EFFECTS OF PWR PRIMARY WATER CHEMISTRY AND DEAERATED WATER ON SCC

Peter L. Andresen, Paul W. Emigh, Martin M. Morra and John Hickling*

GE Global Research, One Research Circle K13A39, Schenectady, NY 12309
*EPRI, 3412 Hillview Ave., Palo Alto, CA 94303
Keywords: Stress Corrosion Cracking, PWR Water Chemistry, High Temperature Water, Boron and Lithium Effects, pH
Abstract
Most, probably all, structural materials have a fundamental
susceptibility to SCC in high temperature water, although their
specific response varies greatly with material and condition, water
chemistry, temperature, stress, etc. The last twenty years of
research has also established that most, probably all, variations of
SCC result from a continuum response associated with a complex
interdependence of many variables. This continuum allows
integration of diverse observations and mechanistic insights to
provide a basis for anticipating and interpreting the effects of
specific variables. This paper discusses these anticipated and
observed SCC effects over a range of high temperature water
chemistries, with particular emphasis on those relevant to PWRs.
Key words: stress corrosion cracking, crack growth rates, high
temperature water, PWR, water chemistry, stainless steel, Ni
alloys, corrosion potential, stress intensity factor.
Introduction
Essentially all structural materials (i.e., iron- and nickel-base
alloys) have exhibited stress corrosion cracking (SCC) under
unirradiated and/or irradiated conditions, in light water reactor
components and/or in laboratory tests [1-7]. Despite the many
field and lab observations and the many common characteristics
(e.g., Figures 1 6), SCC tends to be compartmentalized into
small, unique modes with an inherent implication that different
mechanisms and dependencies are involved. However, the crack
tip is deaerated and at low potential in all cases, so the
environmental conditions under which crack advance occurs in
light water reactor systems are very similar [25,8,9]. Thus, the
primary differentiation between boiling water reactors (BWRs)
and pressurized water reactors (PWRs) is comprised of: coolant
additives that shift the pH at temperature from 5.6 to ~7.2; H
2
fugacity (~50 vs 3000 ppb H
2
); and temperature (274 288 C vs.
290 338 C). Of these, temperature may be the most important
factor for stainless steels; for nickel alloys (where the Ni/NiO
transition can be traversed) both temperature and H
2
fugacity are
important [2,5,6,8].
Viewing SCC growth from the perspective of the crack tip system
is critical to understanding the crack growth response, especially
water chemistry effects. Among all of the variables that affect
SCC, the effect of water chemistry is particularly strong, and
factors that create an altered crack tip environment relative to the
bulk are of greatest significance. Two factors stand out in this
regard: gradients in temperature and in electrochemical potential
in the crack. Gradients in temperature occur in classical heat
transfer situations like PWR steam generators, but also occur in
other situations, e.g., from gamma heating in core components
(e.g., PWR baffle bolts and plates). Actions to mitigate this
particular phenomenon have been undertaken by improving liquid
access to the bolt shank area. Gradients in temperature are
especially important when boiling occurs, because species can
concentrate to very high levels.
Gradients in electrochemical potential result primarily from
oxidants in solution (Figure 7), which are consumed (cathodically
reduced) as they diffuse into the crack by metal corrosion or
reaction with H
2
(or other reductants). This differential oxidant
cell results in a driving force that concentrates anions like chloride
and sulfate into the crack, and drives cations out of the crack.
Because in many cases the pH in the crack is within a few units of
neutral (where the solubility of metal cations is low) charge
neutrality among anions and cations is often balanced by H
+
, at
least in relatively pure water. This leads to the presumption that
in oxidizing water chemistries the crack chemistry is always
acidic; however, unless anions other than OH

are present (e.g.,

chloride or sulfate), there is no mechanism for acidification (the
additional H
+
much be charge balanced by anions other than
OH

