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Role of Thiosulfate in the Corrosion of Steels: A Review

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DOI: 10.5006/1709

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 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
Role of Thiosulfate in the Corrosion
of Steels: A Review
Lokesh Choudhary,‡,* Digby D. Macdonald,** and Akram Alfantazi*
ABSTRACT
Thiosulfate salts have been known to be dangerous corrosion
promoters for over 30 y, when present under typical service
conditions. This paper reviews the role of thiosulfate anion in
causing localized corrosion and/or stress corrosion cracking
of steels. Electrochemical and mechanical aspects associated
with the pitting and stress corrosion cracking of steels in thio-
sulfate-containing environments are thoroughly discussed and
reviewed. In particular, results from the research studies rele-
vant to pulp and paper, oil and gas, and nuclear industries,
where thiosulfate ion is known to be present advertently or
inadvertently, have been analyzed.
KEY WORDS: pitting, steels, stress corrosion cracking,
thiosulfate, volt-equivalent diagram
INTRODUCTION
Thiosulfate (S2O32−) salts play important roles in vari-
ous industries, such as chemical, pharmaceutical,
medical, pulp and paper, nuclear, hydrometallurgy, etc.
Thiosulfate is found as a byproduct chemical in the
paper industry, an image fixing agent in photography,
an antidote to cyanide and arsenic poisoning, and as a
Submitted for publication: March 14, 2015. Revised and accepted:
May 31, 2015. Preprint available online: June 1, 2015,
http://dx.doi.org/10.5006/1709.
‡
Corresponding author. E-mail: lokesh.choudhary@ubc.ca.
*
Department of Materials Engineering, University of British
Columbia, 6350 Stores Road, Vancouver, BC V6T1Z4, Canada.
**
Department of Materials Science and Engineering, University of
(1)
California at Berkeley, Berkeley, CA 94720.
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
ISSN 0010-9312 (print), 1938-159X (online)
CORROSION—Vol. 71, No. 9 15/000187/$5.00+$0.50/0 © 2015, NACE International
fertilizer in the agricultural industry.1-3 In recent times,
thiosulfate anion has been identified as an attractive,
environmentally-benign lixiviant in gold leaching
technologies, in contrast to the commonly used and
hazardous cyanide.4-6 Thiosulfate may also be present
in many other instances such as impurities or un-
wanted species.1,7 It can be found as a consequence of
the aerial oxidation of sulfide or as a metabolic product
of sulfate reduction as produced by sulfate-reducing
bacteria.8-9 Thiosulfate ion is used as a radioactive
iodine “getter” in building spray systems in pressurized
water reactors (PWRs) in the nuclear power industry.
Oil and gas pipelines and sewage systems may also
contain thiosulfate, which ultimately leads to genera-
tion of toxic hydrogen sulfide gas.10-11
As discussed above, thiosulfate salts are versatile
and widely used in many applications and technologies
either advertently or inadvertently. Thiosulfate is con-
sidered to be a very aggressive species, and can cause
environmental degradation of a variety of structural
materials.1,7,12-19 In the mid-nineties, corrosion failures
resulting from the thiosulfate ion were observed in
the pulp and paper industry,20-22 for example, because
of intergranular stress corrosion cracking (IGSCC) in
sensitized stainless steels. Thiosulfate has also been
implicated in causing enhanced environmental degra-
dation of nuclear waste storage containers.7,23 The
leakage of thiosulfate species into the borated water
during layup of the Three Mile Island, Unit 2, PWR, after
the well-known partial core melt-down of Unit 1 in
1987,7,23-25 caused extensive cracking of the Alloy 600
(UNS N06600)(1) and 800 (UNS N08800) steam gener-
ator tubes. Furthermore, in the removal of sulfur from
1147
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
crude oil in preparation for refining, thiosulfate and
other polysulfur species form and have been identified
as causing IGSCC of sensitized Type 304 stainless
steel (SS, UNS S30400), which is now recognized as a
form of hydrogen-induced cracking (HIC).10 The main
forms of corrosion that have been observed in the
presence of the thiosulfate ion in solution are principally
pitting,12-14,26 stress corrosion cracking (SCC),27-29
corrosion fatigue,30 and crevice corrosion.31-32 These are
all dangerous forms of corrosion, which frequently lead
to the failure of infrastructure materials under a wide
range of service conditions.
While localized corrosion and/or environmentally-
assisted cracking of structural materials in aqueous
solutions containing the thiosulfate anion have been
subject of extensive research over the last five decades,
no critical review of pitting and SCC of structural
materials in thiosulfate solution is available, except for
a brief discussion on SCC of sensitized stainless steel
by Cragnolino and Macdonald,24 published in 1982.
They performed a thorough review of the IGSCC of
austenitic sensitized stainless steel at temperatures
below 100°C, with specific emphasis on sulfur species.
Although the role of thiosulfate in causing IGSCC in
sensitized stainless steel was discussed, the review
does not consider the broad corrosion problems en-
countered in other structural materials, as a result of
the presence of thiosulfate anion in aqueous environ-
ments. Given the use of thiosulfate salts in various
industrial applications, the authors find it imperative to
review most of the corrosion research performed on
steels in thiosulfate environments. Hence, in this re-
view, an objective is to summarize and analyze previous
corrosion studies on steels in thiosulfate solutions.
While the emphasis in this review is on thiosulfate, it is
important to note that S2O32− is only one of many
polysulfur oxyanions that exist in the S-H2O system,
depending upon the pH and redox potential of the
environment. In order to illustrate the complexity of
the S-H2O system, this study will discuss other poly-
sulfur species, including the polysulfides (e.g., Sx2−,
x = 2 − 8) and polythiosulfates, that form in this system,
as the need arises. Finally, although the principal
focus of this review is on the stainless steels and more
specifically on the austenitic stainless steels, occa-
sionally other metals and alloys will be included, in
order to illustrate specific modes of interaction of
sulfur-containing species with materials.
THERMODYNAMICS OF THE SULFUR-WATER
SYSTEM
Sulfur Species
Sulfur is an active, multivalent element and forms
many different species, including many oxyanions,
that exist over a range of oxidation states from −2 to 8,33
with many oxidations being fractional because of the
presence of several sulfur atoms having different
1148
oxidation states in the same compound. Some of these
oxyanions are thiosulfate (S2O32−), trithionate (S3O62−),
tetrathionate (S4O62−), pentathionate (S5O62−), sulfate
(SO42−), sulfite (SO32−), dithionite (S2O42−), dithionate
(S2O62−), and persulfate (S2O82−), to name but a few
of the known members. A comprehensive listing of
the various, currently-known sulfur species, together
with the thermodynamic data for their formation, is
given in Table 1.34 This is considered to be the most
comprehensive listing currently available and it pro-
vides the base data for the generation of Pourbaix
diagrams, volt-equivalent diagrams (VEDs), and cor-
rosion domain diagrams (CDDs) that are of immense
utility in interpreting the electrochemistry of the sulfur-
water system. This system is the most complex system
in chemistry after the C-O-H system, with the sulfur
displaying a greater range of oxidation state (−2 to 8,
see Table 1) than does any other element in the peri-
odic table.
Pourbaix Diagrams
Out of all of the known sulfur species listed in
Table 1, S2O32− is an interesting, metastable anion and
deserves particular attention. S2O32− can be oxidized/
reduced, and can disproportionate or decompose under
varying electrochemical and/or chemical conditions.
A typical E-pH (Pourbaix) diagram for the S-H2O system
is shown in Figure 1.42 This diagram does not include
the stability regions for sulfate or bisulfate (which are
thermodynamically very stable), in order to depict
stability regions of the metastable species, such as
thiosulfate, tetrathionate, sulfite, etc. Thiosulfate is
thermodynamically stable only in a narrow, elongated
field in neutral and alkaline solutions, as can be seen
from Figure 1. It tends to undergo chemical decompo-
sition in aqueous solutions. It may oxidize to sulfite,
polythionates, and ultimately to sulfate, or reduce to
elemental sulfur and sulfide (or to polysulfides),
depending upon the redox potential and the pH of the
system. Some of the relevant oxidation, reduction,
and disproportionation reactions involving thiosulfate
ion are given in Table 2.
Equation (1) forms a basis for the determination
of thiosulfate in the solution by iodimetric titration,
which is based on the quantitative oxidation of thio-
sulfate by iodine.2 Equations (8) and (9) show that
thiosulfate has a tendency to disproportionate at a
low pH to sulfur and sulfur dioxide or in alkaline
solutions to sulfide and sulfate (Equation [10]).2,10
Equation (10) also provides a basis for stabilizing
thiosulfate solution by the addition of sulfate.
Thiosulfate was found to be an unintended by-
product of sodium dithionite, a newsprint brightening
agent, and hence, thiosulfate was present in small
amounts in the papermaking process. Thiosulfate acts
as a neutralizer of the chlorine compounds (e.g., Cl2,
HClO) that are used as bleaching agents (Equation [2],
Table 2).1-2 Thiosulfate is helpful in converting toxic
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

TABLE 1
Thermodynamic Data for Polysulfides and Polythiooxyanions34,(A)
Species ΔGfo kJ/mol ΔHfo kJ/mol S0 J/Kmol Cp0 J/Kmol Reference

