F
Thus, elements which have more than one oxidation state (for example, Fe'+ and
Fe^+) will have the species present in equilibrium with seawater controlled not
just by pH but by the solutions redox potential as well. In natural waters the
relative concentrations of such pairs is controlled primarily by the concentration
of dissolved oxygen. In general, the pH and pE values will not deviate much in a
flowing system, but in stagnant areas the oxygen in the water will be stripped
and the pE will fall (for example, crevices).
To illustrate how this information is put to use, consider the oxidation state of
thallium in seawater (ignoring any possible complexes)
T F + + 2e-^ T1 +
The standard electrode potential (E°) for his reaction is - 1 . 2 4 7 V at 25°C. The
redox potential (Eh) of seawater is 0.789 V. Then, if one applies the Nernst equa-
tion, E = B° + RT/rtF In ^ T P + / ^ T 1 + . Thus, 0.729 = - 1 . 2 4 7 (0.0591/2) log
AT1^+/AT1+ and r P + / T l + = lO""". This ratio says that any thallium should be
present almost entirely as TP+. Similar calculations can be carried out for other
elements to determine the species expected inside and outside a pit if one knows
the solution potential.
References
[/] Fontana, M. and Green, N., Corrosion, Vol. 15, Jan. 1959, pp. 25t-31t.
[2] Kolotyrkin, J., Corrosion, Vol. 19, Aug. 1963, pp. 261t-268t.
[3] Szklarska-Smialowska, Z., Corrosion, Vol. 27, June 1970, pp. 223-233.
[4] Parsons, E., Cudd, H., and Lochte, H., "Synthetic Corrosion Pits and the Analysis of
Their Contents," Journal of Physical Chemistry, Vol. 45, 1941, p. 1339.
[5] Petersen, C. W., Soltz, G. C. and Mairs, K. H.. Corrosion, Vol. 30, No. 10, Oct. 1974.
[6] Petersen, C. W., "Solution Chemistry of Pitting Corrosion in Seawater," Ph. D. thesis.
University of Rhode Island, 1974.
[7] Blaedel, W. J. and Meloche, V. M., Elementary Quantitative Analysis, Harper and Row,
New York, 1963.
[5] Riley, J. P. and Chester, R. in Introduction to Marine Chemistry, Academic Press, New
York. 1971, pp. 75-79.
P. E. Morris1
Use of Rapid-Scan Potentiodynamic

Techniques to Evaluate Pitting and Crevice
Corrosion Resistance of Iron-Chromium-
Nickel Alloys
REFERENCE: Morris, P. E., "Use of Rapid-Scan Potentiodynamic Techniques

to Evaluate Pitting and Crevice Corrosion Resistance of Iron-Chromium-Nickel
Alloys," Galvanic and Pitting Corrosion—Field and Laboratory Studies, ASTM
ABSTRACT: Rapid-scan potentiodynamic polarization techniques were utilized
to determine pitting potentials (Ep) for Types 304 and 316 stainless steel in 25°C,
4 percent sodium chloride. Decreasing the test time by increasing the potential
scan rate prevented the development of crevice attack, thereby permitting Ep to
be measured accurately and reproducibly. A close examination of the rapid-scan
polarization curve for Type 304 stainless steel in the potential region above E„
revealed two distinct linear segments. Static potential test results indicated that the
more active linear segment was a response due to pitting attack, and the more noble
linear segment was a response due to crevice attack. These observations suggest
that if a rapid-scan potentiodynamic technique is employed, then pitting and
crevice corrosion resistance might be measured by a single test procedure. In
addition to the effect of potential scan rate, it was found that the test electrode
surface finish is an important consideration in the determination of pitting
resistance or crevice resistance or both.
KEY WORDS: corrosion, pitting, concentration cell corrosion, potentiodynamic

polarization, sodium chloride, iron alloys, corrosion tests
The application of electrochemical methods to the study of pitting and

crevice corrosion has been discussed in numerous publications [1-21 ]. 2
Although several electrochemical techniques have been developed to
determine pitting resistance, none of these have been adopted as a standard
procedure due to their various limitations. In particular, crevice corrosion
of the test electrode during electrochemical pitting evaluations has been a
1
Research scientist, Paul D. Merica Research Laboratory, The International Nickel
Company, Incorporated, Suffern, N. Y. 10901.
2
261

University of Washington (University of Washington) pursuant to L
recurring problem. Several workers [2-7] have reported that crevice attack
occurs before the onset of pits, interferring with measurement of the
pitting potential. For example, Johnson [6] noted that crevice attack
caused a negative shift in the measured breakthrough or pitting potential
(Ej,), whereas a positive shift in Ep with crevice development was observed
in the present study using a similar conventional slow-scan potentio-
dynamic technique.
Crevice corrosion has been easier to study by electrochemical techniques,
and various electrochemical crevice corrosion test electrodes have been
described in the literature [5-11]. These electrodes have been used both to
rank metals by crevice corrosion resistance and for mechanistic studies [12].
In this investigation, the pitting and crevice corrosion of Types 304 and
316 stainless steel were studied to examine the feasibility of developing an
electrochemical test capable of yielding information about both types of
corrosion simultaneously. Since crevices are invariably present at electrode-
holder junctions, consideration was given to using these crevices to provide
information about the electrode's crevice corrosion resistance. The data
presented suggest that if a rapid-scan potentiodynamic technique is em-
ployed, then the responses due to both pitting and crevice corrosion can
be detected, in fact, in a single anodic polarization curve. Furthermore, it
is suggested that it may be possible to rank iron-chromium-nickel alloys in
terms of their pitting and crevice corrosion resistance by comparing certain
portions of their anodic polarization curves. It is also shown that surface
preparation is an extremely important parameter in such comparisons.
Experimental
Specimen and Solution Preparation
Chemical compositions of the test electrode alloys, Types 304 and 316
stainless steel, are given in Table 1. Two types of test electrodes were
employed in this study, a conventional sheet electrode and a special crevice
electrode. The sheet electrodes were rectangular, measuring 8 cm^ in total
area, having been prepared from annealed 0.635-cm-thick sheet. Each
electrode was drilled and tapped in one end for mounting by a method
described previously [22]. The special crevice electrode is shown in Fig. 1.
The crevice was formed by forcing the beveled end of a short rubber tube
section against one surface of the circular specimen. A bolt through the
TABLE 1—Nominal chemical composition (percent) of alloys studied.
Ni Cr Fe Mo
Type 304 stainless steel 9.5 18.5 72.0

Type 316 stainless steel 12.0 17.0 68.0 2.25
MORRIS ON RAPID-SCAN POTENTIODYNAMIC TECHNIQUES 263
6/32 X 2 "
'MACHINE SCREW
LIQUID LEVEL
.TEST SPECIMEN
TEST ^ \_RUB8ER COAT
SURFACE ijj, BUSHING
(TEFLON)
•GASKET
FIG. 1—Electrochemical crevice test electrode assembly.
inside of the tube and the center hole of the specimen kept the specimen
and tube section in alignment. The specimen edges were masked with a
single component epoxy cured at 70°C, so only the specimen within the
crevice area was exposed to the environment.
All exposed alloy surfaces were manually abraded either with dry 180
grit or dry 600 grit paper. These abraded surfaces were rinsed with distilled
water, dried, and degreased with trichloroethylene before immersion in the
test solution. The entire surface preparation was completed 5 min prior to
testing.
All tests were performed at 25°C in a 4 percent sodium chloride solution
which was prepared by dissolving reagent grade sodium chloride in dis-
tilled water.
Apparatus
The polarization test cell was a modified [23] one-litre round bottom
distillation flask with the calomel reference electrode in direct contact
with the test environment.
Potential versus logarithm current density curves were plotted auto-
matically with a commercial potentiostat, motorized potential stepping
unit, logarithmic converter, and x-y recorder.
Procedure
Cathodic and anodic polarization curves were plotted, as described pre-
viously [23,24], by scanning potentials at 60.0 V/h from —2.00 V saturated
calomel electrode (SCE) to the pitting corrosion region until applied

current density reached 5000 MA/cm^. After reaching 5000 /Â/cm^ either
the potential scan was discontinued or the scan direction was immediately
reversed. Only the anodic portions of the polarization curves determined
by these methods are shown and discussed in the present paper.
Two types of supplementary constant potential tests were conducted.
One test series consisted of recording the current densities for a 1-min
period after turning on the potentiostat. In these tests the electrode was
cathodically polarized for 1 min at —2.00 V, just prior to being polarized
at the preselected anodic potential. The other test series consisted of
holding test electrodes at selected potentials for 16 h to determine the
extent and nature of localized attack. Due to the nature of the 180 and 600
grit surfaces, visual examinations for pitting or crevice damage or both
were carried out at a low magnification (X5).
Results
Effect of Scan Rate—The anodic polarization curve in Fig. 2 illustrates a
typical slow-scan (1 V/h) potentiodynamic response for Type 304 stainless
steel (180 grit surface finish on test electrode) starting at the steady state
corrosion potential in a neutral, concentrated chloride environment. A
+1.2
•0.8 -
CREVICE FORMED
AROUND
PITTING MOUNTING GASKET
CONVENTIONAL ELECTRODE
< -0.' 180 GRIT SURFACE FINISH
I-
z
-0.8
•1.2
10 10* 10' 10"

CURRENT DENSITY, /lO/cm'
FIG. 2—Type 304 stainless steel anodic polarization curve and test electrode for a 1.0-
V/h potentiodynamic scan in hydrogen purged, 25°C, 4 percent sodium chloride.
noble Ep value was measured by the active-to-noble potential scan. Revers-

ing the potential scan direction created a hysteresis loop and a repassivation
potential more active than Ej,. Visual examination of the test electrode
subjected to the slow-scan procedure revealed the presence of pits as well
as crevice corrosion around the mounting gasket (Fig. 2).
Increasing the potential scan rate from 1 to 60 V/h and initiating this
scan at —2.0 V yielded a completely different polarization curve (Fig. 3).
The hysteresis loop observed in the rapid-scan test was much smaller. In
addition, there was no visual evidence ( X 5 magnification) of crevice or
pitting attack on the test electrode after polarizing, despite the two decade
increase in anodic current density through the passive potential region.
Note that the same repassivation potential of —0.175 V was observed in
the 1 and 60.0 V/h scans.
Pitting—The 60.0-V/h scan rate caused a more active value for Ep
(Fig. 3) than was observed at 1.0 V/h (Fig. 2). However, the exact value of
Ep was difficult to determine from the rapid-scan curves due to the apparent
gradual slope change of the curves. Additional 60.0-V/h polarization
curves were then determined in which the potential axis was expanded on
the x-y recorder so that only the segment of the anodic curve from —0.300
to +0.400 V was recorded.
The magnified anodic curve segments shown in Fig. 4 revealed that this
area contains two distinct linear regions at more positive locations than Ep,
NO EVIDENCE OF
PITTING OR CREVICE
ATTACK
t 1.2
+0.8
+0.4 -
_i
Ep ond REPASSIVATION POTENTIAL -.175V
< LJJ
I- O
Zco 0.0
UJ u,
f- >
o > -0.4
-0.8 CONVENTIONAL ELECTRODE

