from 0.1, 1, and 5M to 7.5, 8, and 10M, respectively, with an 3. Y. S. Park, J. R. Galvele, A. K. Agrawal, and R. W. Staehle.

assumption of 10 C of the temperature differential between
the metal surface and the bulk of solution.
It is well known that steels exposed in hot concentrated
caustic solution are further attacked if any mechanical stress,
especially tensile stress, is applied.' -3,12,13 So-called caustic
embrittlement could be stimulated by heat transfer. The sub-
ject is of interest from the viewpoints of both science and
engineering, and will be discussed in the future.
Acknowledgment
The authors express thanks to M. Watanabe, H. Taguchi,
F. Takeya, and S. Tokutake, worked hard to conduct a part of
the experimental studies. The program was supported by the
Japan Soda Industry Association.
References
1. T. Hurlen. Electrochim. Acta, Vol. 8, p. 609 (1963).
2. R. L. Jones, J. W. Stratten, and E. D. Osgood. Corrosion,
Vol. 26, p.399 (1970).
Corrosion, Vol. 34, p. 413 (1978).
4. M. J. Humphries and R. N. Parkins. Corr. Sci., Vol. 7, p. 747
(1967).
5. J. E. Reinoehl and W. E. Berry. Corrosion, Vol. 28, p. 151
(1972).
6. M. Yasuda, F. Hine, M. Watanabe, and M. Okada. Zairyo
(J. Soc. of Materials Science, Japan), Vol. 29, p. 1096
(1980).
7. N. Sato. Passivity of Metals, edited by R. P. Frankenthal
and J. Kruger, p. 29, Electrochem. Soc. (1978).
8. H. E. Townsend, Jr. Corr. Sci., Vol. 10, p. 343 (1970).
9. V. Ashworth and P. J. Boden. ibid., Vol. 10, p. 709 (1970).
10. R. J. Biernat and R. G. Robins. Electrochim. Acta, Vol. 17,
p. 1261 (1972).
11. Unpublished data.
12. B. Poulson. Corr. Sci., Vol. 15, p. 469 (1975).
13. M. Kowaka and M. Kitamura. Nippon Kinzoku Gakkai Shi
(Journal of Japan Institute of Metals), Vol. 39, p. 381 (1975).

Effects of Sulfur Compounds on the Pitting

Behavior of Type 304 Stainless Steel in
Near-Neutral Chloride Solutions*

R. C. NEWMAN, * H. S. ISAACS,* and B. ALMAN**

Abstract
Pitting potentials have been measured potentiodynamically for Type 304 stainless steel in
neutral or mildly acidic solutions containing 0.25M NaCI and various concentrations of sulfur
species from 0 to 2 molar. Additions of 0.01 to 0.02M Na 2 S 2 0 3 lowered the pitting potential by
more than 300 mV, while additions of more than 0.5M Na 2 S 2 0 3 inhibited pitting. KSCN showed
similar but less marked effects, while increasing Na 2 S additions up to 0.1 molar (giving H 2 S
and HS at neutral pH) caused an increasing reduction in the pitting potential. Additions of
-

Na 2 S 4 0 6 up to 0.05M promoted pitting, but addition of 0.01M Na 2 S0 3 had no effect. Parallel

pitting potential measurements using a scratch technique gave lower values for the sulfur
containing solutions but a higher value for the plain chloride solution; this effect of surface
deformation was also reflected in the results obtained potentiodynamically on abraded and
electropolished surfaces.

