:(NO
3
+ SO
4
2
)
more relevant for dripping natural waters in under
ground storage.
In this study, crevice stabilization and repas
sivation behavior was examined through slow
scanrate cyclic potentiodynamic polarization (CPP)
testing. From distributions of crevice stabilization
potentials, survival probabilities and crevice genera
tion rates were determined through application of
Shibatas stochastic theory.
1415
Testing was con
ducted over a range of temperatures, pH levels, and
electrolyte ratios (chloride to oxyanion) in order to
establish regression models that expressed critical
potential in terms of these parameters. However,
potentiodynamic scan rate and atrisk surface area
effects can confound determination of meaningful
crevice stabilization potentials. Critical potentials for
stabilization of localized corrosion have been shown
to increase with increasing scan rate and decreasing
electrode area for stainless steels and Nibased
alloys.
14,1617
Therefore, a slow scan rate and samples
containing many crevice sites were used to yield the
lowest and, thereby, most conservative estimates of
critical stabilization potentials. Indeed, researchers
have presented the idea of one critical potential.
16
This is equivalent to the most negative potential at
which stabilization will occur over a large atrisk sur
face area given infinite time or the highest potential
at which repassivation will occur given minimal prior
localized corrosion growth. Therefore, to obtain the
most conservative estimates of survival probabilities
and crevice generation rates, the crevice repassiva
tion potential was also used to generate a more con
servative estimate of crevice stabilization rates.
Crevice Corrosion Repassivation
The repassivation potential, E
r,crev
, is defined as
the potential below which established pits or crevice
corroded regions can no longer grow.
18
Researchers
have investigated the effects of solution composition,
temperature, and accumulated anodic charge on
repassivation for Nibased superalloys, including
Alloys 22, 825, and 625. Amano, et al., found that
potentiodynamically determined repassivation poten
tials for Alloy 625 decrease with increasing chloride
concentrations and increasing temperatures up to
CORROSION SCIENCE SECTION
1044 CORROSIONDECEMBER 2001
125C.
19
In addition, Dunn and Sridhar showed
through a potential step technique that repassivation
times for Alloy 825 increased with an increase in
bulk solution chloride concentration for a given pit
depth and increased with greater pit depth.
20
This
indicates that repassivation kinetics are controlled by
mass transport of chloride ions from the pit or crev
ice region. Gruss, et al., used CPP studies to compare
E
r,crev
of Alloys 22, 825, and 625.
21
Their results indi
cate that E
r,crev
values for Alloy 22 are considerably
higher than those for Alloy 625 or Alloy 825. This
points to the influence of Mo on corrosion resistance.
Moreover, numerous researchers investigating pitting
have shown that repassivation potentials decrease
with increasing pit size.
16,20,22
Increasing pit size has
the dual effect of increasing the effective diffusion
length out of the pit region, which is an important
factor related to dilution of the critical pit chemistry,
as well as increasing ohmic potential (IR) drop be
tween the external surface and the interior of the pit.
However, it has also been seen that repassivation
potentials are independent of prior growth for crevice
corroded regions, as well as deep pits.
20,23
Measure
ments of repassivation potentials for pitting (E
r,pit
) as
a function of accumulated anodic charge (i.e., pit size
or volume of damage) indicate that E
r,pit
remains con
stant only after a certain amount of charge has been
accumulated. In the region where E
r,pit
is independent
of dissolution charge, E
r,pit
is considered to be a con
servative parameter for the longterm prediction of
pitting corrosion.
2026
This argument can also be
applied to crevice corrosion. If the independence of
E
r,crev
and charge is observed for Alloy 625 and Alloy
22, distributions of E
r,crev
can be considered as con
servative estimates of crevice stabilization (E
crev
),
assuming the existence of a single critical potential
as discussed above. This potential can then be used
to develop conservative estimates of survival prob
abilities and crevice generation rates.
This paper describes electrochemical studies
performed to determine the effects of temperature
and electrolyte composition on crevice stabilization
and repassivation. From CPP scans, critical poten
tials for E
crev
and E
r,crev
were determined. Survival
probabilities and crevice generation rates were calcu
lated based on the distributions of critical potentials
and used to characterize the behavior of Alloy 625
and Alloy 22 subjected to different combinations of
temperature and electrolyte composition. Further
statistical analyses were performed to yield charac
teristic equations relating measured parameters (E
crev
or E
r,crev
) to temperature, electrolyte ratio, and bulk
solution pH.
EXPERIMENTAL PROCEDURES
Materials and Test Parameters
The alloys considered in this study are Nibased
Alloys 625 and 22. The alloy compositions and speci
fications are shown in Tables 1 and 2, respectively.
Table 2 shows heat treatments and mechanical prop
erties. Chemical analyses were performed using
vacuum emission spectrography and xray spectrog
raphy in accordance with the requirements of ASTM
B 443
(2)
and ASTM B 575. Table 3 reports character
istic values for chromium equivalencies,
5
pitting re
sistance equivalency numbers,
27
and modified pitting
resistance equivalency numbers,
28
which are indica
tive of the relative corrosion resistance of these al
loys. Laboratory airaged samples were ground and
polished to a 2m rootmeansquare (rms) surface
TABLE 1
Specified Chemical Composition (wt%)
of Alloy 625 and Alloy 22 in AirAged Conditions
Element Alloy 625 Alloy 22
C 0.023 0.007
Cr 21.56 21.58
Co 0.09 1.69
Fe 3.40 3.90
Mn 0.11 0.20
Mo 8.95 12.79
Ni Bal. Bal.
P 0.005 0.005
Si 0.09 0.01
S 0.004 0.001
W 2.79
V 0.13
Al 0.18
Nb + Ta 3.360
Ti 0.26
TABLE 2
Heat Treatment Specifications and Mechanical Properties for Alloy 625 and Alloy 22 in AirAged Conditions
625 22
Heat treatment Millannealed at a minimum of 871C Solutionannealed at a minimum of 1,121C
Micrograin size number 9.0 5.0
Hardness (HRB) 96 91
Tensile strength (ksi) 137.5 119.5
Yield strength (0.2% offset) (ksi) 74.8 59.8
Elongation in 2 in. (%) 46.4 62.0
(2)
ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1045
finish with typical rms values of 1 m on crevice
faces, then stored in lab air for 6 months. Samples
were degreased in acetone (CH
3
COCH
3
), rinsed in
deionized water, and dried at 100C in a vacuum for
3 min.
Crevice samples were tested in a multiple crevice
assembly consisting of a number of grooves and pla
teaus in accordance with ASTM G 78.
29
In this study,
the face of the sample was placed inside a crevice as
sembly consisting of ceramic multiple crevice formers
with 12 plateaus, each with an area of 0.06 cm
2
lined
with polytetrafluoroethylene (PTFE) tape. A torque of
7.92 Nm (70 in.lb) was applied. This arrangement
(Figure 1) created a reproducible tight crevice.
5
The
total wetted area of each specimen was ~8.5 cm
2
in
cluding both the sample face and stem. The crevice
former on the face of the sample created the only
crevices exposed.
Experiments were conducted at temperatures
ranging from 60C to 95C in 5 M lithium chloride
(LiCl) electrolytes at pH levels of 2.75 and 7.75. So
dium sulfate (Na
2
SO
4
) and sodium nitrate (NaNO
3
)
were added in concentrations to yield electrolytes
with molar ratios of chloride ions to total oxyanions
of 10:1 and 100:1, as indicated in Table 4. All elec
trolytes were prepared using certifiedgrade or
certified American Chemical Society (ACS)grade
chemicals and deionized water of 18.2 M resistivity.
Table 4 shows the four electrolyte compositions used
in this study. The electrolyte compositions selected
were motivated by separate work that identified pos
sible concentrated brines developed from evaporation
and rewetting type concentration of natural waters
(e.g., J13) found at the Yucca Mountain Nuclear
Waste Repository.
30
These concentrated solutions
may contain nearly equal concentrations of chloride,
nitrate, sulfate, and other buffering/inhibiting an
ions such as carbonate/bicarbonate. The electrolytes
utilized for this study were selected to probe the
potentialanion concentration (anion molar ratio)
temperature windows of crevice corrosion suscepti
bility and were not intended to exactly represent the
electrolyte concentrations expected in concentrated
J13 waters.