), and the pH increases. Common oxidants in light water

reactors (LWRs) include O
2
, H
2
O
2
, and Cu
+2
.
The primary source of oxidants in LWRs is radiolysis of water,
which forms a variety of oxidizing (esp., H
2
O
2
) and reducing (esp.
H
2
) species. PWRs operate at sufficiently high H
2
(about 30
cc/kg, which is 1.7 atm or 2.68 ppm) that radiolysis is suppressed.
It is important to recognize that reductants like H
2
do not give rise
to potential gradients of consequence. In the absence of oxidants,
H
2
is not consumed in the crack, so there is no gradient in H
2
and
therefore no gradient in potential is formed. Corrosion reactions
do generate H
2
, so cracks can have slightly enhanced levels of H
2
compared to the bulk, but the resulting difference in potential if
the H
2
rises from 30 to 60 cc/kg (very unlikely) is only 17.9 mV at
325 C. Conversely, on the primary side of stream generator
tubing, H
2
can diffuse through the thin-walled tubing to the (low
H
2
) secondary side, but cracks on the primary side are again
unlikely to be as much as 2X lower in the crack, esp. since
corrosion in the crack is generating some H
2
. The effect of such
small potential gradients in LWR water is negligible, even in the
higher conductivity, buffered B/Li solutions used in the PWR
primary. Note that very little ionization of H
3
BO
3
occurs for a
typical beginning of cycle chemistry of 1200 ppm B as H
3
BO
3
and 2 ppm Li as LiOH, the conductivity at 325 C is about 190
S/cm. The same 325 C conductivity and pH (7.22 at
temperature) is achieved in a solution comprised of only 1.4 ppm
Li and 5.8 ppm Cl (which are fully ionic).
Metallurgical and microstructural variables also have a significant
influence on SCC response. Sensitization (Cr depletion) from
thermal treatments or irradiation is widely recognized as
damaging in BWR normal water chemistry, but it plays a small
role in deaerated pure (or near-neutral) water [2-6,8], and this low
corrosion potential condition is achieved catalytically in an
increasing fraction of BWRs using NobleChem [10-11]. The
presence of grain boundary carbides once thought to be uniquely
important in PWR chemistry has been shown to be beneficial in
Proceedings of the 12th International Conference on
Environmental Degradation of Materials in Nuclear Power System Water Reactors
Edited by T.R. Allen, P.J. King, and L. Nelson TMS (The Minerals, Metals & Materials Society), 2005
989
both environments (provided Cr depletion is absent) [4,12,13].
Yield strength also has a strong effect on SCC growth rate in all
water chemistries (e.g., Figure 1). Elevation in yield strength can
originate from many phenomenon surface cold work, weld
shrinkage strains, bulk cold work, irradiation hardening,
precipitation hardening, oxide dispersion hardening, etc. but all
forms appear to produce a similar enhancement in growth rate.
The fundamental basis for the effect of yield strength has been
proposed by both Andresen [5,12-16] and Shoji [17], who argue
that the strain rate at the crack tip under constant stress intensity
factor (K) conditions results from the redistribution of the strain
field in front of the growing crack. This strain gradient is higher
in high yield strength materials because the plastic zone at a given
stress intensity factor is smaller.
The focus of this paper is the effect of water chemistry in the
deaerated regime ranging from pure water through to various
buffered chemistries, including B/Li concentrations relevant to
PWR operation. This will in part be presented in the context of
knowledge of oxidizing water chemistry, and will demonstrate
how ineffective buffering chemistries like B/Li and ammonia are
when oxidants are present.
Experimental Procedures
A variety of heats of commercial stainless steels, alloy 600, alloy
182 weld metal, alloy X750, alloy 22, and alloy 718 have been
evaluated. Some were cold worked by forging various reductions
in thickness, which produces relatively uniform deformation in
two dimensions, as confirmed by EBSD (electron back-scatter
diffraction) measurements of residual strain.
1T or 0.5T compact type (CT) specimens were machined with 5%
side grooves on each side. CT specimens were instrumented with
platinum current and potential probe leads for dc potential drop
crack length measurements of crack length. In this technique,
current flow through the sample is reversed about once per second
primarily to reduce measurement errors associated with
thermocouple effects and amplifier offsets. The computer control
of current reversal, data acquisition, data averaging techniques,
the relationship between measured potential and crack length, and
control of constant stress intensity factor have been presented
previously [18-21]. Data were stored in a permanent disk file
typically once every 1.5 hours. The system measured and stored
the data record number, total elapsed and incremental time, crack
length, temperature, current, corrosion potential, dissolved gases,
influent and effluent conductivity, load and time/date.
Additionally, both operator and automated program messages
describing changes in test conditions and test status were a
permanent part of the data record.
CT specimens were electrically insulated from the loading pins
using zirconia sleeves, and within the autoclave a zirconia washer
also isolated the upper pull rod from the internal load frame. The
lower pull rod was electrically isolated from the autoclave using
an Omniseal pressure seal and an insulating washer. Ground
isolated instrumentation was used for the platinum current and
potential probe attachments to the specimen.
Fatigue crack extension from the machined notch by 0.5 to 2.0