Introduction stepped potentiostatic polarization, potential sweeping and

The resistance of materials to pitting corrosion is often scraping during potentiostatic polarization. The last 6 7 has the
'

characterized by a critical potential. It is known that the
stochastic nature of pitting 1 2 and its tendency to occur at
• but may overestimate the pitting propensity of alloys which
microstructural heterogeneities such as sulfide inclusions 3,4
render the pitting potential a somewhat dubious parameter for
prediction of service performance of large areas of metal.
Some authors have even suggested that the concept of a pit-
ting potential is invalid. 5 . However, the measurement of pitting
potentials by any of several common methods can be used in
alloy development or to derive useful quantitative data on the
effects of electrolyte composition. These methods include
*Submitted for publication November, 1981; revised Feb-
ruary, 1982.
'Brookhaven National Laboratory, Upton, New York.
**University of Pennsylvania, Philadelphia, Pennsylvania.
advantage that the state of the surface is highly reproducible,
derive at least part of their pitting resistance from highly pro-
tective surface films. The presence of scratch debris may pro-
vide crevices which promote pit initiation. Conversely, in cer-
tain instances, it appears that stable pitting is associated with
the undermining and retention of the surface oxide film, which
may be more readily ruptured (leading to repassivation) on a
highly cold-worked surface. 8 Generally, it is adequate to use
potential stepping or slow potential sweeping (-0.1 mV s~')
as standard techniques for studying the effects of electrolyte
composition.
Leckie and Uhlig 9 studied the pitting behavior of Type 304
stainless steel in chloride solutions with and without various
anion additions (SO 42 , CI0 4 - NO 3 - OH ). They showed
- , , -