S22−(−1) 77.685 13.040 28.451 −221.635 35

S32−(−2/3) 71.564 6.600 9.000 −222.744 35
S42−(−1/2) 56.394 9.000 100.000 −226.000 35
S52−(−2/5) 66.666 21.338 139.000 −227.395 35
S62−(−1/3) 68.189 13.300 139.000 −227.395 35
S72−(−2/7) 80.951 16.500 139.000 −227.395 35
S82−(−1/4) 88.272 23.800 171.000 −228.540 35
2−
S (−2) 85.973 33.095 −14.602 −137.154 36, 37
S2O32− (2) −518.646 −648.520 66.944 −237.631 37, 38
S4O62− (5/2) −1,040.253 −1,224.238 257.316 −109.153 37, 38
S2O42− (3) −600.567 −753.538 92.048 −207.684 37, 38
S2O52− (4) −790.876 −970.688 104.600 −200.199 38
S2O62− (5) −969.037 −1,173.194 125.520 −187.730 38
S2O72− (6) −795.090 −1,011.101 188.334 −75.969 39
S2O82− (7) −1,114.868 −1,344.763 244.346 −103.318 37, 38
S3O32− (4/3) −827.187 −951.400 118.001 −198.747 39
S3O62− (10/3) −957.360 −1,167.336 138.072 −180.243 38, 40
S4O32− (1) −957.384 −1,085.099 138.323 −163.272 39
S5O32− (5/4) −1,030.080 −1,159.700 164.004 −118.441 39
S5O62− (2) −955.337 −1,175.704 167.360 −162.782 38
S6O32− (2/3) −1,074.377 −1,205.201 192.037 −69.505 39
S6O62− (5/3) −1,196.975 −1,381.000 321.323 156.185 39
S7O32− (4/7) −1,104.774 −1,236.401 221.413 −18.224 39
HS− (−2) 12.082 −16.108 68.199 −93.618 36–38
HS2− (−1) 11.506 −267.902 −742.317 −195.115 39
HS3− (−2/3) 20.510 −352.402 −1,023.862 −185.042 39
HS4− (−1/2) 27.714 −394.401 −1,156.822 −180.285 39
HS5− (−2/5) 33.017 −419.601 −1,227.058 −177.772 39
HS6− (−1/3) 36.228 −436.299 −1,261.765 −176.530 39
H2S(a) (−2) −28.600 −39.706 125.500 183.667 41
H2S2O4(a) (3) −616.660 −733.455 213.384 155.905 38
HS2O4− (3) −614.471 −749.354 152.716 56.282 38, 39
H2SO3(a) (4) −537.860 −608.898 232.212 0.000 37
H2S2O3(a) (2) −535.576 −629.274 188.280 114.724 38
HSO3− (4) −527.613 −626.219 139.746 −5.304 37, 38
H2SO4(a) (6) −744.526 −909.392 20.083 −176.410 37
HSO4− (6) −755.670 −889.100 125.520 22.589 37, 38
HSO5− (8) −637.440 −775.630 212.129 154.047 36, 38
HS2O3− (4) −532.132 −643.918 127.612 15.095 38
SO32− (4) −486.546 −635.550 −29.288 −280.022 38
SO42− (6) −744.361 −909.602 18.828 −264.944 37, 38
SO2(a) (4) −300.555 −323.005 161.921 311.612 37, 38
SO3(a) (6) −525.637 −635.591 −28.995 0.000 37
HS2O5− (4) −998.490 −1,218.799 −31.229 −532.911 39
HS2O6− (5) −1,073.389 −739.798 1,929.134 6,013.290 39
HS2O7− (6) −1,372.589 −1,253.798 1,311.266 3,950.056 39
HS2O8− (7) −1,510.289 −1,253.798 1,875.687 5,834.817 39
HS3O3− (4/3) −471.386 −718.899 −295.549 −1,415.549 39
HS4O3− (1) −477.382 −760.898 −384.233 −1,711.690 39
HS5O3− (4/5) −480.179 −786.098 −427.308 −1,855.527 39
HS6O3− (2/3) −481.378 −802.801 −447.236 −1,922.074 39
HS7O3− (4/7) −481.974 −815.001 −454.085 −1,944.945 39
(A)
Average sulfur oxidation states are contained in parentheses after the identity of each species.

cyanides into nontoxic products according to Equa-
tion (7).45 Over the last two decades, thiosulfate has
been extensively researched for its use as a leachant in
gold recovery.4,6,43-44 Thus, Equation (3) is of great
importance in the ammoniacal thiosulfate leaching of
gold. The presence of cupric ions is known to accelerate
the oxidation of thiosulfate in aqueous gold leaching
solutions (Equation [3]).46
Equations (6) and (8) also form a significant basis
for replacing difficult-to-handle sour gas environments
(H2S) by more easily managed thiosulfate solutions in
laboratory experiments. Based on literature reports,
thiosulfate can often be used as a substitute for H2S
because it is reduced to H2S when in contact with
carbon steel.10 The corrosion potential of carbon steel in
thiosulfate solutions (at pH ∼2.7 to 3) is reported to be

CORROSION—Vol. 71, No. 9 1149

CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

TABLE 2
Chemical Reactions Involving Thiosulfate
Reaction ΔG0 at 298 K (kJ/mol) Reference Equation

Oxidation
2 S2O32− + I3− = S4O62− + 3 I− −88 2 (1)
S2O32− + 4 Cl2 + 5 H2O = 2 SO42− + 8 Cl− + 10 H+ −829.1 2 (2)
5 S2O32− + Au + Cu(NH3)42+ = Au(S2O3)23− + 4NH3 + Cu(S2O3)35− −14.1 4, 6, 43, 44 (3)
S2O32− + 2 O2 + 2OH− = 2 SO42− + H2O −887.2 45 (4)
S2O32− + ½ O2 + H2O = 2 S4O62− + 2 OH− −61.9 45 (5)

Reduction
S2O32− + 6H+ + 4e− = 2S + 3 H2O −192.8 10, 33 (6)
S2O32− + CN− = SO32− + CNS− −44 45 (7)

Disproportionation
S2O32− + H+ = S0 + HSO3− −3.1 10, 33 (8)
S2O32− + 2 H+ = SO2 + S0 + H2O −18.7 2 (9)
S2O32− + 2 OH− = SO42− + S2− + H2O −53.8 2 (10)

is well borne-out by examining the species listed in

FIGURE 1. E-pH (Pourbaix) diagram for the S-H2O system at 298 K.
The thermodynamically-stable sulfates are omitted for clarity in dis-
playing the metastable species domains. Dissolved sulfur species
activity = 0.001.42
approximately −400 mVSHE,10 which corresponds to the
H2S stable region in a sulfur-water Pourbaix diagram
at room temperature (Figure 1).42 This provides a
thermodynamic basis for the use of thiosulfate solu-
tions as a replacement for toxic H2S solutions in steel
corrosion studies.
The elemental sulfur produced by Equations (6)
and (8) (Table 2) can further reduce or disproportionate
to yield H2S (Equations [11] and [12]).10,33
4S0 þ 4H2 O þ H+ = 3H2 S þ SO2−
4 þ 3H
+
S þ 2H+ þ 2e− = H2 S
Volt-Equivalent (Frost) Diagrams
It is well recognized that the chemistry of sulfur is
more complex than that of any other element in the
periodic table, except for carbon, as noted above. This
Table 1, where it is seen that the oxidation state varies
from −2 (sulfide) to 8 (“persulfate,” or more accurately,
the peroxymonosulfate ion, SO52−) and by noting that
many species have fractional oxidation states corre-
sponding to the presence of two or more sulfur atoms
having different oxidation states. Recognizing the great
complexity of the system, and by further noting that
the oxidation state varies over a wide range, the ques-
tion arises as the best method for displaying the redox
properties of the system. The vehicle chosen for this
purpose is the VED,35 sometimes known as Frost dia-
grams, as inclusion of all of the species listed in Table 1
produces a Pourbaix diagram that is too complex to
convey useful information (note that in a Pourbaix
diagram, the equilibrium information of any given
species is represented as a line, whereas in a VED, the
information is represented as a point). That is why
Pourbaix diagrams for the S-H2O system commonly
restrict the number and type of species included in
construction of the diagram, as is evident in Figure 1.
The volt equivalent (VE) for a species is the equi-
librium potential for the reduction reaction of the
species (e.g., SxOy2−) with respect to elemental sulfur,
as represented by Equation (13):
+ −
y þ 2yH þ 2ðy − 1Þe = ðx=8ÞS8 þ yH2 O
Sx O2− (13)
multiplied by the average oxidation state of sulfur in
the species [z = 2(y − 1)/x]. The VED is then formed by
plotting the VEs for the various species versus the
average oxidation state. In doing so, the standard
(11)
potential is first calculated by using Equation (14):
(12)
ΔR G0
E0 = − (14)
2ðy − 1ÞF
where ΔRG0 is the change in standard Gibbs energy
for the cell reaction, SxOy2− + 2yH+ + 2(y − 1)e− = (x/8)S8
+ yH2O.

1150 CORROSION—SEPTEMBER 2015

 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

TABLE 3
Reduction Reaction for Sulfur Species Used in Defining the
Volt Equivalent34
Species Reduction Reaction

H2S 1/8S8(s) + 2H+ + 2e− = H2S(a)

HS− 1/4S8(s) + H+ + 2e− = 2HS−
S2− 1/8S8(s) + 2e− = S2−
S22− 1/4S8(s) + 2e− = S22−
HS2− 1/4S8(s) + H+ + 2e− = HS2−
S32− 3/8S8(s) + 2e− = S32−
HS3− 3/8S8(s) + H++2e− = HS3−
S42− 1/2S8(s) + 2e− = S42−
HS4− 1/2S8(s) + H++2e− = HS4−
S52− 5/8S8(s) + 2e− = S52−
HS5− 5/8S8(s) + H++2e− = HS5−
S62− 3/4S8(s) + 2e− = S62−
HS6− 3/4S8(s) + H+ + 2e− = HS6−
S8 –
S2O32− S2O32− + 6H+ + 4e− = 1/4S8(s) + 3H2O
FIGURE 2. Volt-equivalent diagram for the S-H2O system at 25°C,
S4O62− S4O6 + 12H + 10e− = 1/2S8(s) + 6H2O
2− +

H2S2O4 H2S2O4 + 6H+ + 6e− = 1/4S8(s) + 4H2O pH = 0.34

HS2O4− HS2O4− + 7H+ + 6e− = 1/4S8(s) + 4H2O
S2O42− S2O42− + 8H+ + 6e− = 1/4S8(s) + 4H2O
H2SO3 H2SO3 + 4H+ + 4e− = 1/8S8(s) + 3H2O
HSO3− HSO3− + 5H+ + 4e− = 1/8S8(s) + 3H2O
SO32− SO32− + 6H+ + 4e− = 1/8S8(s) + 3H2O
H2SO4 H2SO4 + 6H+ + 6e− = 1/8S8(s) + 4H2O
HSO4− HSO4− + 7H+ + 6e− = 1/8S8(s) + 4H2O
SO42− SO42− + 8H+ + 6e− = 1/8S8(s) + 4H2O
S72− 7S + 2e− = S72−
S82− 8S + 2e− = S82−
S7O32− S7O32− + 6H+ + 4e− = 7S(s) + 3H2O
S6O32− S6O32− + 6H+ + 4e− = 6S(s) + 3H2O
S5O32− S5O32− + 6H+ + 4e− = 5S(s) + 3H2O
S4O32− S4O32− + 6H+ + 4e− = 4S(s) + 3H2O
S3O32− S3O32− + 6H+ + 4e− = 3S(s) + 3H2O
S7O62− S7O62− + 12H+ + 10e− = 7S(s) + 6H2O
S6O62− S6O62− + 12H+ + 10e− = 6S(s) + 6H2O
S5O62− S5O62− + 12H+ + 10e− = 5S(s) + 6H2O
S3O62− S3O62− + 12H+ + 10e− = 3S(s) + 6H2O