Electrochemical Testing Methods
The CPP test setup is shown in Figure 2. Open
circuit potentials (OCP) were allowed to stabilize at
testing temperature for ~ 1 h to 3 h prior to polariza
tion. Electrolytes were subjected to natural aeration
conditions. CPP scans were performed using an
upward polarization rate of 0.05 mV/s starting at
50 mV below the OCP. The reverse scan had a down
ward polarization rate of 0.05 mV/s and was termi
nated when net current densities became cathodic.
Reversal of the scan was triggered by a specified cur
rent density. The current density trigger level was set
at different values in order to vary the accumulated
anodic dissolution charge to examine the effect of
accumulated charge (i.e., the amount of damage) on
repassivation. The electrode potential was measured
with respect to a silver/silver chloride (Ag/AgCl)
(saturated potassium chloride [KCl]) electrode
(197 mV vs saturated hydrogen electrode [SHE]) at
room temperature, ~25C. Electrode potentials were
not corrected for the thermal liquid junction poten
tial, which was assumed to be on the order of mV.
31,(3)
TABLE 3
Calculated Values for Pitting Resistance Equivalency
Numbers (PREN), Modified Pitting Resistance Equivalency
Numbers (PRE), and Chromium Equivalencies for
Alloy 625 and Alloy 22 in AirAged Conditions
(A)
625 22
PREN 51.10 63.79
PRE 51.10 73.00
Cr equivalency 50.33 61.57
(A)
PREN = wt%Cr + 3.3wt%Mo + 16wt%N; PRE = wt%Cr +
3.3wt%(Mo + W) + 30wt%N; Cr equivalency = wt%Cr + 1.6wt%Mo
+ 4.3wt%Nb + 7wt%W.
(a)
(b)
FIGURE 1. Multiple crevice assembly arrangement showing: (a) the
entire assembly and (b) a crosssectional view of the crevice region
defined by a ceramic crevice former and deformable PTFE insert.
(3)
According to MacDonald, et al., a high concentration of KCl in
the reference electrode tends to suppress the thermal liquid
junction potential across the boundary between the internal
(high temperature) and external (room temperature) solutions.
CORROSION SCIENCE SECTION
1046 CORROSIONDECEMBER 2001
The potential at which the current permanently ex
ceeded 10
6
A/cm
2
on the forward scan was selected
as a threshold to define the critical crevice potential
associated with E
crev
. Often, E
r,crev
is determined from
a characteristic point on the downward scan. E
r,crev
was determined using both 10
5
A/cm
2
and 10
6
A/cm
2
threshold current densities because this point
was difficult to identify for Alloy 625 and Alloy 22.
Specimens were cleaned ultrasonically in a HCl solu
tion at room temperature for ~3 min in accordance
with ASTM G 1.
32
Posttest analysis included
confocal scanning laser microscopy and mass loss
determination.
RESULTS
Critical Potentials for Crevice Stabilization
and Repassivation
Critical potentials associated with stabilization
and repassivation, E
crev
and E
r,crev
, respectively, were
determined and distinguished from O
2
evolution and
transpassivity based on previous studies in both
nonchloride buffered solution and posttest examina
tion for crevice attack. Figure 3 illustrates typical
examples of potentiodynamic data for Alloy 625 and
Alloy 22. Elog(i) data indicated broad passive regions
with metastable pitting events
33
but were typically
devoid of other features such as anodic peaks over
tens or hundreds of mV. Typical crevicecorroded
surfaces are shown in Figure 4.
Additional experiments at 95C in 10:1 and
100:1 electrolytes were performed to examine the
relationship between E
r,crev
and accumulated anodic
charge. Figure 5 illustrates that E
r,crev
is independent
of charge associated with crevice attack over the
entire range for both alloys in 100:1 electrolyte. Simi
lar results were obtained in the 10:1 electrolyte. The
range of accumulated charge is much smaller for
Alloy 22 because of slower crevice corrosion propaga
tion rates (over similar potential ranges and identical
scan rates) for experiments using both electrolyte
ratios.
Effect of Solution Composition
The effect of solution composition, including
electrolyte ratio and pH, on crevice corrosion was
explored for each alloy. The results for Alloy 625 and
Alloy 22 at 95C are shown in Figure 6. The data are
reported as the cumulative probability for achieving
E
crev
at a specified potential, as pioneered by
Shibata.
14
That is, the cumulative probability is the
probability that an observed critical potential will be
less than or equal to a specified applied potential. In
this study, each datum point symbol in the cumula
tive probability plot reflects one experiment. It should
be noted that a linear cumulative probability plot
indicates a normal distribution.
14,3334
Moreover, a
steeper curve indicates less data variability. Both pH
levels produce statistically similar values of E
crev
and
E
r,crev
. Therefore, only pH 7.75 data is shown. For
example, tests on Alloy 625 in the 10:1 electrolyte
at 95C yielded average E
crev
values of 0.207 t
0.035 V
Ag/AgCl
and 0.197 t 0.046 V
Ag/AgCl
for pH 2.75
and pH 7.75, respectively. In addition, average E
r,crev
values were 0.092 t 0.023 V
Ag/AgCl
and 0.099 t
0.025 V
Ag/AgCl
for pH 2.75 and pH 7.75, respectively.
Therefore, critical potentials are found to be statisti
cally independent of the bulk solution pH over the
range explored.
E
r,crev
is only slightly affected by the initial chlo
ride/oxyanion ratio (Figure 6) when each alloy is con
sidered. A slightly lower median value is seen for the
FIGURE 2. Experimental setup for potentiodynamic testing. The
Ag/AgCl reference electrode (saturated KCl) was maintained at room
temperature through a salt bridge, which contained the same
electrolyte as the reaction cell.
TABLE 4
Electrolyte Compositions Based on Acidified HighStrength Water Composition Modeled by Hydrologists
pH 2.75 (10:1)
(A)
pH 7.75 (10:1) pH 2.75 (100:1) pH 7.75 (100:1) pH 2.75 (1:1)
5 M LiCl 5 M LiCl 5 M LiCl 5 M LiCl 1 M LiCl
0.24 M NaNO
3
0.24 M NaNO
3
0.024 NaNO
3
0.024 M NaNO
3
0.48 M NaNO
3
0.26 M Na
2
SO
4
0.26 M Na
2
SO
4
0.026 M Na
2
SO
4
0.026 M Na
2
SO
4
0.52 M Na
2
SO
4
pH adjusted with HCl Natural pH pH adjusted with HCl Natural pH pH adjusted with HCl
(A)
The electrolyte ratio, given in parentheses, indicates the ratio of chloride anions ot total oxyanions. The 1:1 ratio was used in a limited number
of tests.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1047
100:1 ratio at each pH for each alloy. E
r,crev
is slightly
more negative for Alloy 625. In contrast, E
crev
is more
strongly affected by the electrolyte ratio. Specifically,
E
crev
is lower when the ratio is greater. Figure 6 ex
cludes 1:1 ratio data because of transpassivity in the
pH 7.75 environment prior to crevice stabilization in
scanned tests. The effect of electrolyte ratio is clearly
seen through comparison of results from CPP studies
of Alloy 625 conducted at 95C in pH 2.75 electro
lytes with ratios of 1:1, 10:1, and 100:1. Average
E
crev
values were 0.621 t 0.031 V
Ag/AgCl
, 0.207 t
0.035 V
Ag/AgCl
, and 0.106 t 0.067 V
Ag/AgCl
for the 1:1,
10:1, and 100:1 electrolyte compositions, respec
tively, which are above E
ocp
values near 0.150 V
Ag/AgCl
.
As the electrolyte ratio changes from 100:1 to 1:1,
the average E
crev
value increases by >500 mV. There
fore, the effect of electrolyte ratio on crevice stabiliza
tion is strong, leading to more noble crevice stabiliza
tion potentials as the electrolyte ratio decreases and
the molar content rations of oxyanions increases. In
fact, as the harshness of the environment decreases
when expressed in terms of molar ratio, transpassive
(a) (b)
(a) (b)
FIGURE 3. Cyclic polarization curves showing critical potentials for: (a) Alloy 625 and (b) Alloy 22 in the pH 7.75 (100:1)
electrolyte at 95C.