0010-9312/82/000091 /$3.00/0
Vol. 38, No. 5, May, 1982 ` 1982. National Association of Corrosion Engineers 261
that a well defined relationship existed between chloride ion
concentration and pitting potential as determined with a
stepped potentiostatic technique. It was proposed that in-
creasing additions of other anions shifted the pitting potential
in a positive direction (and eventually inhibited pitting
altogether) by competitive adsorption on the metal surface. It
was considered that the passive surface carried no oxide film,
a view now discredited.
A common modern concept is that the most important
process controlling the résistance of a material to pitting may
be the repair of the passive oxide film rather than its ability to
resist breakdown. Electrochemical noise generated below the
pitting potential in the presence of chloride ions has been
associated with film breakdown and repair 1 ° and a number of
authors consider that passive films may be inherently
labile. 1 ' 2 ' 11 Janik-Czachor, et a1, 12 have reviewed many of these
ideas. Anodic current densities on iron or nickel in the earliest
stages of pit nucleation can attain extremely high values, in
the range 10 to 100 A cm - 2;13 different authors have laid differ-
ing stress on the importance of interfacial pH 14 ' 15 and inter-
facial chloride ion concentration 16 in determining whether or
not stable pitting will proceed. In at least some instances, the
precipitation of a salt film 8 ' 17 ' 18 may play an important role:
although salt films are often regarded as precursors to
passivation (for instance of iron in sulfuric acid 19), they can
also be envisioned as inhibiting oxide passivation during pit-
ting, particularly if they are anhydrous. Even in the earliest
stages of pit nucleation, the electro-transport of nonchloride
anions will slow down the accumulation of chloride ions at the
metal-solution interface, and there can be little doubt 14 ' 16 that
at least some of the inhibiting effects observed by Leckie and
Uhlig 9 can be attributed to simple transport phenomena of this
kind. Clearly, reducible ions such as NO 3 have a more com-
-
plex role than 'inert' species such as C10 4 and SO 42 . An ef-
fect which seems to be significant at low ratios of sulfate to
chloride is 'salting in', or increase in solubility of metal ions,
which may account for the small decrease in pitting potential
of Type 304 steel compared with that observed in a plain
chloride solution. 20
The effects of sulfide inclusions on pitting of steels 3 ' 4
have long been associated with formation of hydrogen sulfide
in the pit environment, as well as with localized weakness of
the passive film and tendency for development of a crevice at
the inclusion-matrix boundary. Hydrogen sulfide both pro-
motes active dissolution and inhibits passivation of a number
of metals, as reviewed by Sury. 21 Comparisons have been
made between H 2 S derived from dissolution of sulfides and
that added to the bulk environment. 22-24
Recently some Interest in the effects of H 2 S on chloride
pitting has arisen in other connections such as the exploita-
tion of geothermal brines. 25 The aggressive effects of the thio-
cyanate ion in destroying passive films on iron 26 and causing
pitting or cracking in stainless steels 27 are also well
documented. Sulfur dioxide has been shown to promote
chloride pitting of stainless steels 28 but some of the effect
was due to pH differences in this case, and a comparison has
not been made at constant pH. The authors noted that the
scratch test was less severe than the potentiodynamic test for
plain chloride solutions but more severe for the S0 2 -saturated
solutions. Some effects of both S0 2 and H 2 S have been
discussed by Masuo, et al.-
The present work aims to generate data from which the ef-
fects of various sulfur species can be examined at roughly
constant bulk pH within the range where the pitting potential
of Type 304 steel is pH-independent in plain chloride
solutions. 9 Special emphasis is placed on the thiosulfate ion,
which has been shown to cause extraordinarily rapid stress
corrosion cracking of sensitized stainless steels 30 ' 31 and may
(in conjunction with chloride) be responsible for unusually
severe pitting corrosion in the paper industry. 32,33 The pitting
potentials are determined potentiodynamically, and a scratch-
ing technique is used to study some effects of gross surface
baring on pit nucleation.
262 CORROSION—NACE
Experimental Procedure
Samples for the electrochemical measurements were cut
from 3.2 mm Type 304 stainless steel plate (Cr 18.88 Wt%, Ni
8.61, Si 0.80, Mn 1.58, C 0.07, P 0.026, S 0.007).
For most of the measurements, the specimen was abrad-
ed on one surface to a 600 grit finish, then ultrasonically clean-
ed in distilled water, and dried with an air jet. The working sur-
face was partially masked with nonreactive tape, leaving a 1
cm 2 area exposed after lacquering over the edges of the tape.
A few measurements were also made on specimens which had
been electropolished in a phosphoric acid/nitric acid mixture.
The electrolyte used in all the measurements contained
0.25M NaCI in deionized water of resistivity > 10 Mohm cm.
Varying amounts of sulfur-containing salts were added as
Na 2 S 2 0 3 , Na 2 S 4 0 6 , KSCN, Na 2 S, and Na 2 S0 3 . All reagents
were of analytical grade. Measurements were made with the
pH adjusted to between 5 and 6.5 except for the more concen-
trated Na 2 S 4 0 6 solutions, which had more acidic pH values
recorded below; the pH adjustments were made by small addi-
tions of hydrochloric acid. In the case of the more concen-
trated sulfide solutions, the change in chloride concentration
would have been appreciable, and therefore a smaller NaCI
concentration was used so as to retain 0.25M C1. The effect
of neutralizing the sulfide solutions to pH 5.5 to 6.5 was to pro-
duce concentrated solutions of H 2 S which degassed slowly
during the experiment; however the toss of H 2 S was not ap-
preciable. For the thiosulfate-containing solutions
measurements were also made at the natura) pH (up to 9.0) ob-
tained following addition of the Na 2 S 2 0 3 .
A glass elecrochemical ceil was constructed in which the
working electrode surface faced vertically upwards and cur-
rent flowed to a platinum wire counter electrode. A saturated
calomel electrode (SCE) was placed in a separate compart-
ment containing a saturated solution of KCI, and connection
was made to the working cel) via a Luggin probe whose open-
ing was positioned 2 mm from the working electrode surface.
Deoxygenation was achieved by bubbling high purity nitrogen
through the working electrolyte, which was at 25 ± 1 C
throughout. Potential control for potential sweeping was by a
PAR potentiostat (model 173) programmed by a PAR signal
generator (model 175). All potentiodynamic measurements
reported in this paper were made at a sweep rate of 0.2 mV s -1
following immersion of the working electrode and switching to
a fixed starting potential of -400 mV (SCE). Potential scan
reversal was generally about 10 mV above the pitting potential
where this was sharp, or at various points where no sharp pit-
ting potential was observed.
Pitting potentials were also measured for critica) elec-
trolyte compositions using a scratching technique. The
specimen was mounted face up in an open cel) containing
counter and reference electrodes, with no Luggin probe. Ex-
posure of the reference electrodes to solutions containing
sulfur species was minimized: considerable drift in the poten-
tial could occur, particularly when thiosulfate was allowed to
diffuse through the protective porous capillary. Scratches ap-
proximately 10 mm by 200 µm were made manually with a dia-
mond scribe, the contact time being typically 50 ms. The
resulting current transients were recorded and stored on
magnetic disks using a digital storage oscilloscope (Nicolet
model 206). Pitting on the scratch was characterized by a
steady increase of the anodic current following an initial par-
tial repassivation; the nature of the attack was studied using a
X50 binocular microscope.
Resuits
Pitting Potential Measurements
Figure 1 shows a potentiodynamic polarization curve for
an abraded specimen in 0.25M NaCI containing 0.01M
Na 2 S 2 0 3 pH adjusted to - 6.0. A few tests were performed us
,
ing electropolished specimens: these gave a pitting potential
-20 mV lower for the plain chloride solution but -20 mV