The equilibrium potential is then given by the

Nernst equation as: FIGURE 3. Volt-equivalent diagram for the S-H2O system at 25°C,


 pH = 10.5.34
2.303RT 1
Ee = E 0 − log 2y (15)
2Fðy − 1Þ aH+ aSx O2−
y

VESO2− − VES2 O2− 2.12 − 1.00

where aSx O2− is the activity of the sulfur oxyanion and E0 = 4 3
= = 0.280ðVÞ (16)
− SOSS2 O2− 6−2
y
aH+ is the corresponding quantity for H+. The VE for SOSSO2−
4 3

SxOy2− is then simply zEe, where z = 2(y − 1)/x. The

reduction reactions used to define the VEs of the
various species are summarized in Table 3.
Figures 2 through 5 display VEDs for the S/H2O
system at pH = 0 and 10.5, and at temperatures of
25°C, 150°C, and 275°C.34 The diagrams are derived for
all sulfur species having unit activity. The first impor-
tant feature is that the slope of a line joining any two
species corresponds to the reduction potential of the
associated couple. This is illustrated by using, for
example, the SO42−/S2O32− couple in Figure 2. The
standard reduction potential E0 for this couple can be
calculated from the VED as:
where VEX and SOSX are the VE and sulfur oxidation
state of the species, X, respectively. In this way, the
standard reduction potential for any conceivable redox
couple formed by a line joining two species in the
VED can be readily calculated. It is known that the
reduction potential generally depends strongly on pH.
Thus, Figure 3 shows a VED for the S/H2O system at
pH = 10.5 and at 25°C. It is evident that the shape of
the diagram is much different than that shown in
Figure 2 for an acidic environment, with most of the
slopes now being negative. The relative positions of
some species have also been changed dramatically.

CORROSION—Vol. 71, No. 9 1151

CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 4. Volt-equivalent diagram for the S-H2O system at 150°C,
pH = 0.34
This observation makes it clear that knowledge of the
pH of a system is vital for defining and studying its redox
chemistry.
Temperature is another important parameter in
defining a VED. Figure 4 shows a VED for the S/H2O
system at pH = 0 and at 150°C. Comparison of
Figures 4 and 2 suggests that, although the shapes
of the diagrams are similar, the relative positions of
some species are significantly different. This arises
because increasing or decreasing the temperature
changes the reduction potential for the relevant spe-
cies and hence modifies the redox chemistry of the
system, as expected.
VEDs are also useful in studying a chemical system
in the following ways. First, if a species lies above a
line joining any two other compounds, this species
will tend to disproportionate into the other two com-
pounds. Thus, in Figure 5, for example, the decompo-
sition of S2O32− in acidic solution is illustrated by
this principle (labeled with red color). It is clear that
S2O32− lies above the line joining S and S4O62−. This
suggests that, although the decomposition of S2O32− is
a complex reaction forming many products, one reac-
tion that may occur is:
+
3 þ 6H → 2S þ 2S4 O6 þ 3H2 O
5S2 O2−
2−
(17)
This reaction is spontaneous because the resulting
change in the Gibbs energy is negative, which may be
confirmed by using the data given in Table 1. This
shows that it is thermodynamically possible for thio-
sulfate, i.e., S2O32−, to undergo a redox self-dispro-
portionation reaction into a reduction product, S, and
an oxidation product, S4O62−. It is reactions of this
type that have led to the partially oxidized or reduced
sulfur species being termed “highly labile.”
Second, if a species lies below a line joining any
two other compounds, the latter will tend to react to
1152
FIGURE 5. Volt-equivalent diagram for the S-H2O system at 275°C,
pH = 0.34
produce the former. A good example is found in the
reduction of sulfuric acid by hydrogen sulfide. Thus,
data plotted in Figure 5 predicts that, at pH = 0 and at
275°C, the following reaction is thermodynamically
favorable:
+
3H2 S þ SO2−
4 þ 2H ⇔ 4S þ 4H2 O (18)
because S lies below the line joining H2S and SO42−
(labeled with green color). Again, use of the thermody-
namic data contained in Table 1 will confirm that this
reaction is spontaneous; that is, the change in Gibbs
energy is negative.
In addition, the interpretation of the diagrams fol-
lows the following rules:
• Any two species connected by a straight line will
tend to react to produce all of the species that lie below
that line. Thus, the reaction of S2− and H2S2O4 is pre-
dicted to generate essentially all other species plotted on
the diagram.
• If a species lies above the straight line joining two
other species, it will tend to disproportionate to produce
the latter. Thus, S22− lies above the line joining HS− and
S32−, so the disproportionation reaction 2S22− + H+ →
HS− + S32− is predicted to occur.
• If several species lie on or close to a straight line
joining two terminal species, the solution will contain all
species in equilibrium at finite concentrations.
The reactivity of any given species toward a metal,
in which a metal sulfide is formed, is measured by the
value of the VE. The more reactive species are charac-
terized by high (more positive) VE values. Indeed the
most reactive species tend to be located in the upper left
quadrant, implying high reactivity and high electron
density being simultaneously present, followed by
species in the upper right quadrant. Species in the lower
quadrants tend to be the least reactive toward a
metal.
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

FIGURE 6. Pourbaix diagram for: (a) Fe-S-H2O, (b) Cu-S-H2O, and (c) Ni-S-H2O at 25°C (S = 1 mol/kg).

Corrosion Domain Diagrams In order to display the thermodynamics of activa-

The well-known ability of sulfide and polysulfur tion in better detail, a new innovative technique of
species, including thiosulfate ion, to activate metals, CDDs has been developed47-49 to characterize, quan-
such as copper, iron, and nickel has significant impli- titatively, whether copper is “semi-noble” or “active.”
cations for the use of these metals and their alloys in These diagrams use the same thermodynamic data that
many industrial and geo-energy applications. Con- are used for constructing a Pourbaix diagram (Figure 6),
struction of the Pourbaix diagrams for iron, nickel, and but the results are presented in a different form. In
copper, all of which are thermodynamically-activated its simplest representation, the corrosion of copper
in the presence of sulfide ion and other sulfur-con- in the absence of sulfur-containing species may be
taining species (including thiosulfate), reveal that ac- written in chemical form as:
tivation occurs by the development of a partial anodic
reaction of metal sulfide formation at potentials that 1
Cu þ H+ ðaqÞ ↔ Cu+ ðaqÞ þ H ðgÞ (19)
are significantly more negative than the potential at 2 2
which the oxide forms, such that hydrogen evolution
becomes a viable cathodic reaction in place of oxygen The change in Gibbs energy for this reaction can be
reduction. This is illustrated by the Pourbaix diagrams written as:
(drawn using HSC Chemistry 6† software package) 1=2
!
f H2 aCu+
shown in Figures 6(a), (b), and (c) for iron, copper, and ΔG = ΔG þ 2.303RT log
0
(20)
nickel, respectively, in the presence of sulfur species. a H+

†
Trade name. which, upon rearrangement yields:

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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
1=2 ΔG − ΔG0
logðf H2 aCu+ Þ = − pH (21)
2.303RT
At equilibrium, ΔG = 0, so that:
Pe = f H2 aeCu+ = 10−ð2.303 RTþpHÞ
e,1=2 ΔG0
(22)
where Pe is termed the partial equilibrium reaction
quotient. For nonequilibrium conditions, the dependent
variable, P, is defined in similar fashion as:
1=2
P = f H2 aCu+ (23)
The condition for spontaneity of reaction then becomes
P < Pe and immunity is indicated by P > Pe. As seen in
Figure 7, the value of log(Pe) at pH = 7 and at 298 K (25°
C) is approximately −15, showing that only a very small
activity of Cu+ combined with a small fugacity of hy-
drogen is needed to render copper immune to corrosion
in a closed system, with P ≥ Pe.
The CDDs were originally developed to describe
the activation of copper in the proposed granitic high
level nuclear waste (HLNW) repository in Sweden,
but the concept is perfectly general. The groundwater
composition in the repository is far from being that
of pure water, and a common contaminant is sulfide
as H2S, HS−, or S2− because of the reducing nature
of the environment.47 Indeed, it is known that sulfide,
and possibly other sulfur-containing species, are
ubiquitous in ground water environments. The corro-
sion of copper is then described as:
2Cu þ HS− þ H+ = Cu2 S þ H2 (24)
where the change in Gibbs energy of the reaction can be
written as:
 
f H2
ΔG = ΔG0 þ 20303 RT log (25)
aHS− aH+
FIGURE 7. Corrosion domain diagram displaying the conditions
under which corrosion is and is not possible.
1154
Thus, in this case, the partial equilibrium reaction
quotient, Pe, is now defined as:
f eH2
Pe = (26)
aeHS−
where
 
f eH2 ΔG0
− 2.303 RT þpH
= 10 (27)
aeHS−
A CDD for copper in the presence of bisulfide ion
(HS−) is displayed in Figure 8. Note that it has the same
form as that shown in Figure 7 for the sulfide-free
case, but that log(Pe) has shifted in the positive direction
by 25 units (Pe has increased by a factor of 1025),
thereby greatly expanding the “Corrosion Possible
(Active)” domain at the expense of the domain of im-
munity. Thus, bisulfide is clearly a powerful activator of
the corrosion of copper, as is observed in practice.
CDDs have also been developed for copper in the
presence of various polysulfur species, and four
examples are presented in Figure 9. For the polysulfur
oxy species, tribithiosulfite (HS3O3−), thiosulfuric acid
(H2S2O3), and bithiosulfate (HS2O3−), the slope of
Pe vs. pH is positive, rather than being negative as it
is for HS− and S32−. The red arrows indicate the value
of P in the proposed Swedish HLNW repository at
Forsmark, based upon estimates of the sulfur species
concentrations via Gibbs energy minimization and
the known (estimated) fugacity of hydrogen. As can
be seen, in all cases the value of P lies well below
Pe, so that even for concentrations (activities) of
≈10−20 M and hydrogen pressure (fugacity) of ≈10−14 atm
(0.101325 kPa) copper is activated toward corrosion
and the formation of Cu2S.
Finally, if the composition of the system is such
that P < Pe and corrosion is spontaneous, then P will
migrate in the positive direction as corrosion products
FIGURE 8. Corrosion domain diagram for copper in water + HS− as a
function of temperature.
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