180 GRIT SURFACE FINISH
-1.2
_L
10 10* I0» 10^
CURRENT DENSITY ^ a / c m ^
FIG. 3—Type 304 stainless steel anodic polarization curve and test electrode from a
60.0-VIh potentiodynamic scan in aerated, 25°C, 4 percent sodium chloride.
+0.3
REGION
fO.2
<tij + .MOV.
\-<J +0.1
^>
g > 0.0
COVENTIONAL ELECTRODE
-0.1 180 GRIT SURFACE FINISH
-0.2 -
10^ 10'
CURRENT DENSITY, fj.a/cm^
FIG. 4—Magnified potential axis in the vicinity of Ep for 60.0-V/h potentiodynamic

scan on Type 304 stainless steel in aerated, 25°C, 4 percent sodium chloride.
each with a characteristic slope. The more active linear region spans from
— 0.175 to —0.060 V and the more noble linear region spans from +0.030
to +0.110 V. For the purposes of the present paper, the passive region,
the two linear regions, and the upper-most (nonlinear) region will be
referred to as Regions A, B, C, and D, respectively (in order of increasing
nobility).
Several constant potential experiments were conducted in an effort to
further explore the behavior of the electrode in Regions A and B. The
current densities obtained during 60 s at potentials were recorded in each
of these regions (Fig. 5). Current density decayed rapidly during the first
few seconds at all potentials. At the potential in Region A, the currents
continued to decay at a slow rate indicating passive film buildup. At the
potential Ep between Regions A and B, the current density reached a
plateau after 30 s. At the potential near the active end of Region B, the
current density reached a minimum after 30 s and then gradually increased.
In order to investigate the possibility that pitting corrosion occurs in
Region B, a test electrode was prepared and held at a potential in Region B
for 16 h. For this test electrode the mounting gasket-electrode junction
was masked with epoxy paint to reduce possible crevice sites. After 16 h,
two large pits developed on one surface as illustrated in Fig. 6, and no
evidence of crevice attack could be found at the edge of the epoxy mask.
I0»
CO
E
o
>-
^ 10^
-.I50V= REGION B
\
a: -*--.l75 = Ep
cr 10 - CONVENTIONAL ELECTRODE
o 180 GRIT SURFACE FINISH
•/
-.200= REGION A
(PASSIVITY)
_i
< _1_ _L
15 30 45 60
TIME. SECONDS
FIG. 5—Current densities on Type 304 stainless steel for initial 60 s at selected applied
constant potentials in aerated, 25°C, 4 percent sodium chloride.
FIG. 6—Appearance of two pits developed on a Type 304 stainless steel test electrode
during 16 h at ^0.100 V [SCE) in aerated, 25°C, 4 percent sodium chloride.
Thus, in Region B pitting occurs and the intersection between Regions A

and B could be considered to define E^,.
Crevice Corrosion—In an effort to identify a potential region corre-
sponding to crevice corrosion, 60.0-V/h potentiodynamic polarization
curves were determined using the special crevice electrode. Fourteen
successive active-to-noble potential scans on this crevice electrode revealed
only crevice attack. No evidence of pitting was found. The complete
curves were recorded only for the odd numbered scans and are shown in
Fig. 7. These curves show that as the crevice propagated with increasing
number of scans, the current density at the active-passive transition in-
creased and then remained constant. Similarly, the hysteresis loop grew
initially, finally becoming constant. These observations indicate that on
continued scanning the crevice environment becomes more aggressive
with time until some limiting combination of environmental conditions is
achieved.
A close examination of the changes in the magnified anodic polarization
curves in the Regions A, B, C, and D (these regions were previously defined
in Fig. 4 and that curve is reproduced as the reference curve in Fig. 8)
revealed that repeated scanning caused progressive crevice attack and noble
shifts in Ep. Note that the magnified curves in Fig. 8 were recorded only on
the even numbered scans of the I4-scan experiment. For the first even
numbered potential scan, Ep coincided with the intersection between the
linear Regions B and C on the reference curve. As the crevice attack
^0.8 POTENTIAL SCAN ,

REVERSED AT 5,000â/tm"^
+0.4
N O . I , E D = O.OV
p o +0.0
UJ <n
(- >
0 > -0.4 CREVICE ELECTRODE
0.
I80GRIT SURFACE FINISH
-0.8
. dii 1^ *• M i * ' M ! iC V.X-XA«>« « # S ^ '

-1.2
10 10' 10' 10*
CURRENT DENSITY /la/cm^
FIG. 7—Effect of 14 successive 60.0-V/h potenliodynamic scans on the anodic polariza-

tion behavior of a Type 304 stainless steel: environment was aerated, 25°C, 4 percent sodium
chloride.
REFERENCE CURVE (NO CREVICE)
aO GRIT SURFACE FINISH
I
10' 10* 10'
CURRENT DENSITY /ia/cm2
FIG. 8—Magnified potential axis in the vicinity of ^^ for successive 60.0-V/h potentio-
dynamic scans on a Type 304 stainless steel electrode; environment was aerated, 25°C,
4 percent sodium chloride.
developed during the subsequent potential scans, the Ep values fell within
the linear Region C on the reference curve. This observation, together
with the observation that only crevice attack occurred on the electrode,
suggests that Region C on the reference polarization curve may be related
to crevice corrosion. However, further studies are necessary to establish
this unambiguously.
Ejfect of Surface Finish—All of the tests discussed thus far were obtained
using Type 304 stainless steel electrodes prepared to a 180 grit surface
finish. This surface finish is comparable to the commercial finishes on some
stainless steel products. However, in the laboratory it is common practice
to test specimens with a finish of 600 grit or finer to enhance visual detection
of pit or crevice development. Other workers have noted that surface
finish can affect pitting behavior [19-21]. In order to confirm that surface
finish is an important variable, the previously described experiments were
repeated using both creviced and noncreviced electrodes with 600 grit
surfaces.
Figure 9 shows that the finer surface finish on the noncreviced electrode
raised £„ in the noble direction, from - 0 . 1 7 5 to + 0.050 V. The polariza-
tion curve obtained using the 600 grit finish was quite similar to the curves
obtained using the special crevice test electrode as shown in Fig. 8. Further-
more, visual inspection of this test electrode after polarizing revealed
evidence of crevice attack around the mounting gasket. Thus, going from
180 GRIT SURFACE FINISH
600 GRIT SURFACE

FINISH
+ .3
+ .2
aEp
.225V
o
Q. CONVENTIONAL ELECTRODES
-Ep-.I75V
-.2 -
REGION
®
I02 10= lO'* 10=
CURRENT DENSITY, /A a/cm^
FIG- 9—Effect of surface finish on the 60.0-V/h potentiodynamic anodic polarization

curve for Type 304 stainless steel in the vicinity o/Ep; environment was aerated, 25°C, 4 per-
cent sodium chloride.
the rougher 180 grit surface to the finer 600 grit surface appeared to increase
pitting resistance but decrease crevice corrosion resistance. It should be
noted that evidence of crevice attack was found ( X 5 magnification) at the
mounting gasket crevice site even within the extremely short time of about
15 s required to measure the applied currents above E^ during the 60 V/h
potentiodynamic scan.
The 60-s current decay characteristics illustrated in Fig. 10, further
describe the eff"ects of mechanical polishing on the pitting resistance of
Type 304 stainless steel. The current densities decayed to less than 1
AiA/cm^ during 45 s at potentials of - 0 . 0 2 0 and - 0 . 1 5 0 V. These po-
tentials corresponded to Regions A and B, respectively, for the rougher
180 grit surfaces. A 16-h constant potential test at - 0 . 1 5 0 V failed to
produce any evidence of pitting attack. Another 16-h constant potential
test just above this E^ produced only crevice attack at the metal-epoxy
interface. These observations further confirmed that the 600 grit surface
finish led to more resistance to pitting than the 180 grit surface finish.
The effect of fine surface finish on crevice corrosion resistance is demon-
strated by the anodic polarization curves shown in Fig. 11. These polariza-
tion curves were those obtained on the fourteenth successive 60.0-V/h
potential scans on the special crevice electrode. While the E^, values were
similar and the repassivation potentials coincided, the current density
continued to increase for a longer period of time on the 600 grit finished
+.050V Ep(FORMERLY REGION C)
-.I50V(F0RMERLY REGION B)
15 30 45
TIME,SECONDS
FIG. 10—Current densities on Type 304 stainless steel for initial 60 s at selected applied
static potentials in aerated, 25°C, 4 percent sodium chloride (600 grit surface finish).
electrode surface after the potential scan was reversed. This suggests that
the crevice was more difficult to repassivate on the finer surface finish.
Generally, a comparison of the data for 180 and 600 grit surface finishes
suggests that finer mechanical polishing promotes increased resistance to
pitting. However, the increase in pitting resistance is accompanied by less
crevice corrosion resistance provided that crevice sites exist.
Having defined the portions of the 60-V/h polarization curve related to
pitting of Type 304 stainless steel, it was decided to also examine the
behavior of molybdenum-containing Type 316 stainless steel. It has been
well established that molybdenum, at levels found in Type 316 stainless
steel, is beneficial for pitting resistance. The polarization curve segments
illustrated in Fig. 12 confirm electrochemically this beneficial effect of
molybdenum. Comparing the measurements on 180 grit surfaces for Type
316 (Fig. 12) and Type 304 (Fig. 9) shows that molybdenum in Type 316
displayed Ep from —0.175 to +0.070 V, reduced the slope of the anodic
curve above £„ ,and noticeably shortened the potential span of Region B.
The noble Ep shift suggests that more oxidizing environments are required
to cause pit initiation in Type 316 stainless steel than in Type 304 stainless
steel.
Assuming, based on this work, that Region C is an electrochemical
response due to crevice corrosion and considering the established fact
t\ .2
POTENTIAL SCAN
tO.8 REVERSED AT S.OOOMO/cm^
Ul
^ • 0 - 4 - CREVICE ELECTRODES ^ _ ^ • f
>
>
_l
0.0
\ I —""^
JH
<
^ -0.4 - 600 GRIT SURFACE FINISH "^^^-t '- 180 GRIT SURFACE FIN
UJ
0- -0.8
n
-1.2
1 1 1 1
10 10* I0» 10^
CURRENT DENSITY â/cmZ
FIG. 11—Effect of surface finish on Type 304 stainless steel after the fourteenth successive
60.0-V/h potentiodynamic polarization scan, environment was aerated, 25°C, 4 percent
sodium chloride.
that lower current density (a steeper slope in Region C) corresponds to

better crevice corrosion resistance, then Type 316 stainless steel (Fig. 12)
should be more resistant to crevice corrosion than Type 304 stainless
steel (Fig. 9).
The anodic polarization curves for Types 304 and 316 stainless steels
obtained using 180 and 600 grit surface finishes are shown in Fig. 13.
Two points are evident from this figure. The first one is that Type 316
stainless steel responds to finer surface finishes in a manner similar to
Type 304 stainless steel. The second and most generally important point is
that any electrochemical comparisons aimed at detecting effects due to
compositional differences must be carried out using identical surface
finishes.
Discussion
Time is an important variable in the study of pitting and crevice corro-
sion. This work has shown that increasing the potential scan rate to
60.0-V/h limited pit and crevice development on the electrode by reducing
the test time. Consequently, reproducible anodic polarization curves were
obtained by eliminating interference from the local environmental changes
that are associated with pit or crevice propagation.
Time is also an important factor in constant potential tests. The low
current density values at or near Ep require long test periods to produce
180 GRIT
SURFACE FINISH
600 GRIT
SURFACE FINISH
REGION CE)
• 0.3
250V
tO.2 •>.nO\l/ RESIGN©