FIGURE 4. Confocal scanning laser micrographs of airaged: (a) Alloy 625 and (b) Alloy 22 after CPP testing at 95C in
the pH 7.75 (100:1) electrolyte. 2D reflected light intensity images. The accumulated anodic charge for each alloy was
~2.5 coul.
CORROSION SCIENCE SECTION
1048 CORROSIONDECEMBER 2001
dissolution could occur instead of localized corrosion
as shown in Figure 6.
The same trends shown in Figure 6 with respect
to solution compositions are seen at lower testing
temperatures. Measurements on Alloy 625 at 60C
and 80C also revealed that bulk solution pH does
not have a strong effect on critical potentials for
repassivation or stabilization. In addition, critical
potentials at a 10
6
A/cm
2
threshold measured in the
pH 7.75 (10:1) electrolyte at 60C were attributed to
transpassive dissolution of the Crrich surface in
stead of localized corrosion. Solution composition
again only has a weak effect on repassivation. Speci
mens tested in the 10:1 electrolyte have slightly more
positive median values of E
r,crev
compared to the
100:1 electrolyte. Results for Alloy 22 at 80C and
85C also showed that the bulk pH did not have an
effect on repassivation or stabilization for specimens
tested in the 100:1 electrolyte. However, the results
in the 10:1 electrolyte differ from both the results for
Alloy 22 at 95C and the results for Alloy 625 over
the entire range of testing temperatures. At pH 2.75,
crevice stabilization potentials for Alloy 22 are well
below experimentally determined transpassive poten
tials. However, repassivation potentials are much
more positive at this condition, indicative of smaller
hysteresis loops on the CPP curves (and small
amounts of dissolution charge). In addition, there
is evidence of increases in anodic current density
caused by transpassive dissolution of the Crrich
oxide on Alloy 22 in the pH 7.75 (10:1) electrolyte.
Effect of Temperature
Experiments at temperatures ranging from 60C
to 95C revealed that critical potentials associated
with crevice corrosion stabilization and repassivation
increased as the temperature decreased. Figures 7
and 8 show the effect of temperature on E
crev
for
Alloy 625 and Alloy 22, respectively, in pH 2.75 and
pH 7.75 electrolytes.
In the pH 7.75 (10:1) environment (Figure 7[a]),
E
crev
for Alloy 625 increased to values above experi
mentally determined transpassive potentials as the
temperature is decreased from 95C to 60C. Testing
at 1:1 ratio led to transpassivity at all temperatures.
All other testing conditions for Alloy 625 yield critical
stabilization potentials well below experimentally de
termined transpassive potentials. However, critical
stabilization potentials for Alloy 22 approach or ex
ceed experimentally determined transpassive poten
tials in the pH 7.75 (10:1) electrolyte at each testing
temperature <95C. Because Alloy 22 exhibits
transpassive dissolution in the pH 7.75 (10:1) elec
trolyte at 85C (Figure 8[a]), the lowest testing tem
perature for Alloy 22 was 80C. In addition, the
average value of E
crev
approaches transpassive poten
tials in the pH 7.75 (100:1) electrolyte.
It can also be seen through Figures 7 and 8 that
the effects of solution composition, specifically the
molar ratio of Cl
625
1 092 0 169 7 233 10
3
(1)
E Alloy V
ratio T C
crev Ag AgCl
( , )
. . log( ) . ( )
/
22
2 369 0 253 1 852 10
2
(2)
The equations were developed from data for Alloy 22
between 80C and 95C, and for Alloy 625 between
60C and 95C using results from tests at 10:1 and
100:1 molar ratios. Through examination of Equa
tions (1) and (2), it can be seen that E
crev
for Alloy 22
is a stronger function of electrolyte molar ratio and
temperature than E
crev
for Alloy 625. This can also be
seen through comparison of Figures 7 and 8, which
illustrates the relationship between average E
crev
val
ues and temperature. Potentials increase to higher
values over a smaller range of temperature for Alloy
22 compared to Alloy 625. In addition, the difference
between stabilization potentials in the 10:1 electro
lyte and those in the 100:1 electrolyte is greater for
Alloy 22 than for Alloy 625. In fact, when the tem
perature is lowered from 95C in the pH 7.75 (10:1)
electrolyte, potentials at the 10
6
A/cm
2
threshold are
associated with transpassive dissolution of Alloy 22
and not stabilization of crevice corrosion.
Transpassive dissolution is observed for Alloy 625
only in the pH 7.75 (10:1) electrolyte at 60C. The 1:1
electrolytes lead to transpassive dissolution prior to
crevice stabilization at all tested temperatures.
Equations (1) and (2) can also be used to predict
E
crev
for a given electrolyte composition and tempera
ture. For example, Gruss, et al., examined the crevice
corrosion resistance of 625 at 95C in chloride elec
(a)
(b)
FIGURE 6. Cumulative probability plot of critical potentials for: (a)
Alloy 625 and (b) Alloy 22 in pH 7.75 electrolyte at 95C. The solid
and dotted lines indicate E
crev
and E
r,crev
, respectively. The vertical
dotted line represents the experimentally determined transpassive
potential for those conditions. Repassivation potentials are
determined using the 10
6
A/cm
2
current threshold.
(4)
Small hysteresis loops associated with the CPP curves on Alloy
22 at these temperatures may render E
r,crev
values
nonconservative.
CORROSION SCIENCE SECTION
1050 CORROSIONDECEMBER 2001
trolytes containing nitrate, sulfate, and fluoride with
ratios of chloride anions to all other anions ranging
from 60 to 19,000.
21
Critical crevice corrosion stud
ies revealed the occurrence of crevice corrosion for
each electrolyte ratio in the range. Application of
Equations (1) and (2) yields critical crevice corrosion
potentials below those associated with experimentally
determined transpassive potentials in agreement
with the results of Gruss. Moreover, the equations
show that if the electrolyte is sufficiently benign (i.e.,
it has a low electrolyte ratio), transpassive dissolu
tion will occur prior to the onset of crevice corrosion.
Through multiple regression analysis, it was de
termined that E
crev
for both Alloy 625 and Alloy 22 is
dependent upon electrolyte molar ratio and tempera
ture but not bulk solution pH. The same holds true
for E
r,crev
. Equations (3) and (4) show the results of
multiple regression analysis for E
r,crev
:
E V
ratio T C
r crev Ag AgCl , /
( , )
. . log( ) . ( )
Alloy 625
0 396 4 277 10 4 787 10
2 3
(3)
E Alloy V
ratio T C
r crev Ag AgCl , /
( , )
. . log( ) . ( )
22
2 455 0 358 2 041 10
2
(4)
The equations were developed from data for Alloy 22
between 80C and 95C and for Alloy 625 between
60C and 95C, using results from tests at 10:1 and
100:1 molar ratios. Equations (3) and (4) show that
critical potentials for repassivation are a stronger
function of electrolyte ratio and temperature for
Alloy 22 compared to Alloy 625. Under certain benign
conditions (i.e., when the electrolyte ratio is small
and the temperature is low), Alloy 22 has much
higher repassivation potentials than Alloy 625. This
can be seen through comparison of Figures 9(a) and
10(a), which illustrates the effect of temperature on
E
r,crev
in the 10:1 electrolyte. When tested at tempera
tures <95C in the 10:1 electrolyte, critical potentials
are well below experimentally determined transpas
sive potentials. However, the CPP curves for Alloy 22
have elevated repassivation potentials.
Survival Probabilities
and Stable Crevice Generation Rates
The effect of solution composition and tempera
ture on stabilization was also explored by assuming
that the cumulative probability plots shown in Figure
6 are linear and therefore indicative of normal distri
butions.
(5)
Figure 11 shows the survival probability
(P
s
) results for Alloy 625 at 95C in the pH 7.75 elec
trolytes. Results suggest that the probability of stabi
lization, (1P
s
), where P
s
is the survival probability
associated with E
crev
, is shifted negatively for the
(a)
(b)
FIGURE 7. Effect of temperature on E
crev
for Alloy 625 in: (a) 10:1
and (b) 100:1 electrolytes. The plots show the average value of the
distributions t1 standard deviation at temperatures of 60, 80, and
95C. The upper and lower dotted lines indicate experimentally
determined transpassive potentials on Alloy 625 for pH 2.75 and
pH 7.75, respectively.