FIGURE 9. Corrosion domain diagrams for copper in the presence of polysulfur species, trisulfide (S32−), tribithiosulfite
(HS3O3−), thiosulfuric acid (H2S2O3), and bithiosulfate (HS2O3−).

build up or reactants are depleted at the interface. This
will continue until P = Pe and if the system is closed, the
system will become stationary at equilibrium. For an
open system, in which products may migrate away
from, and reactants may migrate toward, the interface,
the system will exist in steady state and the metal will
continue to corrode at a rate that is governed by the
rates of mass transport of products from, and reactants
to, the metal surface. Thus, the rate of corrosion
becomes controlled by mass transport processes in the
near-field environment. In the case of copper canisters
in the Swedish HLNW disposal technology, the
near-field environment is compacted, rehydrated
bentonite clay, which is sufficiently impervious that the
canister is predicted to contain the waste for many
hundreds of thousands of years.
Similar diagrams can be derived for iron and nickel,
but to our knowledge this has not yet been done. The
relevance is readily discerned when it is noted that,
in the stainless steels and nickel-based alloys (e.g., Alloy
600), the precipitation of chromium carbides (e.g.,
Cr23C6) on the grain boundaries during sensitization
denudes the boundaries of chromium, thereby pre-
venting the formation of a sulfur-resistant, defective

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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
chromic oxide (Cr2+xO3−y) barrier layer of the passive
film on the boundaries. Thus the boundaries, which
comprise mostly Fe and Ni, become susceptible to ac-
tivation by sulfide and thiosulfate as described above
for copper, resulting in rapid intergranular attack
and IGSCC.
CORROSION OF METALS AND ALLOYS IN
THIOSULFATE SOLUTIONS
As discussed above, several of these sulfur com-
pounds are metastable, hence most often a mixture of
sulfur compound is found in the aqueous solution,
including many, if not most, of those listed in Table 1.
Marcus and Protopopoff50-53 attempted to derive the
conditions of potential and pH for reduction of thio-
sulfate to form adsorbed sulfur on the surfaces of Fe, Ni,
and Cr at 25°C and 300°C in water. They successfully
constructed E-pH diagrams for Fe, Ni, and Cr with
adsorbed sulfur and oxygen in water containing
HS2O3−, S2O32−, H2S, and HS−. The principal motivation
behind their work was to elucidate the experimental
observation that the presence of thiosulfate ions in
aqueous solution were detrimental to the corrosion
resistance of alloys such as stainless steels and various
nickel-based alloys,12-15,21,27,31,54-63 which was
attributed to the formation of adsorbed sulfur on the
metal surface. It was reported that the adsorbed sulfur
layer could cause the observed detrimental effect
by inhibiting the repassivation process. The subse-
quent sections discuss the role of thiosulfate in envi-
ronmental degradation of steels.
Pitting of Steels in Thiosulfate-Chloride Solutions
This section presents a survey of literature related
to localized corrosion/pitting of stainless steels in
thiosulfate-containing solutions, particularly for the
austenitic Type 304 SS or variants thereof. Table 4
contains a condensed summary of papers extracted
from the literature, including information on alloy,
environment, and testing procedure involved, and is
only meant to provide a general overview for comparison
purposes, rather than be an exhaustive review.
Localized corrosion and pitting as a result of thio-
sulfate were first observed in the pulp and paper in-
dustry.21 Thiosulfate is not intentionally added to the
white liquor, but is normally found as an impurity and
its generation is the result of air oxidation of the sulfide
or hydrosulfide, according to the reactions:69
2HS− ðaÞ þ 2O2 ðaÞ = S2 O2−
3 ðaÞ þ H2 O (28)
2Na2 Sx þ 3O2 = 2Na2 S2 O3 þ 2ðx − 2ÞS0 (29)
Therefore, thiosulfate is only present at a very low
concentration. However, even a very low concentration
of thiosulfate has the potential to cause severe cor-
rosion of carbon steel,21 which was the conventional
1156
material of construction of the clarifiers, storage
tanks, digesters, and recausticizing equipment in pa-
per print machines. Wensley, et al.,21 report an in-
crease in the corrosion potential of mild steel with
increasing amount of polysulfides in white liquor. The
presence of sulfide and thiosulfate in the solution were
found to impair the ability of steel to passivate and
hence, for this reason were thought to be corrosion
activators. However, as noted, sulfide and polysulfur
oxyanions, such as S2O32−, S4O62−, etc., can also activate
a metal by giving rise to a partial anodic process (for-
mation of an unprotective metal sulfide) at a potential
that is significantly more negative than that for the
formation of a protective oxide. Those sulfur oxyanions
that do not have donatable sulfur (e.g., sulfite and sul-
fate) are reported to have no effect on the corrosion
rate of mild steel.21
Newman and coworkers studied thiosulfate-
induced corrosion for more than a decade, and inves-
tigated the effect of thiosulfate on the pitting of Types
304 and 316 (UNS S31600) SS using potentiodynamic
and scratching techniques.12-14 Sharp pit initiation was
observed in 0.25 M NaCl + 0.01 M Na2S2O3 solution,
which was characterized by sharp increase in current
(Figure 10), as observed during potentiodynamic
polarization testing.13 The pits formed in thiosulfate
solutions were never observed to repassivate above the
pitting potential and contained a black deposit, which
dissolved in dilute sulfuric acid with the evolution
of H2S.13 This observation suggested the presence of
metal sulfides within the pit, although spectroscopic
analysis was not performed. If the thiosulfate concen-
tration was sufficiently high that the barrier layer
of the passive film was the sulfide (e.g., FeS), then the
black deposit is likely to be the remnants of the passive
film that had collapsed into the pit after initiation.
However, the sulfide may also form by the reaction of
metal cations and sulfide ion resulting from the re-
duction of thiosulfate on the metal surface, with this
mechanism being applicable when the barrier oxide
is a metal oxide.
Further studies by Newman, et. al,14 and Garner15
also showed that thiosulfate ion can pit sensitized
Type 304 SS, even in the absence of chloride ion,
provided that the relative concentration of sulfate and
thiosulfate were within a narrow range. Severe pitting
was observed for the SO42−:S2O32− ratios of 6 to 23.
Hence, the inhibition of pitting of steels as a result of the
presence of sulfate ions in the solution, as observed by
Leckie, et al.,70 may not necessarily be observed if
thiosulfate ion is present. It was further reported that
the thiosulfate pitting occurred not only in the narrow
range of ionic concentration, but also over a limited
range of potential, as shown in Figure 11.14 If the
potential is too oxidizing, the absorbed sulfur species
cannot be generated and the alloy behaves as though
thiosulfate was absent. Consequently, when the
chloride ion concentration is low, no pitting will
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

TABLE 4
Summary of a Few Critical Studies Performed on the Pitting of Stainless and Carbon Steels in Thiosulfate Solutions
Critical Results
Material Environment Testing Details Observed Reference

Type 304 SS 0.25 M NaCl + (0.001 M − 0.1 M) Potentiodynamic and scratch a) Severe pitting for 0.25 M 13
Na2S2O3 electrode measurements NaCl + 0.01 M Na2S2O3
b) Inhibition of pitting for large
concentrations of thiosulfate
(0.1 M Na2S2O3)
Fe-17Cr alloy 0.02 M NaCl + 30 ppm S2O32− Potentiodynamic polarization Pitting was observed and pitting me- 55
and XPS chanism by reduction of thiosulfate into
sulfur on active surfaces of steel
was established and confirmed by
XPS results

Type 304, 316L, 1 M NaCl-(0.0001 M − 1 M) Potentiodynamic a) Maximum pitting observed for 16

and 904L Na2S2O3 polarization the ratio, 1000:1, 100:1 and
at 20°C to 80°C 16:1 for 304, 316L, and 904L
SS, respectively at 80°C
b) Epit decreases with increasing
temperature

Alloy 304 SS 7 × 10−4 M Cl− and 8 × 10−5 M Polarization and Severe pitting was observed 59
S2O32− scratch testing
Alloy UNS 300 mg/L Cl− + (0 to 1,800 mg/L) Cyclic polarization, Pitting and crevice corrosion, 58
S30403 SS SO42− + 50 mg/L S2O32− contact electric resistance pitting is inhibited for Cl−/SO42− ≤ 0.5
technique, scratch tests

Type 304 SS 0.1 M NaCl + (1 mM − 1 M) Potentiodynamic Pitting was depended on 64

Na2S2O3 polarization the thiosulfate/Cl− ratio. Generally no
pitting for thiosulfate/Cl− ≥ 1

Type AISI 6 M NH4Cl + 0.01 M Na2S2O3 Potentiodynamic Pitting corrosion 65

310 SS polarization, XPS
Mild steel 1 M NaCl + (0.01 − 1 M) Na2S2O3 Immersion tests, linear Corrosion markedly increased with 62
solutions saturated with CO2 and potentiodynamic synergistic presence of CO2 and S2O32−
polarization in chloride solution