.+.I40V
REGION (D
• 0.1
•.070V
0.0
-0.1
O
a. -0.2 CONVENTIONAL ELECTRODES
_L.
10^ I0» 10*
CURRENT DENSITY fio/cm 2
FIG. 12—Magnified potential axis in the vicinity of ^^ for 60.0-V/h potentiodynamic

scans on Type 316 stainless steel in aerated, 25°C, 4 percent sodium chloride. Also, effect of
surface finish is illustrated.
visual evidence of attack, which then cause the responses from local
environment changes to interfere. In this study, measuring the current
densities attained at constant potentials during the initial 60 s minimized
this interference and helped to define Ep in terms of passivation kinetics.
A close examination of the anodic polarization curve in the potential
region near Ej, suggests that pits can be developed in constant potential
tests only under certain test conditions. If Region B is extremely narrow
due to inherent pitting resistance, or a fine surface finish or both, then a
potential corresponding to Region B may be difficult to locate. If the
potential selected for a static test lies in Region C instead of Region B,
then crevice attack would be expected to occur. Thus, if crevice attack is
developed in a static potential test, this does not imply that crevice attack
occurs at more active potentials than pitting attack. If may simply mean
that the electrode was held at a potential in Region C.
Sixteen-hour constant potential tests performed in this investigation
produced pits on a 180 grit surface correlating with a well defined Region B
on the polarization curve. Attempts to reproduce this attack on a 600 grit
surface failed, and for this surface finish Region B was poorly defined.
These observations demonstrate how surface finish can cause one to choose
a potential outside the pitting region during a static test.
The effects of surface finish on electrochemical response noted in this
investigation suggest that laboratory data will be of Httle value in antici-
TYPE 316
TYPE 3,6 180 GR,T SURFACE
TYPE 304
600 GRIT SURFACE 600 GRIT SURFACE
TYPE 304
GRIT SURFACE
CURRENT DENSITY fxa /cm^
FIG. 13—Effect of surface finish and alloy composilion on the 60.0-V/h poientiodynamic
polarization behavior in the vicinity of Ep in aerated, 25°C, 4 percent sodium chloride.
pating in-service corrosion behavior unless surfaces comparable to those

used in service are examined. Furthermore, if the surfaces of service
equipment are not uniform, some unexpected corrosion behavior may
develop. In particular, care should be taken in anticipating the corrosion
behavior of ground surfaces adjacent to welded joints, where differences in
finish may exist. The crossing of polarization curves for 600 grit finished
Type 304 stainless steel and 180 grit finished Type 316 stainless steel in
Fig. 13 reveals that under certain conditions surface finish can dominate
electrochemical response. If grinding of welded joints is a requirement in
service, then electrochemical evaluation of this type of surface finish
should be included.
It is also obvious that great care should be taken in selecting a repre-
sentative environment for laboratory evaluation. Referring again to Fig. 13,
it is seen that the anodic polarization curves for a Type 304 stainless steel
specimen with a 600 grit finish and a Type 316 stainless steel specimen
with a 180 grit finish cross over at a noble potential. Thus, the relative
corrosion behavior of these two specimens would be dependent on the
oxidizing power of the corrodant used.
A final point that should be noted is the electrochemical responses of
pitting corrosion and crevice corrosion appear to be revealed on a single
anodic polarization curve. The possibility exists, therefore, that further
research will enable a single electrochemical test to be developed capable

of defining both these forms of localized corrosion. Further studies are in
progress aimed at exploring the relationship between crevice attack and
Region C on the anodic polarization curve.
References
[/] Pourbaix, M., Corrosion Science, Vol. 3, 1963, p. 239.
[2] Schwenk, W., Corrosion Science, Vol. 5, 1965, p. 245.
[i] Leckie, H. P. and Uhlig, H. H., Journal of the Electrochemical Society, Vol. 113, 1966,
p. 1262.
{4] Bond, A. P. and Lizlovs, E. A., Journal of the Electrochemical Society, Vol. 115, 1968,
p. 1130.
[5] Wilde, B. E., Corrosion, Vol. 28, No. 8, 1972, p. 283.
[6] Johnson, M. J. in Localized Corrosion—Cause of Metal Failure, ASTM STP 516,
American Society for Testing and Materials, 1972, pp. Idl-lll.
[7] Broli, Aa, Holtan, H., and Midjo, M., British Corrosion Journal, Vol. 8, July 1973,
p. 175.
[S] Rosenfeld, I. L. and Marshakov, I. K., Corrosion, Vol. 20, 1964.
[9] France, W. D., Jr. and Greene, N. D., Jr., Corrosion, Vol. 24, 1968, p. 247.
[70] Lizlovs, E. A., Journal of the Electrochemical Society, Vol. 117, 1970, p. 1335.
[ll] Suzuki, T. and Kitamura, Y., Corrosion, Vol, 28, No. 1, 1972, p. 1.
[12] France, W. D., Jr. in Localized Corrosion—Cause of Metal Failure, ASTM STP 516,
[13] Pessall, N. and Liu, C , Eleclrochimica Acta, Vol. 16, 1971, pp. 1987-2003.
[14] Lizlovs, E. A. and Bond, A. P., Journal of the Electrochemical Society, Vol. 116, 1969,
p. 574.
[15] Herbsheb, G., Werkstoffe und Korrosion, Vol. 17, 1966, p. 649.
[16] Leckie, H. ?., Journal of the Electrochemical Society, Vol. 117, 1970, p. 1152.
[77] Lizlovs, E A. and Bond, A. P., "An Evaluation of Some Electrochemical Techniques
for the Determination of Pitting Potentials of Stainless Steel," presented at the Annual
Meeting, National Association of Corrosion Engineers, Chicago, III., 7 March 1974.
[75] Jackson, R. P. and Van Rooyen, D. in Localized Corrosion—Cause of Metal Failure,
ASTM STP 516, American Society for Testing and Materials, 1972, p. 210.
[79] Smith, H. A., Metal Progress, Vol. 33, 1938, p. 596.
[20] Isaacs, H. S. and Kissel, G., Journal of the Electrochemical Society, Vol. 119, No. 12,
1972, p. 1628.
[27] Hospadaruk, V. and Petrocelli, J. J., Journal of the Electrochemical Society, Vol. 113,
1966, p. 878.
[22] Greene, N. D. in Experimental Electrode Kinetics, Rensselaer Polytechnic Institute,
Troy, N. Y., 1965, p. 5.
[23] Morris, P. E. and Scarberry, R. C , Corrosion, Vol. 26, No. 7, 1970, p. 169.
[24\ Morris, P. E. and Scarberry, R. C , Corrosion, Vol. 28, No. 12, 1972, p. 444.
STP576-EB/Feb. 1976
Compilation of Literature References on

Pitting Corrosion 1
Aluminum
[/] Aziz, P. M. and Godard, H. P., "Pitting Corrosion Characteristics of Aluminum:
Influence of Magnesium and Manganese," Industrial and Engineering Chemistry,
Vol. 44, No. 8, Aug. 1956, pp. 1791-1795.
[2] Porter, F. C. and Hadden, S. E., "Corrosion of Aluminum Alloys in Supply Waters,"
Journal of Applied Chemistry, Vol. 3, Sept. 1953, p. 385.
[3] Aziz, P. M., "Views on the Mechanism of Pitting Corrosion of Aluminum," Corrosion,
Vol. 9, No. 3, March 1953, pp. 85-90.
[4] Aziz, P. M., "Radioactive Tracers in the Study of Pitting Corrosion on Aluminum,"
Journal of the Electrochemical Society, Vol. 101, No. 3, March 1954, pp. 120-127.
[5] Aziz, P. M. and Godard, H. P., "Pitting Corrosion Characteristics of Aluminum:
Influence of Iron and Silicon," Corrosion, Vol. 10, No. 9, Sept. 1954, pp. 269-272.
[6] KTXL, P. M. and Godard, H. P., "Influence of Specimen Area on the Pitting Proba-
bility of Aluminum," Journal of the Electrochemical Society, Vol. 102, No. 10, Oct.
1955, pp. 577-579.
[7] Aziz, P. M., "Application of the Statistical Theory of Extreme Values to the Analysis
of Maximum Pit Depth Data for Aluminum," Corrosion, Vol. 12, Oct. 1956, p. 495t.
[8] Hagyard, T. and Santhiapillai, J. R., "Pitting Corrosion of Aluminum in Sodium
Chloride Solutions," Journal of Applied Chemistry, Vol. 9, Part 6, June 1959, pp.
323-330.
[9] Bassett, G. A. and Edeleanu, C , "Pitting of Aluminum at Grain Boundaries After
Aging," Philosophical Magazine, Vol. 5, No. 60, Dec. 1960, pp. 1217-1220.
[10] Godard, H. P., "The Corrosion Behavior of Aluminum in Natural Waters," Canadian
Journal of Chemical Engineering, Vol. 38, Oct. 1960, p. 167.
[11] Porter, F. C , "Aluminum and Corrosion: A Review of Progress in 1960," Corrosion
Prevention and Control, Vol. 8, Jan. 1961, pp. 37-43.
[12] Videm, K., "Pitting Corrosion of Aluminum in Contact with Stainless Steel,"
Teknsk Vkeblad, Vol. 108, No. 33, 1961, pp. 775-784 (Norwegian).
[13] Booth, F. F. and Latimer, K. G., "Aluminum Alloys—Corrosion Behavior in an
Industrial Environment," Corrosion Technology, Vol. 9, No. 11, Nov. 1962, pp.
315-320.
[14] Ailor, W. H., Jr. and Reinhart, F. M., "Ten-Year Weathering Data on Aluminum
Alloys," Materials Protection, Vol. 2, No. 6, June 1963, pp. 30-31, 33, 36.
[15] Kaesche, H., "Investigations on the Corrosion of Aluminum," Werkstoffe und
Korrosion, Vol. 14, No. 7, July 1963, pp. 557-565.
[16] Fujiwari, T. and Shingai, T., "On Micro-Pits Produced by Formation of FeAl 3 in
Rolled Plate of Extra Super-Duralumin (7075-T6)," Nippon Kinzoku Gekkai-Si, Vol.
28, No. 9, 1964, pp. 502-507 (Japanese).
1
Compiled by L. C. Rowe, Chairman of a Task Group on Pitting Corrosion under
ASTM Subcommittee G01.05 on Laboratory Corrosion Tests. Many of the references
were contributed by members of the task group; others were obtained from surveys,
indexes, and a search of particular journals. No compilation is ever complete, but these
references provide a good review of the activity in pitting corrosion during the last 15 years.
276