mm was performed typically at 1 Hz at a load ratio (K
min
/ K
max
) R
= 0.5, 0.6 and 0.7 and at a K
max
somewhat below the test value of
about 27.5 MPa\m. Subsequent precracking in the environment
to transition the crack morphology and plastic zone characteristics
was performed by decreasing frequency to 0.001 Hz, then by
introducing a hold time at K
max
(while maintaining R = 0.7), and
finally by switching to fully static load. Testing was performed
using servo-electric testing machines, or servo-hydraulic
machines equipped with a single stage, low flow servovalve to
ensure optimal (non-noisy) response. All systems were equipped
with digital controls that provide improved machine control and
full computer interface/control capabilities, including constant K
control, K rising/falling profiles, and multi-condition tables that
permit different K/R/frequency/hold time conditions to be
sequentially evaluated. Constant K control was employed in most
tests, with load corrections applied after very small increases in
stress intensity, typically <0.1%. To avoid hunting (increases
and decreases in load), any decreases in crack length (as indicated
by potential drop) never produced load corrections.
For tests in pure water, deaerated, demineralized water was drawn
through another demineralizer and submicron filter to ensure
ultra-high purity (0.055 S/cm) and then into a glass column (6.4-
cm diameter by 183 cm long). A low pressure pump provided
positive pressure to the high pressure pump, and drew water from
and recirculated excess water (water that did not go into the high
pressure pump) back into the glass column. The autoclave
effluent was back-pressure regulated, then measured for
conductivity and dissolved O
2
and H
2
. The dissolved gas
concentrations were controlled using mass flow controllers.
Impurities were added to the glass column using a metering pump
controlled by the conductivity meter.
Buffered chemistries were created by pre-conditioning
(equilibrating) a mixed bed demineralizer to the target chemistry.
The water loop then operated as usual in a closed-loop where the
autoclave effluent was continuously demineralized and re-
equilibrated for dissolved gases in the glass column. At elevated
H
2
fugacity (above about 5 cc/kg), the primary impurity released
is Fe
+2
. When absorbed by the demineralizer, it releases primarily
Li
+
, which has a much more pronounced effect on conductivity
than H
3
BO
3
(Figure 8). Thus, the chemistry could be accurately
monitored and adjusted using solution conductivity, a very
reliable measurement.
Tests were performed in 4 liter stainless steel autoclaves at
temperatures and pressures ranging from 288C and 10.3 MPa
(1500 psi) to 340 C and 20.6 MPa (3000 psi). Corrosion
potentials of the CT specimen and a Pt coupon were measured
using a zirconia membrane reference electrode [22], whose
reference potential varies with temperature and pH.
Results and Discussion
A wide variety of materials and conditions have been used to
evaluate the various effects of water chemistry on SCC growth
rates. Broadly speaking, while each material and condition has
some unique characteristics, their primary, mainstream SCC
growth rate response is similar. Figure 2 shows the response of an
unsensitized type 316L stainless steel cold worked by 20%.
While the growth rate is clearly influenced by corrosion potential,
this and many other grades of stainless steel [5,12-16] readily
exhibit crack growth in deaerated, very high purity water (in
Figure 2, the outlet conductivity during the low potential regime
reflects a maximum anionic impurity of < 1 ppb of, e.g., chloride
or sulfate). The same kind of continuum in SCC response is
observed vs. temperature (one of the significant distinctions
between BWRs and PWRs), as shown in Figure 3. In this
particular test, the specimen was exposed only to H
2
deaerated
water, although as Figure 2 suggests, there is generally no long
term effect of prior exposure to oxidizing or reducing conditions.
990
Figures 4 and 5 show that the same SCC growth rate response vs.
changes in water chemistry occurs for nickel-base alloys; similar
observations exist for alloys 82 and 182 weld metal [2,23,24],
alloy 22 [25], and aged alloys X750 and 718 [12,16,26], all of
which exhibit intergranular fracture morphology (e.g., Figure 6).
The similarity in response among these diverse materials vs.
corrosion potential is the result, in part, of a very similar
mechanism of the formation of crack chemistry. Figure 9
compares the passive current density of stainless steel and alloy
600 as a function of extended exposure in oxidizing, N
2
deaerated
or H
2
deaerated, 288 C solutions. After the several-week
exposure, the dissolved gas chemistry was quickly changed to N
2
deaeration, and the polarization response recorded in high purity
water using very sophisticated techniques [27,28]. Contrary to
common perception, the corrosion rate is about 5X higher at low
corrosion potential than at high corrosion potential. The response
is similar for stainless steels and nickel base alloys, and this
translates, e.g., to a similar corrosion potential vs. oxidant
concentration, and a similar consumption rate of oxidants as they
diffuse into the crack (since oxidants are consumed by metal
corrosion reactions). This yields a similar potential gradient and
therefore a similar crack chemistry.
The interplay between corrosion potential and water purity is
described conceptually in Figure 7. High purity water represents
a special case, because the crack chemistry is constrained to shift
alkaline because there are no foreign (non-OH