Type 304 SS (1 to 1,000) mM NaCl + (1 to Galvanostatic and Pitting was observed in a specific thio- 66
1,000) mM Na2S2O3 potentiostatic sulfate/chloride concentration range. No
polarization pitting in only-thiosulfate solutions
AISI 304, 1 M NaCl + 0.01 M Na2S2O3 Crevice corrosion Crevice corrosion penetration rates 31
AISI 316L, testing underwent ten-fold increase in presence
UHB 904L of thiosulfate
304, 316, 317L, (0 to 1,000) ppm Cl− + Weight loss and a) Relative performance of the alloys, 15
Ferralium 254 (0 to 200) ppm S2O32− + potentiostatic tests AISI 304 (sensitized) < 304 < 316
100 ppm SO42− (sensitized) < 317 L < Ferralium 255
(Sensitized) < Ferralium 255
b) Pitting could occur even in the absence
of Cl− if sufficient sulfate is present
for AISI 304 L (SO42−/S2O32− = 6 to 23)
Fe-19Cr-10Ni 0.25 M Na2SO4 + 0.025 M Scratch testing Pitting occurred in limited range of 12
Na2S2O3 potentials and concentrations
16Mn Low-Alloy Bayer solution + 5 g/L S2O32− Polarization and cyclic The presence of thiosulfate decreased 67
steel voltammetry the corrosion rate of steels in alkaline
Bayer solutions containing sulfide ions
AISI 316 0.1 M NaCl + (0.01 to 0.03) M Potentiodynamic, a) Addition of thiosulfate ion to chloride 26, 68
Na2S2O3 potentiostatic polarization, solutions shifted critical pitting tempera-
and SEM ture to lower temperature and decreased
pitting potential
b) The presence of thiosulfate increased
the frequency of metastable pitting
occurrence and the probability of transi-
tion from metastability to stability

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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 10. Potentiodynamic polarization curve for Type 304 SS in
0.25 M NaCl + 0.01 M Na2S2O3 solution (scan rate: 0.2 mV/s).13
FIGURE 11. Summary of thiosulfate pitting in the presence of sulfate,
chloride, and thiosulfate.14
occur. In highly reducing atmospheres, which are
characterized by very low potentials, dissolution of the
metal is too slow to retain the aggressive pit environ-
ment in the face of diffusional dispersion of the pit
contents into the external environment. If a very high
concentration of thiosulfate is present, then it tends
to disproportionate/electro-reduce at a faster rate, thus
neutralizing the acidity of the pit.14
The effect of potential on the corrosion of steels in
thiosulfate solutions can also be explained on the
basis of E-pH diagrams for sulfur species on Fe, Ni, and
Cr at 25°C, generated by Marcus and Protopopoff.51 The
most commonly advanced mechanism of pitting by
thiosulfate is based on the reduction of thiosulfate to
1158
the adsorbed sulfur, which inhibits the repassivation
process26,55,71 once pitting is initiated. However, a
higher concentration of thiosulfate inhibited pitting,
which was attributed to the preferential electro-
migration of S2O32− into pit nuclei, thus preventing the
chloride accumulation in the developing pit and ne-
gating the effect of chloride in breakdown of the film.13 It
was further hypothesized that thiosulfate alone has no
aggressive effect on the passive film, and only aggra-
vates pitting on the bare metal surface once the chloride
has induced film breakdown (although quantitative
confirmation of this speculation was not performed).13
From this, one would conclude that thiosulfate is not
an activating species toward metals such as Cu, Fe,
and Ni, which is at odds with experiment and with
thermodynamics, at least for copper (Figure 9). Fur-
thermore, if the role of adsorbed sulfur is to inhibit
repassivation, the question remains as to why chloride
is needed within the pit to maintain the pit active
when thiosulfate serves that same purpose.
Duret-Thual and coworkers55 attempted to explain
the mechanistic information on passive film breakdown
on Fe-17Cr alloy in thiosulfate solutions using elec-
trochemical techniques and x-ray photoelectron
spectroscopy (XPS). This study provided important in-
formation on the exact nature of the surface reactions
of metallic or passivated surfaces in presence of thio-
sulfate. A lowering of the pitting potential of Fe-17Cr
alloy was reported after thiosulfate addition in the
0.02 M NaCl, as shown in potentiodynamic polariza-
tion scans (Figure 12). The presence of thiosulfate
seemed not to affect the active/passive transition
(as the maximum activation current and passive cur-
rent densities are similar with or without thiosulfate),
but thiosulfate had a pronounced detrimental effect
on pitting (Figure 12), although the data were not
particularly reproducible.
Importantly, surface analysis showed that there
was no reduced sulfur formed when a well-developed
passive film is exposed to the thiosulfate. This also
suggested that the thiosulfate anion and its decompo-
sition products do not penetrate into the passive
FIGURE 12. Potentiodynamic curves for the Fe-17Cr alloy in chloride
and thiosulfate solutions (scan rate: 1 V/h).55
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 13. Model of the surface of the Fe-17Cr alloy after exposure
at corrosion potential to 0.02 M NaCl containing 30 ppm of S2O32−.55
film. However, XPS analyses for Fe-17Cr alloy at the
corrosion potential in 0.02 M NaCl + 0.2 mM S2O32− for
different immersion time periods (20 s, 5 min, and
20 min) clearly show signals corresponding to reduced
sulfur on the bare metal surface. This reduced sulfur
may be a sulfide incorporated into the oxide layer or
might be sulfur adsorbed at the metal/oxide interface,
according to the following reactions:55
M þ S2 O2− + −
3 þ H2 O = M − Sad þ SO4 þ 2H þ 2e
2− (30)
xM − Sad þ ðy − xÞS = Mx Sy ðsulfideÞ (31)
Growth of these sulfide islands with exposure time to
the thiosulfate solution was observed, as shown sche-
matically in Figure 13. It was also hypothesized that the
emerging sulfide islands could represent preferential
sites for the reduction of the thiosulfate, and the sub-
sequent nucleation of pitting.55
The critical factor in thiosulfate-activated pitting
was the chloride/thiosulfate ratio. Laycock16 investi-
gated the effect of temperature and thiosulfate on
chloride-induced pitting of austenitic stainless steel.
A ratio of 250:1 Cl−/S2O32− was found to be most
aggressive at 20°C in 1 M NaCl. However, with increase
in temperature, the pitting potential in any given so-
lution decreased, which is the normally-observed
behavior, while the most aggressive chloride/thiosulfate
ratio increased. The production of thiosulfate by dis-
solution of manganese sulfide inclusions (Equation
[32]) also caused the breakdown of the passive film
when present above a critical concentration (measured
in situ using spectrochemical experiments) in the
presence of chloride ion.54
2MnS þ 3H2 O = S2 O2− +2 þ 6H+ þ 8e−
3 þ 2Mn (32)
As observed by several other authors, Park, et al.,66
found a similar synergistic effect of activated pitting in
thiosulfate-chloride solutions. Webb, et al.,64 studied
the effect of the addition of thiosulfate on the pitting by
sulfide inclusions using electrochemical microcell
measurements. The addition of thiosulfate ion in the
chloride-containing electrolyte increased the rate
of dissolution of single, shallow sulfide inclusions.
Similar to the observations by Newman and other
authors,13-14,58 the higher concentration of thiosulfate
CORROSION—Vol. 71, No. 9
(above critical value, which also depended on the
chloride concentration in the electrolyte) inhibited pit-
ting, perhaps as a result of the specific absorption
of thiosulfate into surface oxygen vacancies, thereby
denying access of chloride ion to these same sites,
which would result in passivity breakdown,72 as pro-
posed by the point defect model (PDM).73
Alloying of steels with molybdenum was shown to
decrease the activating effect of sulfur species.74-75
Marcus and coworkers74-75 have shown that the mo-
lybdenum causes a relative decrease in the surface
coverage of Sads on a corroding surface and thus
reduces the degree of pitting. The decrease in pitting
activation effect of sulfur species in the case of
molybdenum alloying was related to the fact that the
molybdenum caused desorption of sulfur, which
counteracts the detrimental effect of sulfur adsorp-
tion,74 but there is little hard evidence in support for
this postulate. It was further shown that a higher
thiosulfate concentration was required for pit activation
with an increase in the molybdenum content in stain-
less steels.16,66 Thus, Type 316 SS was found to be more
pitting-resistant in thiosulfate solutions compared with
Type 304 SS,14 a phenomenon that, in the PDM,76 is
attributed to complexing between Mo6+ substituted
onto the cation sublattice of the barrier layer of the
0
passive film and the mobile cation vacancies (V3Cr ) that
lead to passivity breakdown by condensing on the
metal/barrier layer interface at a breakdown site. This
complexing can be described in terms of ion-pairing
theory with the interaction energy being given by
Coulomb’s law. Further, the presence of bisulfite in
white water was shown to inhibit the thiosulfate pit-
ting14,20 which is in concert with the prediction of
the PDM.72 Bisulfite was effective in inhibiting pitting
when its concentration approached that of sulfate or
chloride, probably a result of either buffering capacity of
bisulfite or by neutralizing the acidity in the developing
pit,14 or by competitive adsorption into oxygen vacan-
cies in the surface of the barrier layer, as has been
postulated for nitrate inhibition of passivity
breakdown.72
Film Formation in Thiosulfate Solutions
The corrosion resistance of stainless steels depends
on the composition and defect structure of the passive
film developed on the surface.77 Passivity aids in the
kinetic inhibition of various anodic processes at the
interfaces. The passivity of stainless steels is a result of
the spontaneous formation of a thin protective barrier
layer of defective chromic oxide, Cr2+xO3−y (typically
1 nm to 3 nm thick), where x indicates the excess metal
in the lattice in the form of metal interstitials and y
indicates the deficiency of oxygen on the oxygen anion
sublattice of the barrier layer. The passive film generally
comprises a bilayer structure of an inner, defective
chromic oxide layer containing iron, nickel, and chro-
mium metal interstitials and an outer layer of a mixture
1159
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
of iron oxide and a hydroxide.77-78 The inner (barrier
layer) is an n-type semiconductor because of the prin-
cipal point defects being oxygen vacancies
and (primarily) metal interstitials, both of which are
electron donors, and can be described by the formula:
Cr2 + xO3 − y, as indicated previously. Thus, surface
analysis indicates significant presence of iron and nickel,
in the barrier layer of Fe-Cr-Ni alloys and even of mo-
lybdenum-containing alloys, such as Type 316 SS. As
noted above, the Fe and Ni content is attributed to
the presence of the interstitials, Fe3+i and Ni2+
i , respec-
tively, as a result of the transmission of these elements
through the barrier layer lattice, while the molybde-
num is believed to be substituted upon the Cr cation
sublattice as immobile Mo3+ Cr . Electrochemical imped-
ance spectroscopy79 indicates that in the case of Alloy 22
(UNS N06022, nominally [wt%] Ni 58, Cr 22, Mo 13.0,
Fe 3.0, W 3.0), more than 99% of the passive current
is carried by metal interstitials (as opposed to oxygen or
cation vacancies) and the same is found for stainless
steels.
As stated, the thiosulfate ion alone does not have
any deleterious effect on the electrochemical localized
corrosion of stainless steels, because thiosulfate ion,
alone, does not seem to initiate the breakdown of the
protective character of the passive film.13,16,55 It was
further reported that polysulfur species, such as
thiosulfate ion, activate anodic dissolution at the pit
initiation sites, but does not assist in the initial
breakdown of the passive film on the surface of stainless
steels,16 although it may inhibit this event.14 Fig-
ure 1480 shows the anodic polarization curves mea-
sured for stainless steel in solutions containing only
1 mM Na2S2O3 without chloride ion at pH = 3.5, 4.0,
and 5.0. In these solutions, the surfaces of the stainless
steel were completely passivated at the corrosion
FIGURE 14. Anodic polarization of Type 304 SS in 1 mM thiosulfate
solution at different pH values.80
1160
potential.80 However, in presence of anions such as
Cl−, thiosulfate aggravates the localized corrosion/
pitting because of the postulated inhibition of repassi-
vation process generally, as a result of its reduction/
decomposition into adsorbed sulfur.14,16 The stability
of the film formed on stainless steels in thiosulfate
solutions are known to be greatly disturbed by adsorbed
sulfur on steel surfaces.55
It is well accepted that one of the decomposition
products of thiosulfate is elemental sulfur (Equation [6],
Table 2). The corrosion of carbon steel in the presence of
wet elemental sulfur was studied extensively by Hyne,
Macdonald, and Roberts.81-82
Examination of the data displayed in Figures 15
and 16 leads to the following generalizations concerning
the reaction of carbon steel in wet elemental sulfur:
(1) it is a form of acid attack as evidenced from the
observed increase in pH (Figure 15); (2) it is charac-
terized by an induction time that decreases with in-
creasing initial pH with the induction time being greater
under anaerobic conditions than under aerobic condi-
tions (Figure 16); (3) the reaction is autocatalytic, with
the rate after induction being similar under aerobic
conditions and anaerobic conditions (Figure 15); and
(4) during autocatalytic attack, the corrosion potential
becomes more positive.81
Further, the corrosion rate decreases with cycle
number upon cyclical exposure of the steel to wet sulfur
and the atmosphere (Figure 17).82 The ennoblement of
the corrosion potential during the autocatalytic phase
indicates that the reaction is cathodically-controlled,
while the initial induction time is consistent with the
depassivation of the surface and the formation of a
surface phase that catalyzes the cathodic reaction. This
phase is identified as mackinawite, Fe1+yS (y < 0.15),
an electronically-conductive iron (II) sulfide, the
FIGURE 15. Corrosion of carbon steel in wet elemental sulfur as
indicated by the change in the electrical resistance of a carbon steel
wire as a function of time under aerobic and anaerobic conditions at
ambient temperature. The initial and final pH values are indicated
with each curve. Sulfur particle size = 2.38 mm to 4.76 mm.81
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 16. Dependence of the induction time on initial pH for the
corrosion of carbon steel in wet elemental sulfur for aerobic and
anaerobic conditions at ambient temperature.81
FIGURE 17. Corrosion rate of carbon steel in wet elemental sulfur as
a function of time and cycle number upon exposure to sulfur (4 d) and
to the atmosphere (6 d).82
formation of which is encouraged by higher pH re-
sulting in the decrease in induction time. Although yet
to be proven, it appears that direct contact between
solid sulfur and the steel is not necessary and hence it is
likely that the cathodic reactant is a dissolved poly-
sulfide, Sx2− (x = 2 − 5, Table 1), giving the overall re-
action as:
ð1 þ xÞFe þ S2−
y → Fe1þy S þ ðy − 1ÞS
2− (33)
The autocatalytic nature of the reaction arises from
the formation of the polysulfide:
CORROSION—Vol. 71, No. 9
S2− þ ½ðy − 1Þ=8S8 → S2−
y (34)
because y ≥ 2. Mackinawite is known to be pyrophoric,
reacting rapidly with oxygen, but only within a narrow
range of moisture content. This reaction:
Fe1þy S þ 2ð1 þ yÞO2 þ 2H2 O
→ Fe2 O3 þ 4H+ þ 2SO2−
4 (35)
is highly exothermic and is responsible for fires in
sulfide-ore mines and in bulk sulfur shipped in marine
carriers. In the latter case, off-loading of bulk sulfur
from a ship (the T. Akasaka) at Mt. Maunganui in New
Zealand using a bull-dozer in the hold indicated the
presence of black mackinawite contaminating the load
of wet sulfur.83 After some time (matter of h) in the sun,
the black material “disappeared,” as its surface was
converted into “straw-colored” hematite, which blends
with the yellow sulfur, and subsequently the load burst
into flame. The fire, which produced highly toxic SO2,
was extinguished with water by the local fire depart-
ment, but once the sulfur began to dry out again, the
cycle was repeated. This occurred repeatedly, pre-
sumably until all of the mackinawite had been con-
sumed. Similar, anecdotal accounts of mackinawite
fires are available from the mining industry. Finally, the
increase in pH during the autocatalytic phase of the
reaction (Figure 15) is probably a result of the evolution
of hydrogen on the mackinawite surface in parallel with
polysulfide reduction. Iron sulfides have been previ-
ously shown to be highly catalytic toward hydrogen
evolution.81,84
Hemmingsen, et al.,85 monitored the corrosion
process of carbon steel in thiosulfate solution using
electrochemical and optical measurements. In the pH
range of 5 to 9, a dark sulfide film (presumably mack-
inawite) was formed on the steel surface, with the
highest formation rate at pH 9. The film formed at
higher pH thiosulfate solution was found to be more
protective, but the proof was only limited to a visual
observation. This was in contrast to the corrosion rate
measurements of Macdonald, et al.,81-82 which found
no such protection from sulfide films, but the difference
between the two studies may reflect the source of ele-
mental sulfur (thiosulfate decomposition vs. solid S8).
Although Hemmingsen, et al.,85 found that the sulfidic
films are formed in thiosulfate solutions, very little is
known about the structure of films that are formed.
A recent study has attempted to characterize the film
formed on duplex stainless steel in thiosulfate solutions
using electrochemical techniques and XPS.86 They
reported increase in film thickness and decrease in
charge carrier density with applied potential, which is in
agreement with theoretical consequences of PDM.87-88
However, detailed electrochemical and analytical
characterization studies need to be performed in order to
1161
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