-200 -ivu
POTENTIAL (MV SCE)
FIGURE 1 - Potentiodynamic polarization curve for
abraded Type 304 steel In 0.25M NaCI + 0.01 M Na 2 S 2 0 3 ,
showing sharp pitting potential. Scan rata 0.2 mV s 1 .
higher for the solution containing 0.01M Na 2 S 2 03. All pitting
potentials were reproducible to within 5 mV on the same
specimen; 'protection potentials' against pitting varied over
-50 mV depending on pit depth, and have no particular
significante.
Figure 2 summarizes the results obtained for all the solu-
tions examined, showing the following significant features:
1. A minimum pitting potential for an added sulfur anion
concentration of 0.02 to 0.03N for S 2 032 , CNS .
- -
2. A smal) pH effect for the thiosulfate solutions where
the pH was not adjusted to below 7. The magnitude of this ef-
fect Is consistent with that found by Leckie and Uhlig 9 for plain
chloride solutions.
3. Inhibition of pitting (but not crevice corrosion) for addi-
tions of greater than 0.5M S 2 0 32- or CNS . - cant differences were observed for the various solutions at
4. A continuously decreasing pitting potential for in-
creasing (HS + H 2 S) concentration in the range 0.005 to
- scratches were in the range 5 to 10 mC cm -2 . Accordingly,
0.1 M.
5. No effect of 0.01M Na 2 SO 3 .
6. A strong effect of S 4 0 62- at concentrations up to
0.05M. These solutions were markedly unstable, and higher
concentrations ware not examined. These tests were perform-
ed without pH adjustment; the pH varied from 5 to 3 with in-
creasing tetrathionate additions.
All pits formed in the thiosulfate, sulfide, and
tetrathionate-containing solutions contained a black material.
This was readily shown to contain some metal sulfide by
washing, drying, and dissolving in dilute sulfuric acid with
evolution of hydrogen sulfide. The black material became
voluminous after prolonged pitting, and clearly assisted the
formation of very broad, deep, covered pits. In the plain
chloride solution, the pits were more numerous for the same
potential of scan reversal relative to the pitting potential, but
were small and bright. Prolonged polarization at -50 mV
above the pitting potential showed that most of these pits
repassivated at an early stage; typically only one or two pits
grew to a large size. The pits formed in the thiosulfate-
Vol. 38, No. 5, May, 1982 263
i I
,s
—3 —2 —1 0
LOG (SULFUR SPECIES CONCENTRATION,M)
FIGURE 2 - Pitting potential data for Type 304 steel In
0.25M NaCI with additions of sulfur compounds. The
dotted line at + 260 mV represents the 0.2 mV s 1 pit -
ting potential with no additions. Potentiodynamic pit-
ting potentials are shown for Na 2 S 2 O 3 and Na 2 S 4 O 6 with
no pH adjustment (X and • respectively) and for the
following with 5.0 _< pH < 6.5: Na 2 S 2 0 3 (+), KSCN (•),
H 2 S (0). Scratch pitting potentials are indicated by 's'.
Bracketed points are ±50 mV; all others are repro -
ducibie to < 10 mV. Addition of 0.01 M Na 2 SO3 had no ef-
fect on the pitting potential.
containing solutions were never observed to repassivate
above the pitting potential. The protection potentials on
reverse scanning of the potential showed no systematic varia-
tion, as expected for pits of widely varying size: a pit will
repassivate if the localized environment can diffuse away
more rapidly than it is maintained by metal dissolution and ca-
tion hydrolysis.
Scratching Electrode Measurements
These were made initially with a view to ranking the
repassivation rates of the alloy at a fixed potential just below
the lowest protection potential for pitting. However, no signifi-
-250 mV (SCE). Total charge densities passed on the
attention was focused on the repassivation behavior at
somewhat higher potentials. These tests showed that pitting