(5)
Shibatas stochastic theory 14 (Corrosion 33, 7 [1977], p. 243
251) was then applied to analyze the potentiodynamic data in
terms of survival probabilities (P
s
) and crevice generation rates
() according to the procedure outlined in Appendix A. In this
analysis, all potential calculations were made for distributions of
stabilization potentials as well as distributions of repassivation
potentials. Using the distribution of repassivation potentials
yields a conservative estimate of survival probabilities and
stable crevice generation rates following the reasoning presented
earlier.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1051
100:1 electrolyte composition compared to the 10:1
electrolyte composition. That is, the survival prob
ability decreases more readily with increasing poten
tial for the 100:1 electrolyte composition. This effect
is seen more readily for survival probabilities calcu
lated based on E
r,crev
but can be seen for E
crev
as well.
Survival probability analysis of Alloy 22 yields
similar results. Figure 12 shows the results for Alloy
22 in the pH 7.75 electrolyte.
(6)
The effect of a large
standard deviation in critical potentials is reflected in
survival probability data for Alloy 22 specimens
tested in the pH 7.75 (10:1) electrolyte. A broad sur
vival probability curve is observed. However, the ef
fect of electrolyte ratio can still be seen as survival
probabilities start to decrease more readily at higher
potentials for specimens tested in the 100:1 electro
lyte ratio compared to the 10:1 electrolyte ratio. Note
that under certain conditions the survival probability
curve surpasses potentials associated with experi
mentally determined transpassivity. Above these po
tentials, both localized corrosion and transpassive
dissolution must be considered as possible corrosion
mechanisms.
The same trends are seen for experiments con
ducted at testing temperatures <95C. Figure 13
shows the results of survival probability calculations
for Alloy 625 in a pH 7.75 electrolyte at 80C and
60C. The effect of lowered temperature is clearly
seen. Again, the effect of electrolyte composition is
evident through analysis of both stabilization and
repassivation potentials. Survival probabilities are
observed to decrease only at higher potentials and
more gradually with potential for the 10:1 electrolyte
compared to the 100:1 electrolyte. However, the effect
is more noticeable for survival probability calcula
tions based on E
crev
distributions as compared to
E
r,crev
distributions. This is an expected result be
cause cumulative probability plots showed that E
r,crev
distributions in the 100:1 electrolyte were only
slightly lower than E
r,crev
distributions in the 10:1
electrolyte. Therefore, survival probability analysis
using E
r,crev
distributions shows only small differences
between the results for the 10:1 and the 100:1 elec
trolytes. Results for Alloy 22 at 85C and 80C are
shown in Figure 14 at 100:1 molar ratio. The effect of
temperature is clearly seen. As with Alloy 625, the
effect of solution composition is seen as a shift in the
survival probability curve, calculated using E
crev
dis
tributions, to higher potentials for experiments con
ducted in the 10:1 electrolyte compared to the 100:1
electrolyte (not shown). In addition, the effect of elec
trolyte ratio on survival probability is seen through
analysis of E
r,crev
distributions. The E
r,crev
distribution
for the 10:1 electrolyte ratio is shifted to much higher
potentials than the E
r,crev
ratio for the 100:1 electro
lyte ratio. Note that survival probabilities were not
calculated in cases where measured potential distri
butions were associated with transpassivity.
Temperature is also seen to have a strong effect
on survival probability. As temperature is lowered
from 95C to 60C for Alloy 625, survival probability
curves shift to higher potentials (Figure 13). In fact,
survival probabilities could not be calculated for Al
(a)
(b)
FIGURE 8. Effect of temperature on E
crev
for Alloy 22 in: (a) 10:1 and
(b) 100:1 electrolytes. The plots show the average value of the
distributions t1 standard deviation at temperatures of 80, 85, and
95C. The upper and lower dotted lines indicate experimentally
determined transpassive potentials on Alloy 625 for pH 2.75 and
pH 7.75, respectively.
(6)
Similar results were seen at pH 2.75.
CORROSION SCIENCE SECTION
1052 CORROSIONDECEMBER 2001
loy 625 tested at 60C in the pH 7.75 (10:1) electro
lyte because the distribution of critical potentials was
associated with transpassive dissolution (Figure 13).
The effect of temperature is especially notable for Al
loy 22. As temperature is lowered from 95C to 80C,
survival probability curves shift to much higher po
tentials. Moreover, survival probabilities could not be
(a) (b)
(a) (b)
FIGURE 9. Effect of temperature on E
r,crev
for Alloy 625 in: (a) 10:1 and (b) 100:1 electrolytes. The plots show the average
value of the distributions t1 standard deviation at temperatures of 60, 80, and 95C. Average E
r,crev
values are only based
on tests where transpassive dissolution did not occur.
FIGURE 10. Effect of temperature on E
r,crev
for Alloy 22 in: (a) 10:1 and (b) 100:1 electrolytes. The plots show the average
value of the distributions t1 standard deviation at temperatures of 80, 85, and 95C. Average E
r,crev
values are only based
on tests where transpassive dissolution did not occur.
calculated for Alloy 22 tested at 80C and 85C in the
pH 7.75 (10:1) electrolyte because associated stabili
zation potentials were attributed to transpassivity.
Crevice Generation Rates
Survival probability indicates the probability that
crevice corrosion will not stabilize at a given applied
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1053
potential under particular conditions. From the cal
culated survival probabilities, crevice generation
rates (events*cm
2
*s
1
) were calculated according to
the procedure outlined in Appendix A.
(7)
Figures 15
and 16 show stable crevice generation rates for Alloy
625 and Alloy 22 at 95C. These plots show that
stable crevice generation rates approach a maximum
value or plateau at high electrode potentials. That
is, once the potential reaches a certain high value,
the crevice generation rate becomes a very weak
function of potential. In addition, the effect of the
broad standard deviation of the distribution in criti
cal potentials is seen. Distributions with large stan
dard deviations yield broad crevice generation rate
curves, producing some rate of crevice stabilization
even at quite negative potentials.
(8)
If only distribu
tions with similar standard deviations are consid
ered, the effect of electrolyte composition can be seen
in Figures 15 and 16. Moreover, the crevice genera
tion rates at the plateau do not differ between tests
conducted in the 10:1 electrolyte compared to tests
conducted in the 100:1 electrolyte for distributions
with similar standard deviations. However, for the
same applied potential, the crevice generation rate is
generally lower for the 10:1 electrolyte than for the
100:1 electrolyte, as seen in Figures 15(a), 17(a) and
(b), and 18(a) and (b). However, when E
r,crev
is used as
a conservative estimate of generation rates at 95C,
there is little difference between the electrolyte molar
ratio (Figures 15[b] and 16[b]).
The effect of temperature is also seen through
comparison of crevice generation rates as a function
of electrode potential for different temperatures. Fig
ure 17 shows crevice generation rates for Alloy 625
in pH 2.75 electrolyte at 60C and 80C. The effect of
molar ratio is seen in the stabilization rates calcu
lated in this manner, and E
r,crev
provides a more con
servative estimate of rates. For the pH 7.75 (10:1)
electrolyte condition (not shown), stable crevice cor
rosion could be initiated at 80C but not at 60C.
Similar results are seen for Alloy 22 and are shown
in Figure 18 for 85C and 80C, respectively, in
2.75 pH electrolyte. Here, Alloy 22 exhibits its supe
rior resistance. For instance, in the 10:1 electrolyte
even the estimation of rates from E
r,crev
yields
negligible rates <0.5 V
Ag/AgCl
.
Testing temperatures
<80C led to transpassive dissolution, yielding
effective crevice generation rates of zero over all
potentials.
The temperature effect discussed above is more
clearly represented in Figures 19 and 20 for Alloy
625 and Alloy 22 in the pH 2.75 electrolyte at ratios
of 10:1 and 100:1, respectively. These figures show
the crevice generation rate as a function of potential,
calculated assuming that measurements of critical
potentials follow a normal distribution. Therefore,
crevice generation rates are dependent upon the
mean and the standard deviation of the distribution.
For example, in Figure 19(a), the breadth of the crev
ice generation rate curve clearly indicates that the
(a)
(b)
FIGURE 11. Survival probability as a function of electrode potential
for Alloy 625 at 95C in pH 7.75 electrolyte using: (a) E
crev
and
(b) E
r,crev
distributions. The dotted vertical line in (a) indicates
experimental Cr transpassive potentials at 95C for pH 7.75.