) anions to
charge balance the increased H
+
concentration, an inherent
characteristic of acidic solutions. The pH can shift somewhat
alkaline because the excess OH

is balanced by metal cations,

whose solubility increases with pH. When some anionic
impurities are present in high purity water, a gradient in potential
causes them to concentrate in the crack. One implication is that at
low corrosion potential, there is a greater tolerance for more
impurities in the bulk water. Figure 10 shows that there is no
measurable effect of adding 100 ppb sulfate as H
2
SO
4
(0.863
S/cm) until the corrosion potential is increased at about 6130
hours. But if sufficient H
2
SO
4
is added to deaerated water, the
growth rate increases dramatically (Figure 11). Thus, it is the
crack tip chemistry that controls SCC, not the corrosion potential
or bulk impurities per se. The addition of roughly neutral species,
like Na
2
SO
4
, does not have the same effect [8], indicating that at
least a moderate change in pH is needed to produce an effect on
crack growth.
The effect of other species is similarly small provided they alter
pH only to a limited extent. Figure 12 shows the response in tests
in deaerated 4N NaCl at 325 C. 4N NaCl is roughly neutral at
room temperature, but shifts to about pH 4.9 at 325 C. However,
the rate is very similar to that observed in slightly alkaline
chemistries associated with 600 ppm B as H
3
BO
3
and 2.2 ppm Li
as LiOH (Figures 13 and 14), which has a pH
325C
of 7.2. In this
context, it is unsurprising that there is little effect on crack growth
of much smaller pH shifts (e.g., 0.3 units) associated with the shift
from 4.3 to 2.2 ppm Li at 1335 hours.
Figure 15 shows the effect of changing from deaerated pure water
to deaerated 1000 ppm B as H
3
BO
3
and 1 ppm Li as LiOH. There
is a small perturbation in the crack growth rate of cold worked
stainless steel, but this is related to a problem with the high
pressure pump.
While the use of buffering solutions like B/Li and ammonia have
little effect on crack growth, they do not provide buffering (and
protection against accelerated SCC) when oxidants are present.
Figure 16 shows the dramatic increase in crack growth rate on
introducing 200 ppb O
2
to 288 C water containing 1200 ppm B
and 2.2 ppm Li; this observation is later reproduced (Figure 17).
Figure 17 also shows that in deaerated water (low corrosion
potential) the effect of shifting back to pure water, which is
minimal. Figure 18 shows a similar experiment using ammonia,
which has no measurable effect when introduced into deaerated
water at 2761 hours. However, when 200 ppb O
2
is added at 2851
hours, the growth rate dramatically increases and reverses
course when O
2
is removed at 2950 hours.
The limited effect of pH in deaerated water (where the crack tip
pH is not consequentially different than the bulk pH) is consistent
with the slip film rupture oxidation model. In this model there
is an obvious importance of metal oxidation, and in nickel-base
alloys this is greatly affected by traversing the Ni/NiO phase
boundary (Figure 19), since the primary alloy constituent does not
corrode when in the Ni-metal stable regime. The corrosion
potential of structural materials in deaerated water is usually
controlled by the H
2
/ H
2
O reaction (the dashed line marked (a)),
and its proximity to the Ni/NiO phase boundary is not affected by
pH, because both reactions exhibit the same dependency on pH.
At extremes of pH, there is an effect of the soluble species Ni
+
or
HNiO