occurred extremely readily on the scratches when the elec-
trolyte contained 0.01 M Na 2 S 2 0 3 or Na 2 S 4 0 6 - in both cases
the pitting potential was even lower than the 'protection poten-
tials' recorded potentiodynamically. These results are record-
ed in Figure 2. Scratch tests made with 1M Na 2 S 20 3 added
showed no discernable pitting potential, consistent with the
potentiodynamic results. The results obtained in the plain
chloride solution were, in contrast, very difficult to interpret.
At potentials as high as +400 mV (SCE), despite very slow
repassivation of the scratches and copious pitting of the
unscratched surface, no pits could be discerned on the
scratches even after 15 minutes' polarization. The onset of
slow repassivation in the plain chloride solution was quite weit
defined with a critical potential at ~ + 35 mV (SCE). It appears
that in the plain chloride solution, the scratch behaves, in a
sense, like a single elongated pit; however, the current density
is at least one order of magnitude lower than that normally
characteristic of pit propagation.
 Discussion
We focus attention on the resuits obtained with
thiosulfate and sulfide. The following features require inter-
pretation:
1. The strong effect of 0.01M thiosulfate.
2. The sharply decreasing effect as the concentration of
S2032- is lowered below 0.01 M.
3. The inhibiting effect of large concentrations of
thiosulfate.
4. The absence of an inhibiting effect for large concentra-
tions of (HS - + H 2 S).
5. The effects of electropolishing, abrasion and in-situ
scratching for plain chloride and chloride + thiosulfate solu-
tions.
Effects of Thiosulfate and Sulfide
The thiosulfate ion is kinetically unstable, dispropor-
tionating to sulfur and sulfite ions, in solutions of pH , 4. It
can also readily be electrochemically reduced to sulfur or
sulfide ions. 3 °. 35 Conversely, at a sufficiently high potential, it
is expected to oxidize to sulfate: if this occurred at all in the
present work, it did not inhibit pit propagation. The effects of
adsorbed sulfur or sulfide ions on dissolution rate and
passivation tendency of transition metals are well known. 21
We have shown elsewhere that the severity of the in-
tergranular stress corrosion cracking of sensitized stainless
steels in thiosulfate solutions is associated with efficient
generation of sulfur and/or iron sulfide at the crack tip. 34,35 In
addition, ferrous thiosulfate is highly soluble. 34 The more
severe effect of thiosulfate on pitting than hydrogen sulfide at
the 0.01M level (Figure 2) may be expected owing to its ac-
cumulation at rapidly dissolving pit precursor sites; H 2 S, not
being an ion, does not electromigrate. The inhibiting effect of
high thiosulfate concentrations is clearly due to preferential
electromigration of S 2 0 32- into pit nuclei, preventing chloride
accumulation and probably retarding acidification owing to
reactions such as:
S 2 0 3z - + 6H + 4e = 2S + 3H 2 0
Again, H 2 S does not electromigrate and therefore increas-
ing concentrations above 0.01M have an increasing effect. As
far as can be ascertained, the ranking of the sulfur species at
the 0.01 to 0.02M level corresponds also to their relative severi-
ty in the stress corrosion cracking of sensitized steels. 30
The small effect of concentrations of thiosulfate between
0.001 and 0.005M is somewhat surprising given the extreme ef-
fect of the 0.01 M addition. Probably, this sharp threshold con-
centration corresponds to that below which an adsorbed
sulfur layer of sufficient coverage cannot be produced at the
base of a flaw in the passive film before the film begins to heal.
Ouantitative confirmation of this speculation is difficult;