(7)
Note that crevice generation rates > ~10
5
events*cm
2
*s
1
, corre
sponding to a cumulative probability of 5%, are representative of
experimentally determined critical potentials. Crevice generation
rates <10
5
events*cm
2
*s
1
are representative of an extrapolation
of the experimental data to cumulative probabilities below this
5% level.
(8)
A nonzero crevice generation rate below the reversible electrode
potential for metal dissolution would be nonphysical. Such
results might be artifacts of large standard deviations or the
extrapolation of experimental data to cumulative probabilities
<5% in crevice generation rate calculations.
CORROSION SCIENCE SECTION
1054 CORROSIONDECEMBER 2001
distribution for the 60C data has a higher standard
deviation than the distributions for either 80C or
95C data.
5,(9)
Therefore, modified crevice generation
rates are also shown, assuming that each distribu
tion has identical standard deviations, in order to aid
comparison studies on the effect of temperature.
Examination of modified crevice generation rate rela
tionships reveals that, for a particular crevice
generation rate, the potential required to maintain
the arbitrarily selected rate is larger at lower tem
peratures. This is indicative of the beneficial effects
of decreasing temperature on the crevice corrosion
resistance of Alloy 625 and Alloy 22. This relation
ship is clearly shown through plots of potentialvs
temperature in Figures 19 and 20, where potential
refers to the potential below which the specified crev
ice generation rate cannot be maintained. Potential
temperature relationships are also useful in
comparison studies of Alloy 625 and Alloy 22. Fig
ures 19 and 20 reveal that the effect of temperature
on crevice generation rates is more prominent for
Alloy 22 than for Alloy 625. As the temperature is
decreased, the potential required to maintain a par
ticular crevice generation rate increases more rapidly
for Alloy 22 than for Alloy 625, as described by the
slopes of the potentialtemperature curves (Figures
19 and 20). The effect of temperature is particularly
strong for Alloy 22 in the pH 2.75 (10:1) environment
as crevice generation rates fall to negligible levels at
potentials >0.5 V
Ag/AgCl
when the temperature is de
creased <95C. When the temperature is decreased
from 95C to 85C, the slope of the potential
temperature curve is 0.04 V/C, while the transition
from 85C to 80C yields a slope of only 0.005 V/C.
This indicates that, at temperatures <85C in the
10:1 environment, highly oxidizing potentials are
required to maintain any crevice generation rate in
Alloy 22. Crevice generation would not be possible in
1:1 molar ratios. However, lower temperatures could
lead to transpassive dissolution before the onset of
crevice corrosion if high applied potentials were ever
achieved. Comparison of Alloy 625 and Alloy 22
through examination of Figures 19 and 20 also re
veals that potentialtemperature curves are shifted to
higher potentials over all temperatures for Alloy 22
as compared to Alloy 625. Similar trends are seen
for the pH 7.75 environment, as is expected because
distributions of critical potentials are relatively unaf
fected by pH.
DISCUSSION
Crevice Stabilization
Determination of crevice stabilization potentials
and, in turn, stable crevice generation rates, through
potentiodynamic scanning techniques, can be con
founded by scan rate. A slow scan rate approaching a
longterm potentiostatic hold should yield the most
conservative estimate of stabilization potential. How
ever, Baroux argued that there sometimes could exist
a critical scanning rate below which pitting suscepti
bility decreases during testing as a result of time
dependent beneficial modifications in the protective
(a)
(b)
FIGURE 12. Survival probability as a function of electrode potential
for Alloy 22 at 95C in pH 7.75 electrolyte using: (a) E
crev
and
(b) E
r,crev
distributions. The dotted vertical line in (a) indicates
experimental Cr transpassive potentials at 95C for pH 7.75.
(9)
Such variations in standard deviations are attributable to test
ing on a limited number of specimens. Higher sample sizes
would likely yield more consistent standard deviations among
the different test conditions.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1055
oxide.
35
At faster scan rates, the kinetics of localized
corrosion must be taken into account.
35
These pro
cesses are opposing. The question remains as to
what scan rate, if any, should be used to most accu
rately represent shortterm laboratory testing that
could pertain to the conditions during longterm un
derground storage. Depending on thermal manage
ment of nuclear waste containers, the canister wall
temperature for the first 300 years could be above
the boiling point of water,
3637
leading to periods of
dry oxidation and humid air oxidation prior to drip
ping of aqueous solutions that could form concen
trated brines. Therefore, a slow scan rate, or long
term potentiostatic hold on material aged in air to
simulate thermal oxidation might be more represen
tative of the predicted conditions of the nuclear waste
repository.
Thompson and Syrett established the idea of one
critical potential for stabilization based on repassiva
tion potentials.
16
Dunn and Sridhar used a compari
son of repassivation potentials to opencircuit
potentials as a conservative estimate of windows of
susceptibility to localized corrosion in their studies of
the pitting susceptibility of Alloy 825.
20
They rea
soned that the highest repassivation potentials would
be obtained for pits given minimal growth, which
would thereby provide a conservative estimate of the
threshold potential for stabilization of small pits
given infinite time at a given potential. Recall that
E
r,crev
did not change with accumulated anodic charge
(i.e., the amount of damage) in this study. Therefore,
E
r,crev
obtained from potentiodynamic scans might
represent a lower bound of critical potentials that
might be equivalent to longterm potentiostatic re
sults. E
crev
might represent an upper bound. Conse
quently, the effects of electrolyte composition (i.e.,
molar ratio) and temperature on both E
crev
and E
r,crev
determined in this study could be considered to rep
resent the upper and lower bounds of what might be
obtained in crevice stabilization studies under long
term potentiostatic hold.
Effect of Temperature on Stabilization
The strong effect of temperature on stabilization
has also been shown in this study through CPP test
ing. In addition, it has been previously shown that
temperature has a strong effect on crevice corrosion
properties of Nibased alloys and stainless
steels.
11,19,3839
Brigham and Tozier showed that CPP
increase with decreasing temperature for NiCr alloys
containing between 3.04 wt% and 7.30 wt% Mo.
39
This relationship is also seen for critical crevice po
tentials of Alloy 625 in Figure 7 and those of Alloy 22
in Figure 8. Higher temperatures raise metal dissolu
tion rates, hydrolysis reaction rates, oxide dissolu
tion rates, and passive current densities, as well as
the ionic mobility of chloride anions. These factors
may enable the formation of the critical crevice solu
tion at a decreasing potential driving force compared
to lower temperatures, where a greater potential
driving force is required. In addition, the number of
metallurgical surface sites susceptible to nucleation
of localized corrosion increases at higher tempera
tures.
40
The results of Brigham and Tozier showed
that critical crevice temperatures are higher for NiCr
alloys with higher Mo contents.
39
The effect of alloyed
(a)
(b)
FIGURE 13. Survival probability as a function of electrode potential
for Alloy 625 at: (a) 80C and (b) 60C in pH 7.75 electrolyte. Survival
probabilities are calculated using both E
crev
and E
r,crev
distributions.
The dotted vertical lines indicate experimental Cr transpassive
potentials at 80C for the pH of interest.
CORROSION SCIENCE SECTION
1056 CORROSIONDECEMBER 2001
(a)
(b)
FIGURE 14. Survival probability as a function of electrode potential
for Alloy 22 at: (a) 85C and (b) 80C in pH 7.75 electrolyte. Survival
probabilities are calculated using both E
crev
and E
r,crev
distributions.
The dotted vertical lines indicate experimental Cr transpassive
potentials at 80C for the pH of interest.
Mo and W is also seen through comparison of Fig
ures 7 and 8, which present the effect of temperature
on E
crev
for airaged Alloys 625 and 22. The figures
illustrate that critical crevice stabilization potentials
increase more significantly for Alloy 22 compared to
Alloy 625 as temperature is lowered. This would sug
gest that temperature affects metal dissolution prop
erties and possibly metastable crevice corrosion
properties more strongly for Alloy 22 compared to
Alloy 625. Both effects have been confirmed and are
reported elsewhere.
33,41
This may control the transi
tion to stability through formation of the critical
crevice chemistry.
Repassivation of Stabilized Crevices
It is important to note that two types of E
r,crev
can be observed depending on experimental condi
tions.