, and this is expected (and observed) to increase SCC

growth rates. Similar conclusions were arrived at by Morton [29],
who observed that SCC growth rates on alloy X750 were
unchanged (within 10%) over the range of pH
360C
of 6.2 to 8.7
using water chemistries that varied from deaerated pure water
(pH
360C
= 6.2) to water containing LiOH or NaOH (Figure 20).
It is also important to put the role of corrosion potential in
context. A somewhat higher or somewhat lower corrosion
potential that results from changes in pH should never be
interpreted in the same way as shifts in potential that result from
oxidants. Whether the potential is approximately 0.88 V
she
(high
temperature pH of 8 with 30 cc/kg H
2
) or approximately 0.65
V
she
(high temperature pH = 6.5 with 3 cc/kg H
2
) or
approximately 0.52 V
she
(pure water with 1 cc/kg H
2
), there is no
potential gradient of consequence in the crack, and thus the crack
chemistry is not consequentially different than the bulk (metal ion
concentrations might vary by >>10X, but they would be at very
low concentrations and unlikely to affect SCC).
Apart from pH, there is also the prospect that SCC might be
affected by specific ion concentrations, such as lithium, boron,
ammonia, chloride, sulfate, etc. However, these do not appear to
have large effects on crack growth (and therefore are unlikely to
have a large effect on crack initiation). But despite the lack of
evidence of a pronounced effect of these species, more detailed
studies are merited. In this regard, it appears to be important to
differentiate the response of low alloy and carbon steel, where
there is an over-riding importance of MnS inclusions, and it is
possible that coolant additives affect the dissolution rate of MnS.
Chloride in particular, even at very low levels, has been shown to
have a sizeable effect on the behavior of low alloy steels [30].
A primary factor that can influence SCC in the broad near-neutral
pH regime is H
2
fugacity. H
2
readily permeates the crack,
producing roughly a constant H
2
fugacity inside and outside the
crack (as discussed in the Introduction). H
2
directly affects the H
2
/ H
2
O line, with increasing H
2
causing a shift downward (into Ni
metal stability) by 17.9 mV per 2X change in H
2
at 325 C.
Because the Ni/NiO boundary shifts with temperature, as does the
H
2
fugacity coefficient, the H
2
level required to transit the Ni/NiO
boundary is not fixed with temperature, and is not even linear as
991
the temperature is increased above about 340 C (Figure 21). The
lower curve in Figure 21 represents more modern measurements
to directly characterize the Ni/NiO phase boundary using contract
electrical resistance (CER) or direct observation of pure Ni foils
after exposure [31-33].
The effect of H
2
fugacity on SCC of nickel-base alloys has been
evaluated perhaps most thoroughly by Morton and colleagues
[29,31-34], who have demonstrated that the peak in SCC growth
rates occurs close to the Ni/NiO phase boundary. Thus, as H
2
is
increased from low values, the growth rate increases, then
decreases. The magnitude of the effect depends on the material,
with higher strength alloys like alloy 182 weld metal and alloy
X750 exhibiting a greater effect, as shown schematically in Figure
22. Figures 23 25 show examples of the crack length vs. time
when changes in H
2
fugacity are made. As H
2
fugacity is
increased, the dashed line marked a in Figure 19 shifts upwards,
and the Ni/NiO boundary can be crossed (Figure 21). When the
Ni/NiO phase boundary is crossed into Ni metal stability, the dc
potential drop technique typically shows a transient reduction in
(apparent) crack length (or at least retardation in growth rate)
associated with shorting by formation of metallic Ni in localized
areas in the wake of the crack [23,35-37]. While the magnitude of
the SCC growth rate effect can be large, achieving this benefit in
practice may depend on the H
2
fugacity that can be attained.
A final aspect is the effect of water chemistry on the observed
stress intensity factor dependency. At high corrosion potential