however, it is consistent with the observation that thiosulfate
alone has no noticeable aggressive effect on the passive film,
and therefore probably exerts its effect on the bare metal sur-
face following chloride induced film breakdown. The
thiosulfate-chloride system offers some promise as a probe of
film breakdown and repair processes during pitting.
Effects of Surface Finish and in situ Scratching
The promotion of plain chloride pitting by prior elec-
tropolishing has been reported previously 8 and is related to
the retention of a film of high mechanica) integrity over the
growing pit. More recently, Frankenthal and Kruger 36 have
shown that scratches in stainless steels do not preferentially
nucleate pits and have emphasized the role of sulfide inclu-
sions. The effects of bulk chloride concentration on the
relative pitting tendency of different surfaces have not been
studied. The promotion of the chloride-sulfur compound pit-
ting by prior abrasion or, more spectacularly, by in situ
scratching indicates that the important factor here is a high
probability of film breakdown. The black sulfide material form-
264 CORROSION-NACE
ed in the pit protects the contents from rapid dispersion into
the bulk solution and therefore fulfils the same function as the
oxide film covering the pit in the plain chloride solution. For a
given potential, the pits formed in the sulfur-containing solu-
tions will also grow more rapidly owing to enhancement of the
dissolution kinetics by adsorbed sulfur. The very large effect
of scratching on the pitting potential for the solutions contain-
ing 0.01M thiosulfate or tetrathionate may arise in part from
pits nucleated under debris along the edge of the scratch, and
cannot be assigned any fundamental significance. A more Im-
portant effect is the pronounced reluctance of the scratches
to pit in the plain chloride solution; the prolonged (> 15
minutes), rather slow (several mA cm -2 ) dissolution observed
above +35 mV(SCE) may be characterized as resulting from a
high spatial density of short lived pit nucleation events in a
mechanically unstable film.
The effects of sulfur compounds added to the bulk solu-
tion, at the levels used in this work, clearly dominate any ef-
fects of sulfur from the metal. However, the large discrepancy
between the number of pits initiated and the number growing
to an appreciable size in the plain chloride solution may be
related to availability of suitably active sulfide inclusions.
Probably, a scratch placed directly across a suitable sulfide
particle would initiate a pit; this highlights a statistical
drawback of the scratch technique. It appears, however, that
the scratch technique applied in a NaCI-Na 2 S 2 O 3 solution may
be a good method of ranking pitting resistance of relatively
susceptible stainless steels without incurring the statistical
difficulties encountered with plain chloride solutions. Ex-
amination of some other steels is in progress-preliminary
resuits indicate that, above a certain degree of pitting
resistance, small thiosulfate concentrations do not influence
pit initiation as the thiosulfate ion cannot be electrochemical-
ly reduced at the potentials concerned.
Conclusions
1. 0.25M NaCl + 0.01 M Na 2 S 2 0 3 is a very severe pitting
environment for Type 304 stainless steel at 25 C, particularly
when the electrode is subjected to in situ scratching.
2. Effects of various sulfur species at the 0.01 to 0.02N
level rank in the order S 2 0 32- > H 2 S S 4 0 62- > SCN - >>
S0 32- (pH between 4.5 and 6).
3. Concentrations of S 2 0 32- or SCN above -0.02N in-
hibit pitting compared with the 0.02N additions, whereas in-
creasing H 2 S concentrations lead to an increasingly less no-