University of Washington (University of Washington) pursuant to Lic
COMPILATION OF LITERATURE REFERENCES 277
[J7] Koehler, E. L. and Evans, S., "Pitting and Uniform Corrosion of Aluminum by pH
3.5 Citrate Buffer Solution," Journal of the Electrochemical Society, Vol. I l l , No. 1,
Jan. 1964, pp. 17-21.
[18] Murray, G. A. W., "Artificial Pits for Quantitative Studies of Corrosion of Aluminum
Alloys in Natural Waters," Corrosion, Vol. 20, Oct. 1964, pp. 329t-334t.
[19] Kaesche, H., "On Uniform Dissolution and P'tting of Aluminum Electrodes,"
Korrosion, Vol. 16, 1964, pp. 17-19.
[20] Campbell, H. S., "Corrosion and Protection of Aluminum Alloys Underground,"
Journal of the Institute of Metals, Vol. 93, 1964-65, p. 97.
[21] Storchai, E. I. and Turkovskaya, A. V., "Investigation of Susceptibility to Spot and
Pitting Corrosion in Some Aluminum Alloys," Khim Neftyanoe Mashinostr, No. 3,
1965, pp. 32-34 (Russian).
[22] Storchai, E. I. and Turkovskaya, A. V., "Pitting Corrosion of Aluminum Alloys,"
Protection of Metals, Vol. 1, No. 3, May-June 1965, p. 256.
[23] Hijber, W. and Wranglen, G., "Studies on the Mechanism of the Pitting Corrosion
of Aluminum," Current Corrosion Research in Scandinavia, Kemian Keskusliito,
r. y., Helsinki, Finland, 1965.
[24] Bond, A. P., Boiling, G. F., Domian, H. A., and Biloni, H., "Microsegregation and
the Tendency for Pitting Corrosion in High-Purity Aluminum," Journal of the
Electrochemical Society, Vol. 113, Aug. 1966, p. 773.
[25] Freiman, L. I. and Kolotyrkin, Va. M., "Pitting Corrosion of Aluminum in Solu-
tions of Sodium Perchlorate and Chloric Acid," Zaschita Metallov, Vol. 2, No. 4,
1966, pp. 488-490 (Russian).
[26] Elze, J., "Causes and Forms of Pitting of Aluminum Anodized by the GX Process,"
Mitteilungen der Forschungsgesellschaft Blechverarbeitung, Vol. 17, 1966 (German).
[27] Sugimoto, K., Sawada, Y., and Morioka, S., "Pitting Dissolution Behaviors of Pure
Aluminum and SAP (Sintered Aluminum Powders) in Weak Alkaline Aqueous
Solutions of NaCl," Journal of the Japan Institute of Metals, Vol. 30, No. 10, Oct.
1966, pp. 977-984 (Japanese).
[28] Kasen, M. B., Taggart, R., and Polonis, D. H., "The Effects of Environment on
Surface Pit Formation in Aluminum," Philosophical Magazine, Vol. 13, 1966.
[29] Ailor, W. H., "Five-Year Corrosion of Aluminum Alloys at Several Marine Sites,"
British Corrosion Journal, Vol. 1, May 1966, p. 237.
[30] Izaki, T. and Arai, K., "Studies on Pitting Corrosion of Aluminum and Its Alloys
in Neutral Solutions," Journal of the Japan Institute of Metals, Vol. 31, No. 9, Sept.
1967, pp. 1023-1028 (Japanese).
[31] Murray, G. A. W., Lamb, H. J., and Godard, H. P., "Role of Iron in Aluminum on
the Initiation of Pitting in Water," British Corrosion Journal, Vol. 2, No. 6, Nov. 1967,
pp. 216-218.
[32] Penn, J. H. and Murray, G. A. W., "Effect of Acidic Gelatinous Materials on Pitting
Corrosion of Aluminum Hollow-Ware," British Corrosion Journal, Vol. 2, No. 5,
1967, pp. 193-194.
[33] Johnson, W. K. and Wright, T. E., "The Effect of Small Additions of Copper on
the Corrosion Resistance of Aluminum and Aluminum Alloys," Aluminum, Vol. 43,
No. 8, Aug. 1967, pp. 490-496 (German).
[34] Horibe, K., "Studies on Pit Formation on Aluminum Immersed in Artificial Waters,"
Journal of the Japan Institute of Light Metals, Vol. 18, No. 11, Nov. 1968, pp. 579-
585 (Japanese).
[35] Kassayura, V. P. and Zaretskii, E. M., "Anodic Behavior of Aluminum in Solutions
of Sodium Nitrate in the Presence of Chloride Ions," Protection of Metals, Vol. 4,
No. 4, July-Aug. 1968, p. 343.
[36] Tapper, R. W., "Corrosion of Aluminum—Literature Review," British Corrosion
Journal, Vol. 3, Nov. 1968, pp. 285-287.
[37] Tegun, O., "Pitting in Aluminum and its Alloys in Pure Water," Journal of the Japan
Institute of Metals, Vol. 18, March, pp. 127-138.
[38] Sugimoto, K., Sawada, Y., and Morioka, S., "Effects of Matrix Purity and Environ-
ment Factors on the Anodic Pitting Dissolution Behaviors of Aluminum," Nippon
Kinzoku Gakkai-Si, Vol. 32, No. 9, 1968, pp. 842-848 (Japanese).
[39] Ailor, W. H., Jr., "Performance of Aluminum Alloys at Other Test Sites," Metal
Corrosion in the Atmosphere, ASTM STP 435, American Society for Testing and
Materials, 1968, p. 285.
[40] McGeary, F. L., Summerson, T. J., and Ailor, W. H., Jr., "Atmospheric Exposure
of Non-Ferrous Metals and Alloys—Aluminum: Seven-Year Data," Metal Corrosion
in the Atmosphere, ASTM STP 435, American Society of Testing and Materials,
1968, p. 141.
[41] Ailor, W. H., Jr., Evaluation of Aluminum After One-Year Deep Sea Exposure,"
Journal of Hydronautics, Vol. 2, No. 1, Jan. 1968, p. 26.
[42] Bohni, H. and Uhlig, H. H., "Environmental Factors Affecting the Critical Pitting
Potential of Aluminum," Journal of the Electrochemical Society, Vol. 116, 1969, p. 906.
[43] Di Russo, E., Prati, A., and Sacchi, F., "Investigation on the Mechanism of Pitting
Corrosion of Anodized Alloy Al-Mg-Si for Architectural Purposes," Atlumino, Vol.
38, No. 1, Jan. 1969, pp. 3-13 (Italian).
[44] Ailor, W. H., Jr., "A Review of Aluminum Corrosion in Tap Water," Journal of
Hydronautics, Vol. 3, No. 3, July 1969, p. 105.
[45] Ailor, W. H., Jr., "Aluminum Corrosion at Urban and Industrial Locations,"
Journal of the Structural Division, Vol. 95, No. STIO, Oct. 1969, pp. 2141-2160.
[46] Ailor, W. H., Jr., "Aluminum Alloys After Five Years in Seawater," Materials Per-
formance and the Deep Sea, ASTM STP 445, American Society for Testing and
Materials, 1969, p. 115.
[47] Storchai, E. I. and Turkovskaya, A. V., "Use of Charge Curves for Determining the
Potential of Pitting Formation on Aluminum Alloys," Industrial iMboralory, Vol. 35,
No. 6, June 1969, pp. 851-852.
[48] Arora, O. P., Isasi, J. A., and Metzger, M., "Protective Films and Structure-Depend-
ent Corrosion in Aluminum," Corrosion, Vol. 25, No. 11, Nov. 1969, pp. 445-454.
[49] Horibe, K., "Studies on Pit Formation on Aluminum Immersed in Artificial Waters,"
Journal of the Japan Institute of Light Metals, Vol. 19, No. 3, March 1968, pp. 105-
111, 184-188 (Japanese).
[50] Ishida, S., "Some Studies on Pit Formation on Aluminum Immersed in Waters,"
Proceedings of the Third International Congress on Metallic Corrosion, National
Association of Corrosion Engineers, Vol. 1, Houston, Tex., 1969, pp. 179-185.
[51] Richardson, J. A. and Wood, G. C , "A Study of the Pitting Corrosion of Al by
Scanning Electron Microscopy," Corrosion Science, Vol. 10, 1970, p. 313.
[52] Lorking, K. F. and Mayne, J. E. O., "The Corrosion of Aluminum," Journal of
Applied Chemistry, Vol. 11, May 1961, p. 170.
[53] Goto, K., Ito, G., and Shimizu, Y., "Effect of Some Oxidizing Agents on Pitting
Corrosion of Aluminum in Neutral Water," Journal of Japan Institute of Light Metals,
Vol. 20, Feb. 1970, pp. 88-94 (Japanese).
[54] Paydya, B. A., Sampat, S. S., Vora, J. C , and Trivedi, A. M., "Corrosion of Alumi-
num in Salt Mixtures and the Influence of Copper Ions on Corrosion," Werkstoffe
und Korrosion, Vol. 21, No. 10, 1970, pp. 801-803 (German).
[55] Pourbaix, M., "Some Aluminum Corrosion Problems and Their Practical Repercus-
sions," Revue de l'Aluminum, Vol. 386, June 1970, pp. 639-647 (French).
[56] Storchai, E. I. and Turkovskaya, A. V., "Pitting of Aluminum Alloys in Solutions of
of NaCl Without Oxidizing Agent," Zaschita Metallov, Vol. 6, No. 6, 1970 (Russian).
[57] Johnson, W. K., "Recent Developments in Pitting Corrosion of Aluminum," British
Corrosion Journal, Vol. 6, 1971, p. 200.
[55] deDeMichele, S. M. and Galvele, J. R., "Morphology of Pitting Corrosion of Alumi-
num in Different Electrolytes," Metalurgia A.B.M., Vol. 27 (165), Aug. 1971,
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Graphite
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[297] Kolotyrkin, Ya. M., "Pitting Corrosion of Metals," Proceedings of the Second
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1963, pp. 261t-268t.
[298] Schwenk, W., "Theory of Stainless Steel Pitting," Corrosion, Vol. 12, No. 4, April
1964, pp. 129t-137t.
[299] Hoar, T. P., Mears, D. C , and Rothwell, G. P., "The Relationship Between Anodic
Passivity, Brightening, and Pitting," Corrosion Science, Vol. 5, 1965, pp. 279-289.
[300] Greene, N. D. and Judd, G., "Relation Between Anodic Dissolution and Resistance
to Pitting Corrosion," Corrosion, Vol. 21, 1965, p. 15.
[301] Vetter, K. J., "A Thermodynamic Theory of Pitting Corrosion," Berichte der Bunsen-
gesellschaft fur Physikalische Chemie, Vol. 8, 1965, pp. 683-688.
[302] France, W. D., Jr., "Controlled Potential Investigations of Localized Corrosion
Phenomena," Ph.D. thesis. University Microfilms, No. 67-4167.
[303] Hubner, W., "Pitting Corrosion of Passivated Metals," Svensk Kemisk Tidskrift,
Vol. 78, No. 6/7, 1966, pp. 321-355 (Swedish).
[304] Finley, H. F., " A n Extreme-Value Statistical Analysis of Maximum Pit Depths and
Time to First Perforation," Corrosion, Vol. 23, No. 4, 1967.
[305] Kaesche, H., "Mechanism of Pitting Corrosion," Corrosion Traitemenis Protection
Finilion, Vol. 17, No. 8, 1969.
[306] Prazhak, M., Toushek, Ya., and Spanilyi, V., "Role of Anion Absorption in Pitting
Corrosion and Stress Corrosion Cracking of Metals," Protection of Metals, Vol. 5,
1969, p. 329.
[307] Rosenfeld, I. L. and Danilov, I. S., "Electrochemical Aspects of Pitting Corrosion,"
Proceedings of the Third International Congress on Metallic Corrosion, Vol. 1, National
[308] Swann, P. R., "Mechanism of Corrosion Tunneling with Special Reference to
CusAu," Corrosion, Vol. 25. No. 4, 1969, pp. 147-150.
[309] Brown, B. F., "Concept of the Occluded Corrosion Cell," Corrosion, Vol. 26, 1970,
p. 249.
[310] Leckie, H. P., "A Contribution to the Applicability of Critical Pitting Potentials,"
Journal of the Electrochemical Society, Vol. 117, 1970, pp. 1152.
[311] Pourbaix, M., "Significance of Protection Potential in Pitting and Intergranular
Corrosion," Corrosion, Vol. 26, No. 10, Oct. 1970, p. 431-438.
[312] Pourbaix, M., "Metallic Corrosion," Technical Report No. RT-175, Beige D'Etude
de la Corrosion, Brussels, Belgium, June 1970.
[313] Vermilyea, J., "Concerning the Critical Pitting Potential," Journal of the Electro-
chemical Society, Vol. 118, No. 4, 1971, p. 529.
[314] Szklarska-Smialowska, Z., "Review of Literature on Pitting Corrosion Published
Since 1960," Corrosion, Vol. 27, No. 6, 1971, pp. 223-233.
[315] Bosch, R. M. and Defrancq, J., "The Problem of Initiation and Growth in Pitting
Corrosion," Cebelcor Technical Report No. RT-196, Centre Beige D'Etude de la
Corrosion, Brussels, Belgium, June 1971.
[316] Tousek, J., "The Question of the Pitting Corrosion Mechanism," Werkstoffe und
Korrosion, Vol. 23, 1972, pp. 109-112.
[317] Pourbaix, M., "Significance of Protection Potential in Pitting, Intergranular Cor-
rosion, and Stress-Corrosion Cracking," Journal of Less-Common Metals, Vol. 28,
1972, p. 51.
[318] Frankenthal, R. P. and Pickering, H. W., "On the Mechanism of Localized Corrosion
of Iron and Stainless Steel: Part 1. Electrochemical Studies; Part II. Morphological
Studies," Journal of the Electrochemical Society, Vol. 119, No. 10, Oct. 1972, p. 1297
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[319] Ciolac, S., "Corrosion Pitting in Metals: Part 1. Interdependence Pitting-Passivity,
Theory and Development Stages of the Pitting Process; Part II. Methods of Investi-
gation and Protection," Studii Si Cercetari De Cliimie, Vol. 21, 1973, No. 5, pp.
597-610, No. 6, pp. 669-684.
[320] Uhlig, H. H., "Distinguishing Characteristics of Pitting and Crevice Corrosion,"
Materials Protection and Performance, Vol. 12, Feb. 1973, pp. 42-44.
[321] Hisamatsu, Y. and Ichikawa, K., "Etch-Pitting as a Faceting Dissolution Process,"
Corrosion Engineering, Vol. 23, No. 3, 1974, and Proceedings of the Fifth International
Houston, Tex., 1974, pp. 275-280.
[322] Rosenfeld, I. L., "Local Corrosion Process," Proceedings of the Fifth International
Houston, Tex., 1974, pp. 53-73.
[323] Ives, M. B., "Etch Pitting—Theory and Observation," Localized Corrosion, R. W.
Staehle, B. F. Brown, J. Kruger, and A. Agrawal, Eds., National Association of
Corrosion Engineers, Houston, Tex., 1974, pp. 78-103.
[324] Vetter, K. J. and Strehblow, H. H., "Pitting Corrosion in an Early Stage and Its
Theoretical Implications," Localized Corrosion, R. W. Staehle, B. F. Brown, J. Kruger,
and A. Agrawal, Eds., National Association of Corrosion Engineers, Houston, Tex.,
1974, pp. 240-251.
[325] Hoar, T. P.,"Bright Pitting," Localized Corrosion, R. W. Staehle, B. F. Brown, J.
Kruger, and A. Agrawal, Eds., National Association of Corrosion Engineers, Hous-
ton, Tex., 1974, pp. 112-116.
Titanium
[326] Pigott, R. A. and Schreir, L. L., "Micropitting of Titanium During Anodic Oxida-
tion in Formic Acid," Nature, Vol. 189, 21 Jan. 1961, pp. 216-217.
[327] Fischer, W. R., "Study of Pitting Corrosion, Especially on Titanium: Part I. Cor-
rosion Investigations; Part II. Electrochemical Studies," Technische MitteUlangen
Krupp, Ausgabe A. Forschmgsberichle, Vol. 22, No. 3 and 4,1964, pp. 65-82, 125-142.
{328\ Dugdale, I. and Cotton, J. B., "The Anodic Polarization of Titanium in Halide
Solutions," Corrosion Science, Vol. 4, 1964, p. 397.
[329] Posey, F. A. and Bohlmann, E. G., "Pitting of Titanium Alloys in Saline Waters,"
Desalination, Vol. 3, 1967, p. 269.
[330] Kolotyrkin, Ya. N. and Strunkin, V. A., "Pitting of Titanium on Application of an
Alternating Current," Zashchita Metallov, Vol. 6, No. 5, 1970.
[331] Mansfeld, P., "The Effect of Water on Passivity and Pitting of Titanium in Solutions
of Methanol and Hydrogen Chloride," Journal of the Electrochemical Society, Vol.
118, Sept. 1971, p. 1412.
[332] Cotton, J. B., "Pitting Corrosion of Titanium," British Corrosion Journal, Vol. 7,
March 1972, pp. 59-69.
[333] Beck, T. R., "Pitting of Titanium: Part I. Titanium-Foil Experiments; Part II.
One-Dimensional Pit Experiments," Journal of the Electrochemical Society, Vol.
120, No. 10, 1973.
[334] Beck, T. R., "A Review: Pitting Attack of Titanium Alloys," Localized Corrosion,
Tungsten
[335] Maloof, S. R., "Dislocation Etch Pitting Studies on Tungsten Single Crystals Under
Potentiostatic Conditions," Corrosion, Vol. 24, No. 9, Sept. 1968, pp. 283-290.
[336] Stolica, N. D., "Pitting of Tungsten in LiCl-Methanol-HjO Solutions," Proceedings
of the Fifth International Congress on Metallic Corrosion, National Association of
Corrosion Engineers, Houston, Tex., 1975.
Zinc
[337] Kaesche, H., "Investigation of Pitting of Galvanized Steel Tubes and the Effect of
Element Formation on Copper Precipitation," VDI-Berichte, No. 72, 1963, pp. 64-71
(German).
[338] Kamel, R., "Natural Pitting on Cleaved Surfaces of Zinc Crystals," Acta Metallur-
gica. Vol. 11, No. 6, June 1963, pp. 629-630.
[339] Davies, D. E. and Lotlikar, M. M., "Passivation and Pitting Characteristics of Zinc,"
British Corrosion Journal, Vol. 1, Jan. 1966, p. 149.
[340] Lotlikar, M. M. and Davies, D. E., "The Potentiostatic Investigation of the Passivity
and Pitting Characteristics of High-Purity Zinc," Proceedings of the Third Inter-
national Congress on Metallic Corrosion, Vol. 1, National Association of Corrosion
[341] Krug, H. and Borchers, H., "Pitting Corrosion Under Hydrogen Bubbles Adherent
to the Surface of Zinc," Werkstoffe und Korrosion, Vol. 22, No. 4, 1971, pp. 309-311
(German).
Zirconium
[342] Tomiki, T. and Ogawa, S., "Electro-Microscopic Observation on Chemically Etched
Surfaces of Polycrystalline Zirconium," Journal of Japan Institute of Metals, Vol. 24,
1960, pp. 522-526.
COMPILATION OF UTERATURE REFERENCES 293
[343] Kolotyrkin, Ya. M. and Gil'man, V. A., "Effect of Chloride Ions on the Electro-
chemical and Corrosion Behavior of Zirconium," Doklady Akadamie Nauk S.S.S.R.,
Vol. 137, 21 March 1961, pp. 642-645 (Russian).
[344] Gil'man, V. A, and Kolotyrkin, Ya. M., "The Mechanism of the Corrosion Pitting of
Zirconium in Halide Solutions," Doklady Akademie Nauk S.S.S.R., Vol. 143,
21 March 1962, pp. 640-642 (Russian).
[345] Stoops, D. J., Carver, M. D., and Kato, H., "Corrosion of Zirconium in Cupric and
Ferric Chlorides," Non-Atomic Energy Commission Publication 5945, 1962, avail-
able from U.S. Department of the Interior, Bureau of Mines, Washington, D.C.
STP576-EB/Feb. 1976
Summary
The Galvanic and Pitting Corrosion symposia have presented recent