2324,42
The
first is associated with the potential
at which crevice dissolution and cation hydrolysis
do not occur at fast enough rates to maintain a
depassivating solution within the crevice (i.e., true
repassivation by passivating oxide film growth). This
potential is thus associated with a lowering of the
crevicedissolution rate to eventually enable cessa
tion of crevice attack because the depassivating
crevice solution is not maintained. Repassivation of
the crevicecorroded surface occurs. This potential
will be dependent upon time, crevice geometry (i.e.,
gap and depth), temperature, solution composition,
and alloydissolution rate. The first four factors con
trol the masstransport properties of the crevice solu
tion, while the dissolution rate controls the rate of
hydrolyzable cation production. Repassivation on
reverse potential scans will hence be indicated by
reestablishment of passivity at some characteristic
critical potential where dissolution and hydrolysis
rates become slower than the transport rates associ
ated with species exiting the crevice, leading to a
dilution of the crevice solution and an increase of the
crevice pH. Therefore, this potential is not deter
mined solely by material properties. Unfortunately,
potential sweep rate can confound determination
of this potential when all other variables are fixed.
This is because a fast downward potential sweep of
an active crevice will enable a higher crevice corro
sion rate to be momentarily sustained over a range
of lower potentials than sustainable, given infinite
time when steadystate transport conditions are
achieved.
The passive current density is also observed to
be greater on the reverse scan compared to the initial
scan because the newly reformed oxide over just
repassivated crevice sites is thin and defective and
may support cation transmission at higher rates.
Moreover, the solution is acidified from cation hy
drolysis, and the passive current density over all pas
sivated surfaces is usually strongly affected by pH at
the low values attained through formation of a criti
cal chemistry.
5,43
These factors can confound deter
mination of E
r,crev
from Elog(i) data associated with
repassivation of active crevice sites. An E
r,crev
value
representative of true repassivation is most likely ob
served upon slow downward scanning or long holds
during downward potential stepping.
20
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1057
(a) (b)
(a) (b)
FIGURE 15. Crevice generation rate as a function of electrode potential for Alloy 625 at 95C in pH 7.75 electrolyte using:
(a) E
crev
and (b) E
r,crev
distributions. Reported crevice generation rates are normalized to the total electrode area (8.5 cm
2
),
which includes 24 crevice sites, each of area 0.06 cm
2
. The dotted vertical line in (a) indicates experimental Cr transpassive
potentials at 95C for pH 7.75.
FIGURE 16. Crevice generation rate as a function of electrode potential for Alloy 22 at 95C in pH 7.75 electrolyte using:
(a) E
crev
and (b) E
r,crev
distributions. Reported crevice generation rates are normalized to the total electrode area (8.5 cm
2
),
which includes 24 crevice sites, each of area 0.06 cm
2
. The dotted vertical line in (a) indicates experimental Cr transpassive
potentials at 95C for pH 7.75.
The second type of E
r,crev
value is associated with
the OCP of the actively corroding crevice. Below this
potential, the electrochemical reactions at the crevice
surface become net cathodic. This potential, some
times referred to as a deactivation potential,
23
is not
necessarily associated with repassivation. This po
tential will be indirectly dependent on crevice geom
etry because it affects the pit chemistry that can de
velop (e.g., the pH and the presence of oxidizing and
reducing species). The pit chemistry, in turn, affects
cathodic kinetics, but this potential is more directly
governed by the preexisting pit chemistry, tempera
CORROSION SCIENCE SECTION
1058 CORROSIONDECEMBER 2001
(a)
(b)
FIGURE 17. Crevice generation rate as a function of electrode
potential for Alloy 625 at: (a) 80C and (b) 60C in pH 2.75 electrolyte.
Rates are calculated using both E
crev
and E
r,crev
distributions. Reported
crevice generation rates are normalized to the total electrode area
(8.5 cm
2
), which includes 24 crevice sites, each of area 0.06 cm
2
.
The dotted vertical lines in (a) and (b) indicate experimental Cr
transpassive potentials at 80C and 60C, respectively, for the pH of
interest. Only airaged samples are considered.
ture, cathodic kinetics, and alloy electrochemical
dissolution properties that normally affect any mixed
potential. This latter type of E
r,crev
will most likely be
observed upon fast downward potential scanning of
an active crevice (as seen elsewhere
24
) because the
concentrated crevice solution composition in an ac
tive crevice has little time to become diluted at rapid
scan rates (i.e., steadystate transport conditions are
not achieved). It is usually the most conservative of
the two values of E
r,crev
because it is often associated
with more negative potentials associated with the
OCP of the metal in the pit environment.
24
Caution
is necessary, however, since this potential can be
corrupted by prior crevice corrosion if induced at
very high potentials. The Cr
6+
and Mo
6+
species gener
ated at such high potentials are oxidizers that posi
tively shift the crevice OCP more than is possible
from protons alone and lower valencestate metal
cations. Cragnolino observed this in studies on
Alloy 22.
25
For pitting corrosion, the repassivation potential
has been shown to be dependent upon the total an
odic charge collected.
24,26
Such a dependency is more
likely when the first definition of repassivation poten
tial
applies and when corroded sites determine the
geometric factors that impede transport (i.e., pitting),
not when a synthetic crevice former creates the ge
ometry that controls transport. This is because the
masstransport properties of an open pit can be
heavily influenced by pit depth (and, therefore, disso
lution charge). Such dependency of the repassivation
potential on anodic dissolution charge is not seen
for the crevice corrosion phenomenon studied here
(Figure 5). The reason for this is that masstransport
properties are apparently dominated by the geometry
of the crevice former defined by the ceramic crevice
washer and deformable PTFE insert, rather than by
the depth of crevice corrosion penetration itself. As
shown in Figure 1(b), the distance x
crit
is implicated
to be >r, where x
crit
is the crevice depth from the
mouth to the active site and r is the crevice penetra
tion depth.
Comparison of Alloy 625 and Alloy 22
The alloys can be compared based on threshold
potentials as well as crevice generation rates deter
mined through analysis of E
crev
and E
r,crev
distribu
tions. Comparison of crevice generation rates shows
a somewhat larger difference between Alloy 22 and
Alloy 625 as the temperature is dropped when the
results from the 100:1 electrolyte are compared to
those from the 10:1 electrolyte. This is consistent
with the multiple regression analyses of E
crev
and
E
r,crev
distributions (Equations [1] through [4]), which
reveal critical potentials for Alloy 22 to be a stronger
function of electrolyte ratio and temperature com
pared to Alloy 625. It should also be noted that crev
ice generation rates for Alloy 625 as well as Alloy 22
subjected to a 1:1 environment at any potential
would be expected to drop to rates much lower
(incomplete distributions do not allow these rates to
be calculated) than those calculated for the 10:1 or
100:1 environments over the same range of applied
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1059
(a)
(b)
FIGURE 18. Crevice generation rate as a function of electrode
potential for Alloy 22 at: (a) 85C and (b) 80C in pH 2.75 electrolytes.
Rates are calculated using both E
crev
and E
r,crev
distributions. Reported
crevice generation rates are normalized to the total electrode area
(8.5 cm
2
), which includes 24 crevice sites, each of area 0.06 cm
2
.
The dotted vertical lines indicate experimental transpassive potentials
at 80C for the pH of interest.
potentials, indicating the importance of defining the
pertinent environment. Moreover, the effect of tem
perature on the corrosion resistance of Alloy 625 and
Alloy 22 was shown to be the largest single factor of
this study influencing the difference between the two
alloys. Results from critical stabilization potential
studies, multiple regression analyses, and subse
quently, calculations of survival probabilities and
crevice generation rates reveal that Alloy 625 and Al
loy 22 can exhibit similar crevice corrosion properties
at 95C in the brine solutions studied here. However,
at lower testing temperatures there is a significant
difference between the alloys. A direct comparison
can be made using the 80C data shown in Figures
17 and 18 for Alloy 625 and Alloy 22, respectively.