ble pitting potential. These observations are consistent with
preferential electromigration being responsible for the inhibi-
tion. Additions of >0.5M Na 2 S 2 0 3 or >0.1M KSCN inhibit pit-
ting compared with plain chloride solutions.
4. Formation of porous sulfide deposits probably has im-
portant effects in retaining pit contents and promoting pitting
in sulfur-containing electrolytes.
Acknowledgment
This work was performed with support from the Depart-
ment of Energy, Division of Basic Energy Sciences, under con-
tract number DE-ACO2-76CH00016.
References
1. N. Sato. J. Electrochem. Soc.,Vol. 123, p. 1197 (1976).
2. T. Shibata and T. Takeyama. Corrosion, Vol. 33, p. 243
(1977).
3. G. Wranglen. Corros. Sci., Vol. 9, p. 585 (1969).
4. Z. Szklarska-Smialowska. Proc. Conf. Localized Corrosion,
p. 312, NACE (1974).
5. J. L. Crolet, L. Seraphin, and R. Tricot. C. R. Hebd. Seances
Acad. Sci. (C), Vol. 280, p. 333 (1975).
6. N. Pessall and C. Liu. Electrochim. Acta, Vol. 16, p. 1987
(1971).
7. C. J. Semino, P. Pedeferri, G. T. Burstein, and T. P. Hoar.
Corros. Sci., Vol. 19, p. 1069 (1979).
8. H. S. Isaacs and G. Kissel. J. Electrochem. Soc., Vol. 119,
p. 1628 (1972).
 9. H. P. Leckie and H. H. Uhlig. J. Electrochem. Soc., Vol. 113,
p. 1262 (1966).
10. G. Okamoto, K. Tachibana, S. Nishiyama, and T. Sugita.
Proc. Conf. Passivity and its Breakdown on Iron and Iron-
Base Alloys, (Honolulu, 1975), p. 106.
11. J. Yahalom. Ref. 10, p. 121.
12. M. Janik-Czachor, G. C. Wood, and G. E. Thompson. Br.
Corros. J., Vol. 15, p. 154 (1980).
13. H. H. Strehblow and M. B. Ives. Corros, Sci., Vol. 16, p. 317
(1976).
14. J. R. Galvele. J. Electrochem. Soc., Vol. 123, p. 464 (1976).
15. J. L. Crolet, L. Seraphin, and R. Tricot. Mem. Sci. Rev.
Metall., Vol. 73, p. 1 (1976).
16. H. H. Strehblow and J. Wenners. Proc. EUROCORR 77, 6th
International Congress on Metallic Corrosion, p. 671
(1977).
17. K. E. Heusler and L. Fischer. Werkstoffe Korros., Vol. 27, p.
551 (1976).
18. T. R. Beck and R. C. Alkire. J. Electrochem. Soc., Vol. 126,
p. 1662 (1979).
19. J. G. Hines. Electrochim. Acta., Vol. 10, p. 225 (1965).
20. R. A. Casper, P. L. Jensen, H. Ozog, and H. S. Isaacs. Oak
Ridge National Lab. Report No. ORNL-MIT-184 (1974).
21. P. Sury. Corros. Sci., Vol. 16, p. 879 (1976).
22. J. L. Crolet, L. Seraphin, and R. Tricot. Mem. Sci. Rev.
Metall., Vol. 74, p. 281 (1977).
23. S. Brennert. Ref. 16, p. 255.
24. S. Brennert and G. Eklund. Scand. J. Metall., Vol. 5, p. 16
(1976).
25. J. P. Carter and S. D. Cramer. Paper No. 203, Corrosion/80,
Chicago, 1980.
26. K. Ogura and N. Sato. Corros. Sci., Vol. 19, p. 737 (1979).
27. A. M. Danilov, R. L. Baru, V. A. Timonin, and L. I.
Makhonina. Sb. Nauchn. Tr. Vses. Nauchno-Issled.
Zashch. Met. Korroz., Vol. 5, p. 21 (1977).
28. R. C. Scarberry, E. L. Hibner, and J. R. Crum. Paper No. 245,
Corrosion/79, Atlanta, 1979.
29. M. Masuo, T. Tanigawa, Y. Ono, and N. Ohashi. Boshoku
Gijutsu, Vol. 27, p. 565 (1978).
30. H. S. Isaacs, B. Vyas, and M. W. Kendig. Paper No. 26, Cor
rosion/81, Toronto, 1981; submitted to Corrosion.
31. R. C. Newman, K. Sieradzki, and H. S. Isaacs. Proc. Conf.
Environmental Degradation of Engineering Materials,
Virginia Polytechnic Institute, 1981, p. 163. VPI (1981).
32. D. F. Bowers. Preprint, Corrosion/79, Atlanta, 1979.
33. D. F. Bowers. Proc. Conf. Mill Closure: Problems and Solu
tions, Chicago, 1980, p. 23. The Institute of Paper
Chemistry, 1980.
34. H. S. Isaacs and R. C. Newman. Proc. H. H. Uhlig 75th
Birthday Symposium, Denver, 1981, p. 120. The Elec
trochemical Society (1981).
35. R. C. Newman, H. S. Isaacs, and K. Sieradzki. Met. Trans.
(submitted 1981).
36. R. P. Frankenthal and J. Kruger. J. Electrochem. Soc., Vol.
125, p. 403 (1978).