laboratory and field corrosion study results in a broad spectrum of cor-
rosive environments that include controlled clean and polluted air, distilled
water, 3.5 percent sodium chloride solutions, tap water, seawater, hot
brine solutions, organic solutions, and dry high resistivity to wet low
resistivity soils.
Pitting is a form of localized corrosion attack which can lead to early
failure. Galvanic corrosion has also been the reason for many premature
failures. Unfortunately, there are numerous engineering alloys that are
highly susceptible to pitting corrosion, for example, the stainless steels
and the 2000 and 7000 series aluminum alloys. The aluminum alloys are
additionally susceptible to galvanic attack since they are anodic to all other
engineering metals (and their alloys) except magnesium and zinc.
The paper by Baboian on electrochemical techniques for predicting
galvanic corrosion covers potential, current, and polarization measure-
ments. Although each of these can be useful in determining galvanic effects,
he has pointed out that measurements should be made in the actual environ-
ment to which materials are exposed. Where potential and current measure-
ments have limitations with regard to localized galvanic corrosion, polari-
zation techniques can be quite useful in predicting the susceptibility to
this type of corrosion.
The examination of the galvanic attack of aluminum alloys by ferrous
and nonferrous cathodic materials in aqueous media by Mansfeld and
Kenkel presents, in effect, a galvanic series for these galvanic couples in
specific media. Although some may quarrel with the relatively short
test duration, it is obvious that their data can provide a basis for preliminary
design.
Compton found that the distribution of cathodic protection current
between members of copper steel and stainless steel aluminum in galvanic
couples varied by a ratio 940 to 0.05 as the relative areas were varied from
100:1 to 1:100. Polarization and current distribution measurements have
295

shown that at about a 1:1 ratio of cathode to anode, cathodic protection

does not appear to be practical.
The method for performing corrosion tests of weldments by Compton
and Turley is a straight-forward approach to determining the susceptibility
of weld and heat affected zones to accelerated galvanic corrosion attack.
Of the nine ferrous and nonferrous weldment systems tested, there was
only one wherein the base metal would provide cathodic protection to the
smaller surface areas of the weld and heat affected zones.
The galvanic corrosion tests of Shick and Mitchell on underground
cable materials using the galvanostatic polarization technique to determine
potential and current density established that semiconducting polyethylene
jacketing of power cables becomes the cathode of a galvanic cell (poly-
ethylene coupled to concentric neutral copper wires) because the poly-
ethylene contains carbon particles. Another significant result is that aerated
soil increased the corrosion rates by orders of magnitude as compared
to deaerated soil.
Escalante and Gerhold in their galvanic coupling of stressed stainless
steels to the anodic materials iron, zinc, and magnesium at six different
underground sites found that the higher strength work-hardened stainless
steel alloy Type 301 was inferior to alloy Type 304 and 26 Cr-lMo in its
resistance to cracking. Alloy Type 301 consistently cracked at stresses
that were only 22 to 36 percent of the alloy's yield stress as compared to
alloys Type 304 and 26 Cr-lMo that never failed even though the stress
levels were from 34 to 93 percent of yield stress. Since there was no failure
of noncoupled Type 301 specimens, it is concluded (rightly so) by Escalante
and Gerhold that cracking is the result of hydrogen embrittlement that
occurs due to the cathodic reaction at alloy Type 301 cathode.
An extensive galvanic corrosion investigation in the Panama Canal Zone
including atmosphere, soil, and seawater environments has been described
by Pelensky et al. They describe test techniques and initial results of this
work.
Specimens of galvanized steel sheet were exposed to polluted and clean
air by Spence and Haynie. They show that corrosion of zinc film is essen-
tially a linear function of time. Although weight losses were approximately
the same in both environments, uniform corrosion of the zinc occurred in
the polluted exposure, whereas pitting was observed in the clean air
environment.
Covington describes the pitting problems encountered in titanium tubes
in heat exchangers handling hot saturated brine. Two types of pits appear:
symmetrical pits about 0.6 cm in diameter which are associated with
scratches containing iron, and irregular pits believed to be associated with
salt plugs.
The studies by Cornwell et al of pitting of copper tubing by domestic
water conclude that in certain types of domestic waters the presence of
of carbon residue from the tube manufacturing operations will result in
SUMMARY 297
pitting failure in a period of only three months. The authors' solution to