Stable crevice generation rates were calculated for
Alloy 625 in each electrolyte composition. However,
in the pH 7.75 (10:1) electrolyte, crevice generation
rates could not be calculated for Alloy 22 at 80C
because apparent stabilization potentials were as
sociated with transpassivity. However, finite crevice
generation rates would still be possible for Alloy 625
under the same conditions. This point is also rein
forced from Figures 19 and 20. An applied potential
that is >100 mV more positive is required to achieve
the same crevice stabilization rates chosen on Alloy
22. In addition, for lowpH environments where
transpassivity occurs at highly oxidizing potentials
compared to neutral or highpH environments, crev
ice generation rates remain low at high potentials for
Alloy 22 in the pH 2.75 (10:1) electrolyte compared to
Alloy 625. Thus, Alloy 22 is shown to be more resis
tant than Alloy 625 to crevice corrosion stabilization.
PotentialBased Criteria for Localized Corrosion
A common approach used to assess localized
corrosion resistance is to compare the conditions
that the alloy would be subjected to in service to the
potentialtemperatureelectrolyte composition win
dow of susceptibility. Typically, this is done by com
parison of E
ocp
to the critical potentials expected,
such that when E
ocp
E
r,crev
crevice corrosion is ex
pected and when E
ocp
< E
r,crev
it is not. The present
study has taken an initial step in mapping the win
dows of susceptibility expressed in terms of critical
potentials, survival probabilities, and crevice genera
tion rates for Alloy 625 and Alloy 22 in brine solu
tions at various molar ratios and temperatures.
Combining such probabilistic analysis with the above
potentialbased criteria indicates that the boundaries
between safe and susceptible windows can be shifted
in potentialtemperatureelectrolyte composition
space depending upon the probability of crevice
attack deemed acceptable. This advances the assess
ment of crevice corrosion risk beyond mere state
ments of number of mV, C, or concentration units
that pertinent conditions differ from the window of
susceptibility.
In the present study, E
ocp
for airaged specimens
ranged from ~ 0.0 V
Ag/AgCl
to 0.150 V
Ag/AgCl
(25C)
with ~90% certainty in all test solutions at 95C.
Using cumulative probability plots and standard de
viation statistics for E
r,crev
, survival probability, and
crevice generation rates in the 100:1 electrolyte, it
can be seen that there is a very low but finite prob
ability of crevice attack on Alloy 22 at 95C based on
CORROSION SCIENCE SECTION
1060 CORROSIONDECEMBER 2001
(a) (b)
(c) (d)
FIGURE 19. Crevice generation rate as a function of electrode potential (left) and corresponding generation potential
temperature relationships (right) for: (a) Alloy 625 and (b) Alloy 22 specimens in the pH 2.75 (10:1) environment. Reported
crevice generation rates are normalized to the total electrode area (8.5 cm
2
), which includes 24 crevice sites, each of area
0.06 cm
2
. The solid lines illustrate crevice generation rates calculated assuming E
crev
measurements follow a normal
distribution and are therefore based on exact values of the mean and the standard deviation. The dotted lines illustrate
crevice generation rates assuming normal distributions, but also assuming that each distribution has the same standard
deviation taken to be the lowest standard deviation from the original data. The mean from the original data is preserved
and used. Potentialtemperature relationships indicate the potential required to achieve a specified crevice generation rate
at a particular temperature and are based on the assumption of one standard deviation for all distributions.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1061
(a) (b)
(d) (c)
FIGURE 20. Crevice generation rate as a function of electrode potential (left) and corresponding generation potential
temperature relationships (right) for: (a) Alloy 625 and (b) Alloy 22 specimens in the pH 2.75 (100:1) environment. Rates
are calculated using E
crev
distributions and are presented for testing temperatures of 60, 80, and 95C for Alloy 625 and 80,
85, and 95C for Alloy 22. Reported crevice generation rates are normalized to the electrode area (8.5 cm
2
), which includes
24 crevice sites, each of area 0.06 cm
2
. The solid lines illustrate crevice generation rates calculated assuming E
crev
measurements follow a normal distribution and are therefore based on exact values of the mean and the standard deviation.
The dotted lines illustrate crevice generation rates assuming normal distributions, but also assuming that each distribution
has the same standard deviation taken to be the lowest standard deviation from the original data. The mean from the
original data is preserved and used. Potentialtemperature relationships indicate the potential required to achieve a specified
crevice generation rate at a particular temperature and are based on the assumption of one standard deviation for all
distributions.
CORROSION SCIENCE SECTION
1062 CORROSIONDECEMBER 2001
the values of the parameters in Figures 6 through 10,
11 through 14, and 16 through 20. This probability
decreases yet remains finite in the 10:1 electrolyte
and is unknown but likely very low at the 1:1 ratio. It
is interesting to note that a crevice generation rate of
only 10
14
events*cm
2
*s
1
(Figures 19 and 20) trans
lates into one event on 10
4
cm
2
of surface area over
1,000 years if taken literally. Unfortunately, very low
probabilities and generation rates per unit surface
area can represent a credible risk if the structure
exposes large areas for long times. It is evident from
similar reasoning that, in order to have the chance of
actually observing such rare attack experimentally in
the laboratory, a large number of crevice sites must
be tested over a finite time period in order to increase
the atrisk crevice surface area sufficiently, assum
ing such low probabilities apply. In other words, a
few specimens are insufficient to assess the chance
of crevice corrosion at such low probabilities. Yet the
longterm exposure of large surface areas, given long
term underground storage of many waste packages,
creates the possibility that such low probabilities
cannot be ignored. Alternatively, it might be argued,
using a deterministic approach to crevice corrosion
susceptibility, that critical crevice solutions could not
physically form at the negative potentials where
probabilistic analysis based on statistical distribu
tions of data argue that there is a nonzero chance of
attack. However, the two philosophies can be merged
if the statistical approach reflects the rare possibility
of an extremely tight crevice and unusually vulner
able metallurgical site, etc. In this case, a determin
istic approach might predict the same result when
applied to such rare and locally severe conditions.
The potential scanning methods used here could
find no evidence of crevice attack at potentials below
the transpassive potential range in the 1:1 electro
lyte. Recall that this molar ratio approaches those
achieved by concentration of dripping solutions on
waste canisters at the proposed Yucca Mountain
Nuclear Waste Repository.
30
Hence, the probability
of crevice stabilization would be expected to fall to
almost zero in the 1:1 electrolyte at similar E
ocp
.
Equations (2) and (4) provide a means to estimate
E
r,crev
at 95C or even 105C from the 1:1 molar ratio
case if the expressions are robust enough to enable
calculations over this range of conditions (outside the
range of experiments used to construct the relation
ships). The resulting critical potentials at 105C of
0.424 V
Ag/AgCl
(E
crev
) and 0.312 V
Ag/AgCl
(E
r,crev
) (at 25C)
for Alloy 22 still exceed E
ocp
by several hundred mV.
(10)
If the temperature is decreased to 95C, then E
crev
rises to 0.61 V
Ag/AgCl
and E
r,crev
rises to 0.516 V
Ag/AgCl
(at 25C). Therefore, it is reasonable to speculate that
the probability of crevice attack does approach zero
at opencircuit potentials ranging from 0.0 V
Ag/AgCl
to
0.150 V
Ag/AgCl
(25C) in the 1:1 electrolyte based on
assumptions of normal probabilities, etc., obtained
from studying stabilization rates and survival prob
abilities in the 100:1 and 10:1 ratio electrolytes. Fur
ther, it is interesting to note that these estimated
critical potentials are well above the opencircuit
potentials reported in the longterm crevice testing
conducted at Lawrence Livermore National Labs.
41
Although the 1:1 electrolyte used here (Table 4) dif
fers in exact composition from the acidified concen
trated and saturated solutions used in longterm
testing, the molar ratios of some of these solutions
are close to 1:1 Cl

:(NO
3
+ SO
4
2
) and contain nearly
1 M Cl
:(NO
3
+ SO
4
2
) cannot support stable crevice cor
rosion at E
ocp
. It is also interesting to note that crev
ice corrosion of Type 304 stainless steel was also
inhibited in 1:1 ratios of Cl
:(NO
3
+ SO
4
2
) in 17 mM
NaCl. Here, nitrate was found to be a stronger inhibi
tor than sulfate and provide a greater benefit than
that afforded by competitive migration.
45
CONCLUSIONS
Repassivation potential is a more reproducible pa
rameter than stabilization potential given its nar
rower statistical distribution. Both parameters
produced roughly normal distributions. Potentiody
namically determined repassivation potentials at
95C are similar for both alloys in 100:1 and 10:1
molar ratio environments and do not depend on pH
or accumulated anodic charge associated with crev
ice corrosion. The effect bulk of electrolyte composi
tion on repassivation potential is small at 95C.