The Effect of Surface Treatments and

Electrochemical Methods on the
Pitting Potentials of Zirconium
in Chloride Solutions*

DONALD R. KNITTEL, * MICHAEL A. MAGUIRE,

A RTURO BRONSON, * * and JONG-SHENG CHEN `"

Abstract
The effect of surface treatments and electrochemical methods on the corrosion (E r ), pit
nucleation (E n p), and critical pitting (E c p) potentials have been investigated for zirconium in
aqueous chloride solutions. Specimens were tested in the milt annealed, SiC abraded,
chemical polished, electropolished, air annealed, and vacuum annealed conditions. E r was
determined by open circuit, nulling, and polarization methods. E n p was determined by poten-
tiostatic, potentiostep, and potentiodynamic methods. E c p was determined by a potential
back-step and a scratch method. The pitting morphology at the surface show radal pit growth.
E r and E n p depend on the surface preparation and environment, but E c p does not depend on
surface preparation or previous potential history. The SiC abraded surface yields the most
reproducible pitting corrosion data and behaves similarly to the as-received milt annealed sur-
face condition. The poteniostatic, scratch and back-step techniques yield the same pitting
potential.

Introduction techniques have been reported, but no universally established

The value of electrochemical techniques for studying the cor- procedure is applicable to all alloy/environment combinations.
rosion characteristics of metals and alloys in electrolyte en- Our objective for this study was to determine the best electro-
vironments, in particular localized corrosion phenomena, have chemical techniques which measure the pitting characteris-
been emphasized for the past 30 years. 1-14 Many experimental tics of Zr.
The electrochemical parameters under investigation are
*Presented during Corrosion/81 (Paper 158), April, 1981, Tor- the open circuit or corrosion potential (E r ), the pit nucleation
onto, Ontario; revised January, 1982. potential (E n p), and the critical pitting potential or repassiva-
'Teledyne Wah Chang Albany, Albany, Oregon. tion potential (E c p) (Figure 1). The meaning of these
"Dept. of Metallurgical Engineering, University of Arizona, parameters has been discussed elsewhere. 3-14 This study has
Tucson, Arizona. investigated the effect of surface temperatures and electro-
0010-9312/82/000093/$3.00/0
Vol. 38, No. 5, May, 1982 1. 1982, National Association of Corrosion Engineers 265