understand the kinetics of film growth on steels in gas-enhanced, environmentally-assisted cracking

thiosulfate solutions at different conditions (in presence studies.19,30,100-103
and absence of chloride, different pH, temperature, etc.). Kappes, et al.,11,19,30 further confirmed the claims
Finally, the reader may question the relevancy of of Tsujikawa, et al.,10 and clarified some unsolved
the work performed on carbon steel in contact with wet issues related to the solutions’ chemistry, kinetics of
elemental sulfur, but the relevancy is dictated by two H2S generation, hydrogen permeation, and film for-
factors: (1) thiosulfate decomposes to produce ele- mation on carbon steel in thiosulfate-brine solutions.
mental sulfur on a metal surface, and (2) sensitized They proposed that the acid brines containing 10−4 M
stainless steel grain boundaries in the 300 series and 10−3 M S2O32− could be used for replacing con-
stainless steels, at least, contain insufficient chromium tinuous bubbling of dilute H2S/N2 mixtures in tests of
to form a passivating, defective chromic oxide barrier the degradation of carbon steels, with H2S partial
layer and hence are reasonably approximated by a pressures ranging between 0.03 kPa and 0.56 kPa.11
Fe/Ni alloy or by carbon steel, recognizing that nickel
behaves similarly to iron in its interaction with sulfur Stress Corrosion Cracking of Sensitized
in aqueous solution. Stainless Steel
SCC of sensitized austenitic stainless steels was a
STRESS CORROSION CRACKING OF STEELS well-known phenomenon in the petroleum refining in-
dustry for many decades. SCC of sensitized alloys also
IN THIOSULFATE SOLUTIONS
became notorious in the mid-1990s with the cracking
Stainless steels are found to be susceptible to SCC of sensitized Alloy 600 steam generator tubes in the
in various aqueous environments such as caustic Three-Mile Island pressurized water reactor coolant
solutions,89-90 borate solutions,24 chloride solutions,91 circuits under wet-layup conditions. The presence of
and sulfur-containing environments.56,92-93 In partic- thiosulfate was attributed to contamination of the re-
ular, the sulfur species (such as polysulfides, sulfur actor coolant by the building spray solution that would
oxyanions) have been reported to cause SCC failures of be used to fix radioactive iodine in the case of a loss-of-
steels in a variety of applications,24,92-98 including in coolant accident and failed fuel. Early laboratory work
the nuclear, pulp and paper, and petroleum industries. performed on various steels showed significant sus-
SCC of stainless steels is generally initiated by the ceptibility to SCC even in dilute thiosulfate solutions (as
destruction of the passive film followed by the growth of low as 0.1 ppm).27,56,92-93,104-106 Isaacs, et al.,104
a pit to a critical dimension at which a crack will studied the SCC of sensitized Type 304 SS in thiosulfate
nucleate. solutions containing boric acid using constant exten-
sion rate tests. Without the addition of boric acid in
the thiosulfate solution, a very low concentration of
Use of Brine-Containing Thiosulfate Solutions to
thiosulfate (6 × 10−7 M or 0.1 ppm) was required to
Simulate the Sour Gas Environment cause SCC. However, with boric acid addition, a higher
Sour gas environment found in the petroleum thiosulfate concentration was required to cause
industry has hydrogen sulfide (H2S) as a main con- cracking (Table 5), suggesting an inhibiting effect of
stituent. H2S is identified as one of the most toxic, H3BO3 on the susceptibility of the steel to cracking.
flammable, and corrosive substances.10,99 Hence, The inhibitive effect of the boric acid on SCC can be
performing sour gas experiments in a laboratory envi- explained by reduction in the flow of thiosulfate ions
ronment could be quite troublesome and dangerous. into the crack because of the ability of borate anions to
Moreover, the equipment required to ensure safety in
H2S environments is also very expensive. With these TABLE 5
views in mind, a research group (Tsujikawa, et al.10) CERT Results of Type 304 at Nominal Strain Rate of
with the Japan Society of Corrosion Engineering de- 1.0 × 10−6 s−1 in Thiosulfate and Boric Acid
veloped a solution containing thiosulfate ions, which Solutions104,(A)
can be used to mimic the sour gas environments that
Heat Concentration of Strain at
are generally found in the petroleum industry. The
Treatment Na2S2O3 (ppm) H3BO3 (M) fracture (%)
reactions and thermodynamics associated with the H2S
generation by thiosulfate ions are presented in the A,S 0.01 0 72*
Thermodynamics of the Sulfur-Water System section A,S 0.1 0 38
A,S 0.1 0.18 70*
(Equations [6], [8], [11], and [12]). It was suggested that A,S 0.1 0.18 78*
the solution containing thiosulfate ions can be used for A,S 1 0.18 11
examining the pitting/SCC tendency of steels in sour A,S 1 0.18 9
gas environments without using H2S gas.10 The use of A,S 10 0.18 6.5
thiosulfate ion as a substitute for H2S environment A,S 100 0.18 4
A 10 0.18 71*
proved to minimize the hazards associated with H2S
testing. Several other research groups since then (A)
S: sensitized 24 h at 600°C; A: annealed 3 h at 1,100°C; *: no
have used thiosulfate solutions to perform sour SCC