Repassivation potential increases significantly in
100:1 and 10:1 environments as the temperature is
decreased <95C for both alloys. Moreover, multiple
regression analysis showed that E
crev
and E
r,crev
are
stronger functions of temperature and electrolyte
composition for Alloy 22 than for Alloy 625. Thus,
as temperatures are lowered from 95C, E
crev
values
increase to such an extent for Alloy 22 compared to
Alloy 625 that they easily approach or exceed trans
passive potentials at equivalent electrolyte ratios.
Electrolyte composition and molar ratio also have
a stronger effect on crevice stabilization potentials
than bulk solution pH at all temperatures tested.
CPP tests at 95C in the pH 2.75 (1:1 ratio) electro
lyte led to an average stabilization potential that was
500 mV higher than that of the pH 2.75 (100:1 ratio)
(10)
Assuming that E
ocp
during full immersion tests is pertinent for
the case of a thin film of electrolyte from water drips.
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1063
electrolyte. Therefore, crevice corrosion susceptibili
ties were very low if 1:1 molar ratio solutions were
used. Similarly, the 10:1 molar ratio yields more
positive stabilization potentials than the 100:1 molar
ratio at all temperatures. This implies that, when the
electrolyte ratio is low, transpassive dissolution may
occur at positive applied potentials instead of the on
set of crevice corrosion.
There was little distinguishable difference between
crevice stabilization potentials for bulk pH values of
2.75 and 7.75 for either alloy, indicating little effect
of bulk solution pH on crevice corrosion susceptibil
ity over this range.
Electrolyte ratio and temperature have a strong
effect on calculated survival probabilities and crevice
generation rates for both Alloy 625 and Alloy 22.
Specifically, for low electrolyte ratios and tempera
tures, survival probabilities remain high and crevice
generation rates remain low even at elevated poten
tials. However, temperature has a stronger effect on
Alloy 22 than on Alloy 625. When subjected to the
(10:1) electrolyte at temperatures <95C, crevice gen
eration rates are very low for Alloy 22. At high poten
tials, the onset of transpassive dissolution occurs
before crevice corrosion.
Comparison of E
r,crev
, as a conservative measure of
crevice stabilization, to OCP data at 100:1 and 10:1
ratios suggests that there is a nonzero probability of
crevice corrosion at these molar ratios at 95C. The
probability of attack approaches zero as the tempera
ture is lowered. Moreover, if similar OCP are com
pared to estimated E
r,crev
values in 1:1 molar ratios,
crevice corrosion is not expected for either Alloy 625
or Alloy 22 based on the large difference in potential
(E
r,crev
E
ocp
) and the expected low crevice generation
rates at E
ocp
. This is consistent with longterm crevice
corrosion tests conducted elsewhere at OCP.
ACKNOWLEDGMENTS
This work was performed under the auspices of
the U.S. Department of Energy by Lawrence Liver
more National Laboratory (LLNL) under Contract
W7405ENG48. This work is supported by Yucca
Mountain Site Characterization project, LLNL. The
authors acknowledge Perkin Elmer Instruments and
Scribner Associates for their ongoing technical sup
port for the Center of Electrochemical Science and
Engineering at the University of Virginia.
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APPENDIX: SURVIVAL PROBABILITY
AND STABILIZATION RATE CALCULATIONS
Survival probability, P
s
(t), is defined as the pro
portion of unattacked crevice specimens at time, t. In
a given time, P
s
(t) can be estimated from the following
equation:
P t
n t
N
s
( )
( )
+
1
1
(A1)
where N is the total number of specimens examined
and n(t) is the nth specimen that failed at time t.
14,4647
The parameter P(t) is used for measurements of in
duction times determined potentiostatically and can
be used to calculate generation rates according to the
equation:
( )
ln ( )
t
d P t
dt
s
(A2)
This can be modified for potentiodynamic data at a
constant upward scan rate
14,48
according to the
equation:
ln ( )
d P E
dE
s
(A3)
where is the generation rate and is the scan rate,
E/t. P
s
(E) is the survival probability out to an ap
plied potential E given by:
P E
n E
N
s
( )
( )
+
1
1
(A4)
where n(E) is the number of failed specimens at E,
and N is described above.
According to Stewart and Williams, reliable esti
mates of (E) require testing of a large number of
specimens.
48
In this study, only 5 to 10 specimens
were examined at each test condition. Therefore,
crevice generation rates were determined using the
procedure detailed below, relying on the assumption
of a normal probability distribution.
14,48
Each step of
the procedure is illustrated using the data for air
aged Alloy 625 samples tested in the pH 2.75 (10:1)
electrolyte at 95C.
A cumulative probability plot was generated
for the raw experimental data. A linear cumulative
probability plot indicates a normal distribution, and
most distributions were approximately linear when
plotted in this format.
14,3334
The probability density
function for normally distributed data is given by the
equation:
f E E ( ; , ) exp ( ) /( )
[ ]
1
2
2
2 2
(A5)
where E is a measured critical potential that is part
of the distribution (i.e., E
crev
or E
r,crev
), is the mean
for the subset of nominally identical specimens, and
s
2
is the standard deviation of the same. The cumula
tive probability, P
c
(E < E
crit
), is the probability that
any given measurement will fall below the specified
value, E
crit
, and can then be determined by integrat
ing Equation (A5) from to E
crit
:
33,49
P E E f E dE
c crit
E
crit
( ) ( ; , )
<
(A6)
For the data presented in this paper, a normal distri
bution was a good assumption or was reasonably as
sumed for all distributions of E
crev
or E
r,crev
unless all
measured potentials in the distribution were attrib
uted to transpassivity. Distributions associated with
transpassivity were not considered in the analysis of
survival probabilities and stable crevice generation
rates. Therefore, distributions that were not associ
ated with transpassivity were represented by the
equation for the probability density function for nor
mally distributed data (Equation [A5]) using all ex
perimentally determined values to produce the
sample mean and standard deviation. The cumula
tive probability was then calculated through applica
tion of Equation (A6) for a chosen range of potentials
using a statistical analysis or spreadsheet software
package. The range of potentials was chosen such
that the cumulative probability at low potentials ap
proached zero and the cumulative probability at high
potentials approached one. Figure A1 shows a cu
CORROSION SCIENCE SECTION
CORROSIONVol. 57, No. 12 1065
mulative probability plot for the raw experimental
data and the associated fit to a normal distribution.
It should be noted that a linear cumulative probabil
ity plot indicates a normal distribution.
14,3334
In Step 1, cumulative probabilities were calcu
lated for a range of critical potential values. Assum
ing N approaches infinity, the survival probability,
P
s
(E), was expressed as a limit based on Equation
(A4). This is equivalent to Equation (A4) where the
discrete value n(E) in the term n(E)/(1+N) has been
replaced by a continuous function for n(E) where N
approaches infinity:
P E
N f E dE
N f E dE
s
N
E
crit
( )
( ; , )
( ; , )
lim
( )
+
1
]
1
'
1
1
(A7)
Equation (A7) was then evaluated using the fact that
'
+
1
1
(A8)
which can then be reduced to:
P E P E E
s c crit
( ) ( ) < 1 (A9)
Figure A2 shows the results of the survival probabil
ity calculations.
FIGURE A1. Cumulative probability plot for E
crev
showing fit of data
to a normal distribution for airaged Alloy 625 samples tested in the
pH 2.75 (10:1) electrolyte at 95C.
FIGURE A2. Survival probability as a function of electrode potential
calculated for potentiodynamic data for airaged Alloy 625 samples
tested in the pH 2.75 (10:1) electrolyte at 95C. Each symbol
represents the calculated value for P
s
(E) at a potential E.
FIGURE A3. Crevice generation rate as a function of electrode
potential showing an increase in (E) with potential for airaged Alloy
625 samples tested in the pH 2.75 (10:1) electrolyte at 95C.
The crevice generation rate for a total electrode
area A was then calculated using Equation (A3).
Application of Equation (A3) entails calculating the
slope of the ln[P
s
(E)] vs E curve between consecutive
points on the graph and multiplying by the negative
of the scan rate. The result was then divided by the
sample area to determine the potentialdependent
crevice generation rate per unit area, (E), as shown
in Figure A3.