this problem is to reduce the carbon contamination through abrasive
cleaning.
This position is questioned by Cohen who maintains that it has never
been conclusively demonstrated that carbon films on the inside diameter
of copper water tubing are the cause of pitting corrosion. Cohen's position
is that the cause of pitting in copper water tubes is the chemical make up
of a given water system and that the proper solution to this problem is to
treat the corrosive water through the addition of lime or caustic soda.
Cornwell et al, in response to Cohen, agree that pitting of copper water
tubing is related to specific waters, but their test results show that carbon
free tubes did not pit in the same waters that caused rapid failure of carbon
containing copper tubes. It is apparent from the data presented by both
parties that the pitting corrosion of copper water tubes can be related to
both water chemistry and residue carbon films. The service experience
related by both parties support their particular position (carbon removal
versus water chemistry control), and there is little doubt that both are
correct for the case histories given.
Mansfeld covers the pitting behavior of titanium, nickel, 6061 aluminum
and Type 304 stainless steel in methanol in the presence of sulfates or
chlorides. The behavior of metals in these environments contrast sharply
the behavior in aqueous systems. For example, titanium corrodes rapidly
in anhydrous methanol because passivation cannot occur. However,
additions of water at a concentration as low as 0.6 percent leads to passiva-
tion of the titanium.
The review on "Measurement and Evaluation of Pitting Corrosion"
by Rowe elaborates on the visual nondestructive and destructive techniques
that are used to determine density of pits (number/cm^) and maximum
depth of pitting attack. This review came about through the development
of a Recommended Practice for Measurement and Evaluation of Pitting
Corrosion by ASTM Subcommittee GDI.05 on Laboratory Corrosion
Tests.
The basic approach presented by Rowe is to visually examine metals
at low magnification to determine the general magnitude of pitting attack.
It is correctly emphasized that metal weight loss alone is not a satisfactory
procedure for the determination of the extent of pitting. The destructive
cross sectioning of pits to provide microscopic measurement or the pro-
gressive machining to the bottom of a pit can provide accurate measure-
ments but these techniques are costly, time consuming, and impractical
where numerous specimens are involved. The nondestructive measurement
techniques of a micrometer or a dial indicator with a sharp tungsten tip
or a microscope with a graduated focusing knob are more rapid but do
have the limitation of not being able to measure those pits that are not
completely open to their bottom.
Rowe makes a most valid point that measurement of maximum pit

depth or the average of a number of deepest pits is often the most mean-
ingful method of demonstrating the magnitude of pitting corrosion. An
equally important test of the effect of pitting is the change in mechanical
properties of the corroded material. These can include ultimate and tensile
yield strength, elongation, and reduction in area. The measure of the effect
of pitting on the fatigue strength of a material is most important when the
material is to be exposed to cyclical stress in a corrosive environment.
Crews proposes a statistical treatment of pitting corrosion data which
calculates the prediction intervals of pit depth which can be used to obtain
quantitative estimates of service life or corrosion rate in normally en-
countered environments. The statistical treatment in this paper utilizes a
prepared computer program which provides calculated values of both the
regression and the distribution, expressed as prediction intervals of pit
depth for times both within the exposure period of the test and extrapolated
exposure times.
The crevice corrosion test cell presented by Anderson offers a new
method of determining susceptibility of a material to localized corrosion.
The advantages of the new test configuration are that it provides 40 small
crevices per specimen, is inexpensive to produce, and can be used to
statistically predict corrosion initiation and propagation.
Anderson's tests on stainless steel, copper, and nickel alloys were per-
formed in seawater. However, the test fixture uses the plastic material
Delrin which is highly resistant to many corrosive environments such as
acid and alkali solutions, and it could, therefore, be used in these environ-
ments.
Petersen uses a unique apparatus to duplicate the environment of a pit.
Although this is a difficult if not an impossible task, the results of his work
show some interesting correlations between corrosion of carbon steel and
solution changes within a cavity. He finds a correlation between pH change
and reaction of magnesium and calcium in the electrolyte.
The problem associated with measurements of the critical potentials of
stainless steels is covered by Morris. Using the rapid-scan potentiodynamic
polarization technique, crevice corrosion can be prevented, thereby per-
mitting accurate and reproducible measurement of the pitting potential.
The compilation of literature references on pitting corrosion includes
sections on aluminum, copper, electroplated coatings, environmental
effects, graphite, iron and steel, iron-chromium-nickel alloys, nickel, test
methods, theoretical, titanium, tungsten, zinc, and zirconium.
Thus, the authors of the papers have presented a wide range of test
techniques and results in various environments with a range of materials.
This information represents the cumulative efforts of many years of work
and is presented herein as a guide to present and future investigations.
STP576-EB/Feb. 1976
In ex
A ASTM exposure racks, 98
Atmospheric exposure, 94, 98, 106
Aluminum and aluminum alloys, 14, Clean air, 132, 138
21-28, 31, 32, 35, 4 1 , 42, Galvanic, 94
50-54, 62 Panama Canal Zone, 94
1100,28,40,43 Polluted air, 141
2024, 26, 28, 32, 37, 40, 43 Atmospheric pollutants
2219, 40, 43 Effect on materials, 132
4043, 62 Effect on pitting, 136
5052,212-214
Nitrogen dioxide, 133
5086, 63
Ozone, 133
5356,63
Sulfur dioxide, 133
6061, 23, 26, 40, 43, 61-63, 96,
Autoclave tests, 148
103-112, 189
7075, 22, 28, 32, 37, 38, 43, 96,
B
103-112
Compatibility with dissimilar Bimetallic couples (see also Gal-
materials, 42 vanic couples and Dissimilar
Corrosion potentials, 23 metals), 48
Corrosion rates, 23 Brine solutions, 147
Galvanic corrosion, 20 Pitting of titanium, 147
Galvanic series, 26 Buried structures (see also Soils), 69
Literature references on pitting,
276 C
Maximum pit depth, 212
Pipeline, 214 Carbon
Pitting probability, 212 Effect on pitting of copper tubes,
Power cables, 71 162, 166, 177, 178
Area ratio, 15, 32, 36, 38, 50, 52, Residue in copper tubes, 156,
54, 55, 66, 79, 139, 237, 157, 163, 174, 175
238, 240, 241 Calcium, 253-255

300 INDEX
Cadmium, 23, 25, 32, 40, 43 70Cu-30Ni, 10,233,237

Carbon black (CB) test, 158, 176, Corrosion products, 178
178 Literature references on pitting,
Case histories, 117 280
Catchment principle, 36, 38 Pitting corrosion, 171
Cathodic control, 78 Potentials in water, 162
Cathodic protection, 48, 54 Copper tubes in cold water service,
Cathodic current, 90 155, 156
Composite structures, 48 British standard specification,
Current density distribution, 48 157, 158, 172
Galvanic couples, 33, 67, 105, Cleaning, 172
112, 150 Effect of alloying, 169
Protection voltage, 48 Effect of carbon residues, 162,
Seawater, 48 166, 177
Weld materials, 62 Effect of drawing lubricants, 156
CB number, 158-171, 177 Effect of temper, 167, 175
Round-robin testing, 177 Effect of water composition, 164
Chemical analysis techniques Factors affecting corrosion, 156
Atomic absorption, 244 Cobalt and cobalt alloys
Electron microprobe, 204 Haynes 188,25,41
Emission spectrography, 247 Concentration cell corrosion, 231,
Karl Fischer titration, 181 237, 261
X-ray diffraction, 141, 246 Area ratio effects, 238
X-ray fluorescence, 247 Critical oxygen level, 138
Cleaning procedures, 59 Under-deposit corrosion, 119
Abrasive, 171-173 Water-Hne attack, 119
ASTM Recommended Practice, Corrosion fatigue, 117, 125
101, 204 Corrosion products
Chemical, 98, 101, 168, 178 Analysis, 141, 246
Standard techniques, 22 Bridge over pit, 252
Ultrasonic, 86 Carbon steel tubes, 122
Coatings for corrosion protection, Collection and identification, 204
117, 126 Copper, 178
Inorganic conversion, 46 Galvanized steel-clean air, 142-
Metallic, 46 144
Copper and copper alloys, 11, 15, Galvanized steel-polluted air,
17, 22-28, 32, 40, 43, 4 9 - 144, 145
52, 71, 155-179, 192, 233, Iron, colloids, 259
237 Titanium, 150
122 alloy, 155 Zinc, 139-141
360 brass, 96, 103-112 Cost of corrosion, 129
INDEX 301
Crevice corrosion (see also Concen- Effect of potential difference (see

tration cell corrosion), 102, also Galvanic couples), 39
103,105 Distilled water, 26, 28
Area ratio effects, 237, 241
Electrode assembly, 262
Electrode-mount interface, 270 E
Evaluation, 261
Initiation and propagation, 16, Eddy-current testing, 157, 160, 206
235, 239 Electrochemical instrumentation, 5,
Inseawater, 231,234 43
Morphology, 236, 238, 240 Operational amplifier, 13, 45
Probability, 236, 239 Potentiostat, 12, 45, 182
Potential regions, 268 Zero resistance ammeter, 11, 44,
Stainless steels in seawater, 234 58, 87
Standard specimen, 232 Electrochemical techniques
Statistics, 231 Applications and precautions, 7
Test method, 232 Cathodic polarization, 186, 189
Types of crevices, 231 Cathodic protection, 48, 54
Current (see also Galvanic current) Critical pitting potential, 185
Alternating, 69 Current measurement, 11, 46, 58,
Continuous monitoring, 12, 48 88
Diffusion current density, 39 Evaluation of crevice corrosion,
Distribution, 52 261
Leakage, 69 Evaluation of pitting corrosion,
Measurement, 11, 46, 58, 88 261
Protection, 50, 55 Examination of fused joints, 56
Current-time curves Galvanic currents, 11, 21, 43-45,
Galvanic, 12, 14, 24-30 58
Galvanostatic polarization, 48,
D 71, 75, 77
Passive current density, 184
Delamination Polarization measurement, 15,
Aluminum alloys, 112 16, 39
Depth gage, 208 Polarization resistance, 190
Dew Potential measurement, 8, 15, 59,
Light cycle, 134 87
pH,139-141 Potentiodynamic polarization, 16,
Dezincification, 103 261
Diffusion current density, 33,39 Predicting galvanic corrosion, 5
Dissimilar metals, 22, 26, 42, 48, Soil measurements, 86
56, 81, 102-112 Electromagnetic testing, 206
302 INDEX
Electron microprobe analysis, 140, Electrochemical techniques, 5, 43