1162 CORROSION—SEPTEMBER 2015

 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

carry the current in place of thiosulfate alone. At a lower

concentration of thiosulfate, the borate ions would
essentially carry all of the anionic current from the
cathodic sites external to the crack, and so thiosulfate
would not be transported into the crack enclave.
Furthermore, the borate ions are nonaggressive, and
inhibit dissolution and cracking by forming a less
soluble salt layer or by allowing efficient repassiva-
tion of the crack tip after a brittle microfracture event.
Cracking of sensitized Type 304 SS is electro-
chemically controlled and SCC was found not to occur
at potentials less than −0.5 VSCE.104 The maintenance of
an acidic environment at the crack tip seems to be a
necessary condition for SCC, and a decrease in pH
was shown to increase the crack nucleation rate.107
Thus, the reason for inhibition of SCC at potentials
below −0.5 VSCE can be attributed to the decrease in the
acidity (increase in the pH) at the crack tip at such
low values of potential, and inhibition of dissolution of
iron in chromium-depleted grain boundaries or the
inhibition of the injection of atomic hydrogen into the
matrix ahead of the crack tip (see below), because of the
increase in pH at the crack tip. Furthermore, the rate of
cracking was found to increase with increased FIGURE 18. Potential-pH diagram for Fe-S-H2O system at 298 K (not
potential.104 considering SO42−). Severe cracking ranges are indicated by
arrows.56
Newman, et al.,56 followed up the study conducted
by Isaacs, et al.,104 and reported on the role of the
metastable sulfur anion, S2O32−, in the cracking of Based on the discussed thermodynamic argu-
sensitized stainless steel. These metastable anions are ments, Newman, et al.,56 disregarded the hydrogen
readily converted to elemental sulfur at the advancing embrittlement mechanism for SCC of sensitized steels
crack tip surface, which retards the repassivation in thiosulfate solution, but explained their results on
and increases anodic dissolution.71 Similar to the in- the basis of intermittent brittle fracture of the grain
hibitive effect of borate ions observed by Isaacs, et al.,104 boundaries, assisted by local formation of strain-
the addition of sulfate ions to a dilute thiosulfate so- generated martensite and sharpening effect of anodic
lution also inhibited SCC. The molar ratio of sulfate to dissolution. Crack initiation occurred by repeated film
thiosulfate required for inhibiting SCC is ∼20 for a rupture at grain boundaries followed by formation of
6 × 10−4 M S2O32− concentration. grain boundary martensite film ahead of the crack tip.
The region of cracking susceptibility was placed Further dissolution sharpens the crack, which facili-
on a potential-pH diagram of Fe-S-H2O system tated the localized grain boundary separation and thus
(Figure 18). The results from the studies on SCC in IGSCC, as similarly observed in the other studies.104
sensitized Type 304 SS by Matsushima in polythionic However, as we will see next, this mechanism does not
acid at pH ∼1,108 Dhawale, et al.,109 in borated thio- account for the supra-grain dimension (greater than
sulfate solution, and Newman, et al.,56 in 0.5 M one grain) of the brittle microcracks.28-29
Na2S2O3 are included. Coincidently, all three of these Other authors92,107 supported the mechanism
studies showed maximum cracking susceptibility in the developed by Newman, et al.,56 for the SCC of sensitized
Fe2+ and S stability fields. This further confirmed the stainless steel in thiosulfate solution, and similarly
claim that the formation of elemental sulfur plays an proposed the enhancement of anodic dissolution by
important role in promoting intergranular cracking and thiosulfate ions, and contribution from embrittlement
enhancing the dissolution of chromium-depleted grain associated with the formation of strain-induced mar-
boundaries, as described earlier. Newman, et al.,56 tensite. Wells, et al.,107 attempted to explain the fluc-
further suggested that the sulfur effect on hydrogen tuation in corrosion potential and corrosion current
entry into metal matrix with consequent embrittlement pulses associated with the nucleation of microcracks
cannot be ruled out. However, a very low equilibrium and their movement in the role of IGSCC. The degree of
partial pressures of hydrogen (∼10−17 atm, 101.325 × sensitization of the stainless steel was also shown to
10−17 kPa) and hydrogen sulfide (∼10−12 atm, 101.325 × affect the SCC susceptibility in thiosulfate solutions.
10−12 kPa) at pH 3 and upper cracking potential of The specimens sensitized for 1 h to 4 h did not undergo
340 mVSHE may primarily suggest the dissolution SCC, while the specimen sensitized for more than 4 h
mechanism of SCC instead of H-based mechanism. underwent IGSCC.28,107