204 Laboratory studies, 20
Electroplated coatings Magnitude, 21
Literature references on pitting, Panama Canal Zone, 94
280 Prediction, 5
Ellipsometry, 202 Pitting, 14, 102-112, 152
Environmental chamber, 133 Ranking of aluminum-metal cou-
Environmental effects ples, 25
Literature references on pitting, Tests, 5
280 Theoretical considerations, 33
Environmental Protection Agency Underground, 81
(EPA), 132 Underground power cables, 69
Environments Weld material, 66
Concentrated brine, 147 Galvanic couples (see also Dissim-
Distilled water, 26, 28 ilar metals)
Galvanic corrosion, 28, 39 Aluminum alloys, 4130 steel, 14,
Marine, 95 23, 31
Seawater, 9, 48, 49, 57, 62, 63, Aluminum 2024, copper, 35
94 Aluminum 6061, metals and al-
Soils, 73, 77, 83, 85, 86, 100 loys, 26, 102-112
Tap water, 26, 28 Aluminum 7075, cadmium, 23,
Tropical, 95 32
Underground, 69 Aluminum 7075, copper, 22, 28
Exfoliation, 103 Aluminum 7075, Ti-6A1-4V, 22,
102-112
Aluminum 7075, zinc, 23, 32
Aluminum 7075, Type 304 stain-
Failure analysis, 117
less steel, 22, 110
Faraday's law, 33, 79
Atmospheric, 94
Field failures (see Service failures)
Cathodic protection, 33, 67, 105,
Fused joints (see Welded joints)
112, 150
Copper, carbon steel, 11, 48
Copper, iron, 15
Galvanic corrosion Copper, Type 304 stainless steel,
Air, soil, and sea environments, 16
94 Copper, Type 409 stainless steel,
Aluminum alloys, 20 11
Composite structures, 48 Copper, Type 430 stainless steel,
Effect of area ratios, 32, 50, 52, 11, 16
54,55 Combination of magnesium AZ31,
Effect of corrosive environment, Type 316 stainless steel,
28,39 4340 steel, 6061 and 7075
Effect of dissimilar metal, 22, 39 aluminum, 360 brass, 400
INDEX 303
Monel, and Ti-6A1-4V, Chromate inhibitor, 119

102-112 Cupro-nickel tubes, 119
Dissimilar metals, 22, 26, 42, 48, Monel tube sheets, 147, 153
56, 81, 102-112 Titanium tubes, 147
SCPE, lead/tin alloy, 79, 80 Tube deposits, 119
SCPE, copper, 79, 80 Hydrogen embrittlement, 81, 90, 92
Seawater, 94
Soil, 94
Stainless steel, magnesium, 87
Stainless steel, metals, 16, 89,
102-112
Welded joints, 56 Inhibitors
Galvanic current, 5, 11, 12, 14, 22, Anions, 181
26, 28, 32, 33, 37, 40, 4 4 - Chromate, 119
46,59, 6 2 , 6 6 , 7 3 , 7 8 , 8 7 , 8 9 Organic, 156, 173
Continuous monitoring, 12, 46 Ion concentrations
Current density, 33, 35, 40 Calcium, 253-255, 258
Measured versus true, 14 Chloride, 39, 180,249,257
Measurement, 11, 21, 43 Hydroxyl, 247
Welded specimens, 60, 67 Iron, 251,258
Galvanic series Magnesium, 248-253, 258
Based on metal potentials, 10, 40 Mass balance calculations, 255
Factors affecting position, 10 Nitrate, 193
For aluminum, 26 Perchlorate, 180, 193
For seawater, 9 Phosphate, 180, 193
Ranking, 25, 26 Sodium, 255, 256
Galvanized steel, 132, 135-142 Sulfate, 180,200,258
Effect of dew, 141 Iron, 6, 8, 15, 83, 86, 87, 190, 199,
Lead inclusions, 139 256-258
Moisture nucleation sites, 139 Colloids, 259
Pitting, 132 Corrosion products, 259
Potential, 142 Ductile, 220-227
Pourbaix diagram, 145 Gray cast iron pipe, 217, 229
Graphite In titanium scratches, 149
Literature references on pitting, In aluminum pit, 204
282
Nodular, 217
Pitting in seawater, 243
H Iron-chromium-nickel alloys (see
also Stainless steels), 261
Heat exchanger Literature references on pitting,
Carbon steel tube failure, 118 283
304 INDEX
Optical, 88
Scanning electron, 139, 141-143
Lead, 8 Military equipment, 95
Lead-tin alloy, 71, 78 Mixed-potential theory, 5
Literature references on pitting cor- Moisture nucleation sites, 146
rosion
Aluminum, 276
Copper, 280 N
Electroplated coatings, 280
Environmental effects, 280 National Bureau of Standards
Graphite, 282 (NBS), 81, 218
Iron and steel, 282 National Committee on Materials
Iron-chromium-nickel alloys, 283 Policy, 129
Nickel, 288 Nernst equation, 260
Test methods, 289 Nickel and nickel alloys, 10, 25, 43,
Theoretical, 290 187, 199
Titanium, 292 65Ni-35Cu, 233, 237
Tungsten, 292 HastelloyC, 233, 241
Zinc, 292 Incoloy 825, 233, 237
Zirconium, 292 Inconel 625, 233, 241
Localized corrosion, 117 Inconel718, 25, 40
Literature references on pitting,
288
M Monel, 147, 152
MoneUOO, 96, 103-112
Magnesium and magnesium alloys,
Pitting morphology, 192
83, 86, 87, 88, 248-253
Nondestructive testing, 203, 206
AZ-31,96, 102, 104-112
Acoustic emissions, 207
Marine environments (see Seawater)
Eddy current, 157, 160, 164, 165,
Metal-ion corrosion, 237
206
Area ratio effects, 240
Electromagnetic, 206
Methyl alcohol, 181, 182
Hydrostatic, 120, 129
Acid additions, 181, 189, 193,
Magnetic field, 206
194
Penetrants, 207
Anhydrous, 181
Radiographic, 119, 124, 206
Aqueous, 181
Sonics, 206
Decomposition potential, 202
Ultrasonics, 206
Water additions, 181, 182, 195,
197, 199
Microscopy O
Calibrated focus, 202
Interference, 209 Operational amplifier, 13, 45
INDEX 305
Spherometer, 209
Pitting corrosion
Panama Canal Zone, 95, 98 Artificial pit, 243
Galvanic corrosion, 94 Autocatalytic, 141
Passivation Copper tubes in water, 155, 156,
Titanium, 195, 197 160, 171
Passivity, 184, 197, 199 Effect of alloying, 169
Passive films, 10, 196, 202 Effect of carbon residues, 155,
pH 156, 162, 177, 178
Effect on potential, 142 Effect of pH, 156
Measurement in pits, 246 Effect of temper, 167
Microelectrode, 246 In England, 175
Profile in simulated pit, 256 Data interpretation, 217
Variations, 75, 259 Definition, 203
Phosphorus-deoxidized copper, 168 Density, 205
Pipeline Effect of chloride, 180, 196
Servicelife, 213, 227 Effect of pH, 146, 153
Pits Effect of scratches, 149-153
Acidic conditions, 153 Effect of sulfates, 180, 200
Active, 173 Effect of water, 164, 194
Density, 205 Effect of pollutants, 136
Detection by nondestructive meth- Effect on mechanical properties,
ods, 206 214
Examination, 204 Evaluation, 203, 261
Identification, 204 Galvanic couples, 102-112, 152
Macropit, 244 Galvanized steel, 132
Morphology, 120, 122, 148-153, Heat exchanger tube, 120
190-197, 205, 208, 211, Initiation and propagation, 16,
267 139, 150
pH within, 246 Literature references, 276
Size and distribution, 205 Loss in mechanical properties,
Solution chemistry, 246-257 214
Pit depth measurements, 207-210, Macropit, 244
217, 218, 220, 229 Measurement, 203, 218
Average, 210 Methods to determine extent, 207
Depth gage, 208 Morphology, 120, 122, 148-153,
Machining, 208 190-197,205, 208, 211,267
Maximum, 210-214 Organic media, 180, 186
Metallographic, 207 Protection, 16
Micrometer, 208 Rate of attack, 137
Microscopic, 209 Solution chemistry, 243-257
306 INDEX
Statistical calculations, 217 Test cell, 263

Steam condensate line, 120 Weld zones, 61
Steam generator line, 129 Polarization curves
Test cell, 244 Aluminum and stainless steel in
Theoretical (literature references), seawater, 52-54
290 Aluminum 6061 in CH3OH plus
Titanium tubes, 147 H2SO4, 196, 197
Zinc, 138, 140 Carbon steel 1006 in 5 percent
Pitting evaluation, 209 sodium chloride, 15
Burst pressure, 215 Copper in CH3OH plus H2SO4,
Metal penetration, 210 198
Standard charts, 209 Copper in 5 percent sodium chlo-
Statistical, 211 ride, 15
Pitting factor, 211 Copper and steel in seawater,
Pitting potential, 185 50-52
Aluminum alloys, 23, 39 Effect of scan rate, 264
Copper, 160, 167 Effect of surface finish, 269
Effect of chloride, 196 Galvanic couple regions, 17
Effect of crevices, 262 Hysteresis loop, 265, 268
Effect of hydrochloric acid, 188 Iron in 5 percent sodium chloride,
Effect of water, 187 9
Regions, 266, 273 Iron in CHaOH plus H^SO*, 198
Titanium, 195 Iron in 1.0 N sodium sulfate, 6
Pitting probability, 211,212 Lead in 5 percent sodium chlo-
Platinum, 192 ride, 9
Platinum group metals, 16 Nickel in CHÔH plus HaS04,
Polaristat, 48 191
Polarization Pitting regions, 266, 273
Activation, 6 Platinum in CH3OH plus H2SO4,
Anodic, 9, 10, 16, 183-201, 261 199
Cathodic, 49, 62, 186,263 Stainless steel
Cathodic control, 55 Type 304 in CH3OH plus
Concentration, 63, 66 H2SO4, 193
Galvanic couple, 12, 50 Type 304 in sodium chlo-
Galvanostatic, 48, 71, 75, 77 ride, 264-274
Measurement, 5, 15, 39, 77 Type 310 in 5 percent so-
Prediction of localized corrosion, dium chloride, 10
15 Type 434 in 5 percent sodi-
Potentiodynamic, 9, 10, 16, 261 um chloride, 10
Potentiostatic, 39, 183-201 Titanium in CH3OH plus H2SO4,
Resistance, 58, 190 189
INDEX 307
Titanium 75A in CH3OH plus Crevice corrosion, 236, 239