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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 19. Measured coupling current between the crack and the external surfaces upon SCC in sensitized Type 304 SS in
0.5 M thiosulfate solution illustrating periodicity in the current.28-29
Contrary results on the mechanism were re-
ported by Gomez-Duran, et al.28-29 By measuring the
coupling current between the crack tip and external
surfaces, the crack was shown to grow via a series
of microfracture events, which induced periodic noise in
the coupling current (Figure 19).
Assuming that the microfracture events are semi-
circular of radius r, B/2r such events must occur on
average along the crack front for the crack to advance by
the distance r, where B is the thickness of the C(T)
specimen. If the frequency of the microfracture events is
f, then the crack growth rate (da/dt) is:
da fr
= = 2f r2 =B
dt B=2r
Rearrangement of Equation (36) yields the microfrac-
ture dimension as:
sffiffiffiffiffiffiffiffiffiffiffiffi
envelope” estimation may be written r≈ D=f , where D
B da
r= dt
(37)
2f
For the 4 h sensitization case, the crack growth rate,
da/dt = 1.7 × 10−6 cm/s, B = 1.416 cm, and f =
0.01 s−1 to 0.1 s−1, which yield a microfracture di-
mension of 35 μm to 108 μm. The lower end of this range
is of the order of the grain size of the steel, while the
upper end is supra-grain size of approximately 3 times
the average grain size. In the opinion of the authors
(Duran and Macdonald28-29), this dimension is too large
to be accounted for by brittle mechanical fracture
resulting from the existence of strain-induced mar-
tensite on the chromium-depleted grain boundaries
alone. The only viable explanation is HIC. Thus, the
decomposition of thiosulfate can be written as:
+ −
3 þ H → S þ HSO3
S2 O2−
indicating that the polysulfur oxyanion is acid unstable.
Transport of S2O32− into the acidified crack via
1164
migration in response to the coupling current will result
in deposition of atomic sulfur at the crack tip. Noting
that a high acidity also promotes some hydrogen evo-
lution on the brittle fracture surface, and that atomic
sulfur has been postulated to inhibit the recombination
of hydrogen atoms on the surface,110 thereby promoting
the entry of hydrogen into the steel, the involvement
of hydrogen in the fracture process is mechanistically
reasonable. Thus, it is envisioned that the hydrogen,
once it enters the steel at the crack tip or at juxtapo-
sition surfaces on the microfracture flanks, is trans-
ported by the stress field ahead of the crack tip and
recombines within creep-induced voids on the chro-
mium-depleted grain boundaries, or simply embrittles
(36)
the strain-induced martensite, resulting in a fracture
dimension that is determined by the distance ahead of
the crack tip (which commensurate with the transport
properties of hydrogen). Thus, as a “back-of-the-
pffiffiffiffiffiffiffiffiffi
is the diffusivity of hydrogen and f is the frequency of
the microfracture events (0.01 s−1 to 0.1 s−1). While the
exact composition of the chromium-depleted zone is
unknown, it is expected that the grain boundary
chromium concentration is of the order of 10 wt%.
Elboujdaini111 gives hydrogen diffusivity data for
Fe-Cr-Ni alloys as a function of composition and from
these data, D = 10−6 cm2/s was selected. Thus, r is
estimated to range between 32 μm and 100 μm, in
reasonable agreement with the value estimated from the
noise in the coupling current combined with the known
crack growth rate. This lends credence to the postulate
that hydrogen plays an important role in causing
SCC in sensitized Type 304 SS in 0.5 M thiosulfate
solution. Thus, there is consensus on the part of de-
position of S in the neighborhood of the crack tip by
thiosulfate reduction or thiosulfate disproportionation
(38) and its role in retarding passivation and/or hydrogen
injection. Sulfur species are reported in other studies
to effectively catalyze the entry of atomic hydrogen into
the metals and alloys, including stainless steels.110,112
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
Thus, on balance, the principal role of thiosulfate in
enhancing the crack growth rate in sensitized Type
304 SS is to promote the entry of hydrogen into the
matrix ahead of the crack tip. The observation of higher
coupling current between the crack and the external
surfaces was attributed to the either enhancement of
rate of anodic dissolution or the rate of hydrogen in-
jection/brittle microfracture at the crack tip, in syner-
gistic presence of tensile loading.
Several other studies also reported the ability
of S2O32− to induce SCC by transforming into H2S and
S,10,24,102-103 which could catalyze the ingress of hy-
drogen, but might also inhibit repassivation. Thus, the
entry of atomic hydrogen in steels in H2S environ-
ment suggests that hydrogen embrittlement is the
predominant mechanism, which could cause brittle
fracture by transport of H ahead of crack front. This
may result in pressurization of voids on the grain
boundary by H2 and cause enhancement of the hy-
drostatic stress. If the enhanced stress exceeds the
fracture stress of the matrix, the ligament between the
crack tip and the void will fracture, resulting in a
microfracture event. This, in turn, will lead to a higher
frequency of brittle fracture and hence, to a higher crack
growth rate. On the other hand, reaction of hydrogen
with segregated metalloids may cause decohesion of
the grain boundaries, again resulting in enhanced
crack growth rate.28
The majority of studies have been conducted at
ambient or at moderate temperatures. Lee, et al.,113
evaluated the effect of S compounds on SCC at tem-
peratures between 50°C and 200°C. Thiosulfate solu-
tions (air-saturated with 104 ppm Cl−) were reported to
cause the IGSCC at 50°C to 150°C, but to inhibit IGSCC
at 200°C. It is suggested that at lower temperatures
(50°C and 100°C), the formation of the less protective
mackinawite film is responsible for SCC, as breakdown
of mackinawite by chloride ions is possibly much easier
than that of an oxide film. In contrast, at higher tem-
peratures, a more protective film, i.e., troilite, forms,
which may have attributed toward the SCC immunity at
200°C.113 These results are corroborated by the results
of the U-bend testing on Type 321 SS (UNS S32100,
nonsensitized), which indicated that the susceptibility
to SCC decreases with an increase in temperature from
80°C to 300°C (which was explained on the basis of
formation of more compact Cr2O3 oxide film and the
Fe3O4 corrosion product film formed at higher tem-
perature).102 An alternative explanation is that with
increasing temperature the crack environment becomes
increasingly aggressive, such that crack blunting
occurs.
Stress Corrosion Cracking of Nonsensitized Steel
SCC of nonsensitized steels have been also reported
in the thiosulfate solutions containing chloride
ions.10,95-96,100-102,114 Type 304L SS (UNS S30403) was
reported to suffer SCC in the 4 M chloride solution
CORROSION—Vol. 71, No. 9
FIGURE 20. The stress vs. strain curve for the duplex stainless steel
in 20% NaCl solution in the absence and in the presence of S2O32− at
80°C.100
containing from 10−3 M to 10−1 M S2O32− at 353 K, and
crack propagation was found to increase slightly with
increasing concentration of S2O32−. However, at the
very low concentration of 10−4 M S2O32−, the Type 304L
SS did not undergo any SCC.101 This was attributed to
the higher pitting potential and probably higher
repassivation rate at this thiosulfate concentration. In a
follow-up study by the same authors, it was reported
that the potential also controlled the SCC of Type
304L SS in chloride solutions containing thiosulfate
ion.114 From the slow strain rate tensile testing (SSRT),
the observed maximum stress in the stress-strain curve
was reported to decrease with increasing potential,
which may primarily be as a result of the high proba-
bility of pitting events at less noble potentials leading
to more crack initiation events.114
In a very recent study, the SCC behavior of du-
plex stainless steel (LDX 2101†, UNS S32101) was
studied using the SSRT technique and found to be
susceptible to SCC in 20% NaCl solution at 80°C in the
presence of thiosulfate.100 For the solutions contain-
ing thiosulfate ions, the highest susceptibility to SCC
was observed for 10−3 M thiosulfate (Figure 20). At
higher concentrations of thiosulfate, the selective cor-
rosion of ferrite became competitive with SCC, which
only led to generalized selective attack of ferrite phase,
thus reducing the SCC susceptibility,100 possibly
through crack blunting.
CORROSION PROBLEMS BECAUSE OF
THIOSULFATE: AN INDUSTRIAL
PERSPECTIVE
All of the data discussed indicate that the presence
of thiosulfate may induce severe pitting/SCC problems
in sensitized and/or nonsensitized steels even at a
very low thiosulfate concentration. Thiosulfate ion is
known to be a dangerous corrosion promoter. As
mentioned, thiosulfate corrosion problems are observed
in various industries, especially in pulp and paper,
nuclear, and petroleum industries.
1165
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
During kraft pulping process, 5% to 10% sodium
hydroxide (NaOH) and sodium sulfide (Na2S) solution at
170°C (∼150 psi, 1.03425 MPa) are used to convert
wood chips into chemical pulp by cooking chips in large
digesters. The oxidation of sulfide ions used in this
process may generate thiosulfate. Moreover, a slight
change was made in brightening chemistry by the ad-
dition of sodium hydrosulfite (Na2S2O4), in order to
protect aquatic life in the rivers,20 which could generate
thiosulfate anion as a metastable byproduct of the
Na2S2O4. The presence of thiosulfate anion in the
pulping process caused cracking/pitting of not only
cast martensitic and sensitized austenitic SS rolls, but
also of bronze. Preventive measures were taken to
minimize the deleterious effect of thiosulfate by using
more corrosion resistant alloys such as Type 316L SS
and duplex stainless steel. Also, S2O32− is now mini-
mized by much more careful chemistry control. Many
other chemicals are now used and some like sulfite
(SO32−) and carbonate (CO32−) are present in sufficient
concentrations that they inhibit pitting (Figure 21).
In the case of the petroleum industry, the sulfur
present in sour crude oil, as an impurity in feedstock,
produces iron sulfide scale. When equipment is opened
to the atmosphere for inspection and repair during
shutdowns, these scales are exposed to oxygen and
moisture. Subsequently, this leads to the formation of
polythionic acids (H2SxO6, x = 3, 4, 5) and other
oxyanions, such as S2O32−, which can cause pitting
corrosion and SCC, unless preventive measures are
implemented. The synergistic presence of thiosulfate
and chloride ions in some nuclear reactors that use
Alloy 800 tubing is also speculated to cause severe
corrosion problems.7 The difficulty with this hypothesis
is that there is no obvious source of sulfate or thio-
sulfate, because of the tight water chemistry con-
straints in nuclear power reactors. However, there have
been several incidents of failure of steam generator
tubing, including the notorious event at the Three Mile
Island nuclear power plant in Pennsylvania in 1979,
where the root causes have been quite evident. In the
case of Three Miles Island, the reason for these failures
was identified as being leakage of the building spray
solution, which contained thiosulfate to fix radioactive
FIGURE 21. Schematic of the pitting caused by thiosulfate anion in
presence of acid-formers, but inhibited by neutralizers.20
1166
iodine in the event of a loss-of-coolant accident, into the
boric acid/lithium hydroxide primary coolant.7
Thiosulfate corrosion may also present a problem
for gold-leaching hydrometallurgical circuits. In
general, cyanidation is a very effective and preferred
gold leaching technique. However, because of the en-
vironmental concerns over the safe usage of cyanides,
alternatives to the cyanidation technique have been
researched extensively in last decade. In this effort, the
use of environmentally-benign thiosulfate solutions
for gold leaching has recently gained widespread re-
search and commercial interest. In fact, the use of
thiosulfate has also become attractive in the leaching of
copper-gold complexes and carbonaceous gold ores,
which could not be satisfactorily leached using cyani-
dation.44 Thiosulfate leaching may also present eco-
nomic benefits, as thiosulfate salts are considerably
cheaper than cyanides.6 As discussed, thiosulfate may
cause the localized corrosion/SCC of stainless steels,
which are widely used as construction materials in
hydrometallurgical applications for preparing/building
plant infrastructures. There have been no studies
reported in the literature that are related to the elec-
trochemical corrosion of stainless steels in thiosulfate
solutions relevant to gold leaching technologies. More-
over, the thiosulfate gold leaching process is still in
its developmental stages and the long-term impact of
the thiosulfate species and leach conditions on plant
infrastructure is not yet well known. Hence, if the
thiosulfate gold leaching technology is to be success-
fully implemented, there is a definite need for devel-
oping material selection guidelines for thiosulfate
solutions relevant to thiosulfate gold leaching circuits.
CONCLUSIONS
Because thiosulfate has been implicated as an
aggressive species in variety of industries, this review
provides a brief summary of the literature to date. The
following general conclusions can be drawn:
v The presence of thiosulfate ions causes severe
localized corrosion/pitting of stainless steels in the
synergistic presence of chloride and/or sulfate ions.
There exists a critical ratio of thiosulfate and chloride
ion in order to cause severe pitting of stainless steels. In
most of the studies, this ratio of thiosulfate/chloride
was found to be less than one.
v There is a general consensus on the role of adsorbed
sulfur in causing pitting of stainless steel by the ac-
celeration of anodic dissolution and the retardation
of repassivation. Sulfur is generally produced by the
reduction of thiosulfate ions on the film-free surfaces of
alloy substrate.
v Thiosulfate ion alone does not appear to play any role
in breaking down the passive film, and cannot cause
any localized corrosion/pitting, which may be attrib-
uted to the inability of thiosulfate ions to be reduced into
absorbed sulfur on the intact compact passive film, but
CORROSION—SEPTEMBER 2015
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
it may do so by dissociation. In general, there have been
very limited studies concerning the characterization
of passive film formation in thiosulfate solutions. Be-
cause film formation greatly affects localized corrosion,
including SCC, this area needs further exploration.
v Thiosulfate ion causes SCC of sensitized and non-
sensitized stainless steels. The SCC process was elec-
trochemically controlled. Contradictory results have
been reported on the mechanism of SCC of sensitized
stainless steel in thiosulfate solutions. Some of the
studies reported the grain boundary cracking through
generation of strain hardened martensite, while other
studies reported the HIC to be the predominant
mechanism (mainly because of the role of sulfur in
catalyzing entry of atomic hydrogen into the metals/
alloys). The most viable mechanism, based upon the
available data, is one that contains elements of both
strain-induced martensite formation on the grain
boundaries and embrittlement by hydrogen produced
at the crack tip with its entry into the steel being
promoted by adsorbed sulfur, which inhibits the hy-
drogen atom recombination reaction.
v Thiosulfate-brine solutions can be used for substi-
tution of low concentration H2S gas environment to
evaluate the SCC/corrosion resistance of steels in sour
environment without using H2S, which could help in
minimizing the hazards associated with H2S testing.
v The detrimental role of thiosulfate in various indus-
trial applications (papermaking, petroleum, nuclear,
and hydrometallurgy) has been described. The need
for corrosion characterization of structural materials in
alkaline thiosulfate solutions relevant to hydrometal-
lurgical applications is identified.
ACKNOWLEDGMENTS
The authors greatly acknowledge the financial
support by the Natural Sciences and Engineering
Research Council of Canada (NSERC) and Barrick Gold.
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