HCl, 182-184, 200 Protective coatings, 46, 117, 126
Titanium 75A in organic media
plus H2SO4, 201 R
Zinc in 5 percent sodium chloride,
Radiographic inspection, 119, 124,
9
206
Polyethylene
Reference electrodes
Semiconducting (SCPE), 71
Copper-copper sulfate, 86
Potential
Saturated calomel, 182
Critical, 15, 16
Silver-silver chloride, 160
Critical breakdown, 16, 173, 184
Constant, 186, 266, 270, 273
Copper tubes, 163
Corrosion, 8, 21, 23, 28, 162 Salt evaporators, 147
Equilibrium, 6 Salt plugs, 152
Galvanic, 28 Seawater, 9, 49, 57, 62, 63, 94
Measurement, 8, 46, 59, 87, 160 Artificial, 244
Mixed, 6, 8, 15, 17 Barnacle growth, 112
Open circuit 57, 63, 75, 92 Cathodic protection, 48
pH influence, 142 Composite structures, 48
Pitting, 23, 39, 160, 167, 185, Crevice corrosion, 231, 234
187, 195, 262, 266, 273 Exposure, 100, 105, 233
Protection, 50 Flume, 233
Repassivation, 265, 270 Galvanic corrosion, 94
Solution, 260 Immersion racks, 100, 104, 110
Variation with time, 11, 162-168 Oxygen concentration corrosion,
Welded specimens, 60, 67 238
Potential, pH behavior Panama Canal Zone, 94
Zinc, 142 Pitting of iron, 243
Potential, time curves Service failures
Copper tubes in water, 162-168 Carbon steel high-pressure steam
Copper-nickel in seawater, 11 condensate line, 119
Nickel in seawater, 11 Carbon steel steam generator
Stainless steel in seawater, 11 blow-down line, 129
Potentiostat, 12,45, 182 Carbon steel tube heat exchanger,
Pourbaix diagram 118
Galvanized steel, 145 Carbon steel waste line, 124
Zinc, 145 Case histories, 118-129
Power lines, 69 Cause of equipment failures, 118
Pressure tests, 215 Copper tubes in cold water serv-
Probability ice, 155, 172
308 INDEX
Copper tubes in United Kingdom, Specimen preparation, 21, 49, 59,

177 75, 85, 95, 135, 233, 263
Ductile iron pipe underground, ASTM Recommended Practice G
227 1, 204
Estimated life, 228 Neutral wire electrode, 71
Salt evaporator, 147 Stainless steels, 15, 16, 25, 50, 5 2 -
Steel pipe underground, 227 54, 81, 82, 83, 87, 88
Power cables in soil, 69 6X, 233,241
Welds in seawater, 64 26CR-1MO, 82, 90, 92
Shepard cane, 86 26Cr-6.5Ni, 83, 90, 92
Silver, 25, 40, 43 CA-15, 235
Sodium, 255, 256 CA-8M, 235
Sodium chloride, 9, 10, 12-15, 21 Mechanical properties, 82
24-26, 28, 31, 32, 37, 73, PH13-8MO, 21
263-274 Pitting morphology, 194
Sodium sulfate, 6, 73 Stressed, 85
Soil Type301,82, 88, 90, 92
Aggressive, 227 Type 304, 10, 16, 17, 22, 28, 82,
Burial, 69, 94, 102, 108 90, 92, 189, 199, 232, 237,
Chemical analysis, 73 262, 264
Polarization measurements, 77 Type 304 L, 26, 28, 32
Properties, 83 Type 310, 10
Resistivity, 86, 91, 221 Type 316, 10, 96, 102, 104-112,
Specimen exposure and removal, 231, 237, 262, 271
86 Type 409, 11
Test site variations, 83-85, 94, Type 430, 11, 16
100, 221, 228 Type 434,10
Types, 83, 220 Standards
Soil resistivity, 91,221 ASTM Method E 3, 205
Measurement, 86 ASTM Recommended Practice G
Solution chemistry, 243-259 1, 101, 204
Solution potential, 260 ASTM Recommended Practice G
Sonic testing, 206 16, 235
Specimens ASTM Specification D 1141, 245
Atmospheric, 96, 98 NACERP-01-73, 204
Coupled, 21,96 Statistical analysis, 203, 217
Crevice, 232 Statistics, crevice corrosion, 231
Galvanic, 76 ASTM Recommended Practice G
Seawater immersion, 49, 97 16, 235
Soil burial, 86, 97, 102 Probability plot, 235
Welded, 57 Statistics, pitting
INDEX 309
Confidence limits, 219 Test cell

Extreme valve probability, 213, Polarization, 263
219 Simulated pit, 245
Log-normal distribution, 219 Test methods (see also Electro-
Maximum pit depth, 210-214 chemical Techniques)
Prediction intervals, 217, 219, Autoclave, 148
221-230 Carbon black (CB), 158, 176,
Probability test, 211, 212 178
Regression calculations, 219, 221 Crevice corrosion, 232
Statistical analysis, 132 Eddy current, 157, 160, 206
Steam condensate line Environmental, 133
Corrosion fatigue of carbon steel, Galvanic, 5, 21
Low-frequency cyclic loading, 289
124 Seawater immersion, 105
Steam generator Test racks
Carbon steel blow-down lines, ASTM exposure racks, 98
129 Chill, 135
Steel Laboratory tube testing, 159
4130, 14, 23, 25, 28, 31, 32, 40, Monel, 98
43 Seawater, 100, 104
4340,96, 102, 104-112 Site tube testing, 159
Bessemer pipe, 229, 230 Test sites
Carbon, 11, 15, 17, 50-52, 220- Atmospheric, 98
227 Panama Canal Zone, 95, 98
Carbon steel service failures, 117 Seawater, 100,233
Galvanized, 132, 135-142 Soil, 83, 100,221,228
Literature references on pitting, Thallium in seawater, 260
282 Time of wetness, 134
Localized corrosion, 117 Dew-light cycle, 134
Stress corrosion, 81 Tin, 25, 41
Strain gages, 85 Titanium and titanium alloys, 147,
U-bend specimens, 85 152, 181, 193-195
Corrosion products
Titanium chloride, 150
Titanium dioxide, 150
Tafel Titanium hydride, 153
Equation, 5 Effect of methyl alcohol plus
Extrapolation, 62 acids, 181, 193
Slope, 192 Effect of organic solvents, 194
Tap water, 26, 28, 159, 160 Heat exchangers, 147
310 INDEX
Literature references on pitting, Hard, untreated, 157

292 Passivating effect, 195
Mechanism of pitting, 149, 150 Softened, public supply, 157
Passivation, 195, 197 Tap, 26, 28, 159, 160
Pitting in hot brine, 147 Treatment, 176, 177
Ti-6A1-4V, 22, 25, 26, 28, 32, Water line attack, 121
40, 96, 103-112, 181, 186 Welded joints, 56, 274
Ti-75A, 181, 186 Cathodic protection, 62
Tropical environments, 95 Field failures, 63
Tungsten Filler metal ( F M ) , 56,63
Literature references on pitting, Galvanic corrosion, 66
292 Galvanic couples, 62
Galvanic susceptibility, 67
U Heat affected zone (HAZ), 56,
60-64
Underground corrosion (see also Parent metal (PM), 56, 60, 63
Soil) Seawater corrosion, 56
Galvanic, 81 Specimen, 57
NBS tests, 218 Weld metal, 61
Stressed stainless steel, 81 Wenner bridge, 86
Underground power distribution
cable, 69
Concentric neutral wires, 69
Galvanic corrosion, 69 Zero resistance ammeter, 11, 44, 58,
Laboratory tests, 73, 74 87
U. S. Army Tropical Testing Sta- Zinc, 8, 22, 25, 26, 28, 32, 35, 40,
tion, 95 43, 83, 86, 87, 136
Corrosion products, 139-141
W Carbonate, 139
Hydroxide, 140
Waste line, 124, 126 Oxide, 140
Coatings, 126 Sulfate, 141
Water Lead inclusions, 139
Aggressive, 176 Literature references on pitting,
Compositional analysis, 161 292
Distilled, 26, 28 Pit initiation sites, 139
Distribution systems, 155 Potential, pH behavior, 142
Domestic, 155 Zirconium
Effect of composition on pitting, Literature references on pitting,
166, 176 292

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GALVANIC AND PITTING

ASTM SPECIAL TECHNICAL PUBLICATION 576

List price $29.75

American Society for Testing and Materials

Printed in Cockeysville, Md.

Manual of Industrial Corrosion Standards and Control, STP 534 (1974),

Corrosion in Natural Environments, STP 558 (1974), $29.75, 04-558000-27

ASTM Committee on Publications

Jane B. Wheeler, Managing Editor

Electrochemical Techniques for Predicting Galvanic Corrosion—ROBERT

Laboratory Studies of Galvanic Corrosion of Aluminum Alloys—FLORIAN

Current Density Distribution on Composite Structures Under Cathodic Protec-

Electrochemical Examination of Fused Joints Between Metals—K. G. COMPTON

Galvanic Corrosion of Underground Power Distribution Cable Materials—

Galvanic Coupling of Some Stressed Stainless Steels to Dissimilar Metals

Localized Corrosion Attack on Carbon Steel—Case Histories of Service

Pitting of Galvanized Steel in Controlled Clean Air Environments—J. w.

Pitting Corrosion of Titanium Tubes in Hot Concentrated Brine Solutions—

Pitting Corrosion in Copper Tubes in Cold Water Service—F. J. CORNWELL,

Pitting Caused by Chlorides or Sulfates in Organic Media—FLORIAN MANSFELD 180

Interpretation of Pitting Corrosion Data from Statistical Prediction Interval

Calculations—D. L. CREWS 217

Statistical Aspects of Crevice Corrosion in Seawater—D. B. ANDERSON 231

Solution Chemistry of Pitting of Iron in Artificial Seawater—c. w. PETERSEN 243

Use of Rapid-Scan Potentiodynamic Techniques to Evaluate Pitting and Crevice

Corrosion Resistance of Iron-Chromium-Nickel Alloys—p. E. MORRIS 261

Compilation of Literature References on Pitting Corrosion 276

Galvanic and pitting corrosion are widely different forms of degrada-

Electrochemical Techniques for Predicting

REFERENCE: Baboian, Robert, "Electrochemical Techniques for Predicting

Corrosion of metals can be treated by application of the mixed potential

>?act = ±/8 log 4- (1)

Copyright^ 1976 by ASTM International www.astm.org

Copyright by ASTM Int'l (all rights reserved); Fri Jan

CUMENT DENSITY Ima/cm')

FIG. 1—Activation polarization curves for a reversible electrode system.

FIG. 2—Polarization behavior of iron in 1.0 N sodium sulfate.

One of the most important applications of the mixed potential theory to

^ 3P *"• ^ ^*^°" '^^

TOTAL OXIDATION RATE

LOG CURRENT DENSITY

FIG. 3—Mixed potential behavior of galvanically coupled Metals A and B.

less. Also, it is important that the measurements be conducted in the actual

(Table 1) is correct for the 5 percent sodium chloride environment. Meas-

lO-l 10» 10' 102

FIG. 6—Variation of corrosion potential with time for nickel 90 to 10 copper-nickel.

FIG. 7—Schematic circuit of elementary zero resistance ammeter.

resistance ammeter circuit. The magnitude of the galvanic current provides

auxiliary and working electrode terminals. A null balance is thus main-

FIG. 10—Schematic circuit of a zero resistance ammeter using an operational amplifier

using Strip chart recorders. The reference electrode in Fig. 10 is only

g 10» 10-2 10° 10= 10* lo' 10"

10-1 10° 10' 10^ 10^

FIG. 13—Schematic potentiodynamic polarization curve for stainless steel in 5 percent

LOG CURRENT DENSITY

LOG CURRENT DENSITY

FIG. 14—Schematic polarization curves showing corrosion behavior oj stainless steel

LOG CURRENT DENSITY

The following electrochemical techniques are used in predicting the

Laboratory Studies of Galvanic Corrosion

^ 3P "• ^ ^^°" '^^