(high growth rates apparently produced by a crack tip chemistry
that is significantly shifted in pH), a dependency of about K
2
to
K
2.5
is observed (Figures 26 29), while at low corrosion
potential (lower growth rates associated with a broadly neutral pH
in the crack), a dependency of about K
3.0
is observed. These
observations have been made using one of two techniques
fatigue precracking at the K value of interest, followed by
transitioning to constant K and an intergranular crack
morphology; or using a sophisticated test control methodology
that decreases K in proportion to crack advance (dK/da). K is
controlled primarily by crack length, either directly (K o\a) or
indirectly by the residual stress profile that changes through-wall.
Thus, laboratory studies must mimic the changes in K during
testing abrupt changes in K, or change made at a constant rate
vs. time (dK/dt) will tend to produce crack arrest when more
representative techniques would not, which yields non-
conservative data.
Apart from such unrepresentative test techniques, different K
dependencies can be observed. One reason is due to extensive
crack branching, which often occurs as at higher Ks. Multiple
crack branching (bifurcation) produces a decrease in the actual K
at each crack tip, so this does not represent a mechanistic
disconnect, but rather an additional factor that must be accounted
for when calculating the K of a given component or crack.
Alternatively, when the linear elastic fracture mechanics criteria
are violated, there is excessive plasticity and growth rates
increase. This is particularly evident in cold worked and
irradiated materials that have a low (or zero) strain hardening
coefficient [12,13,16]. A purely anomalous reason for very
shallow K dependency can occur when large data sets are
agglomerated for analysis. Unless tests are performed with the
best techniques and experimental controls, and ideally using the
same material and even a single specimen, there is a lot of
variability in the measured growth rates. While grouping such
data is a great way to build confidence in a general disposition or
bounding growth rate, it dilutes the actual dependencies, often
severely. The effect of corrosion potential is the single most
widely studied and pronounced effect, but a statistical evaluation
of over a hundred data after screening of data obtained only
from good laboratories revealed no statistically relevant effect
(Figure 30), the trend is dramatically different than the accepted
response (e.g., Figure 1). This is also true of stress intensity
factor, sensitization, water purity, alloy chemistry /
microstructure, temperature, etc.
Conclusions
The effect of water chemistry encompassing changes in
corrosion potential that are large (from O
2
) or smaller (from H
2
),
impurities (like chloride and sulfate), and buffering additives (like
B/Li and ammonia) is used to demonstrate that SCC growth
rates follow a well-behaved continuum in response across a wide
range of temperatures, structural materials, and environments. In
PWR environments, small changes in pH from anticipated
changes in chemistry have no measurable affect on crack growth
rate. Even changes from deaerated pure water to deaerated B/Li
environments have limited, if any, effect. However, the
introduction of O
2
overwhelms any buffering effect of B/Li or
ammonia, giving rise to rapid growth rates. The continuum
response and mechanistic insight provide a invaluable basis for
anticipating and interpreting the effects of specific variables.
References
1. Proc. 1
st
11
th
Int. Symp. on Environmental Degradation of
Materials in Nuclear Power Systems Water Reactors,
NACE / ANS / TMS, 1983 2001.
2. F.P. Ford and P.L. Andresen, Corrosion in Nuclear
Systems: Environmentally Assisted Cracking in Light Water
Reactors, in Corrosion Mechanisms, Ed. P. Marcus and J.
Ouder, Marcel Dekker, p.501546, 1994.
3. P.L. Andresen and F.P. Ford, Life Prediction by
Mechanistic Modelling and System Monitoring of
Environmental Cracking of Fe and Ni Alloys in Aqueous
Systems, Materials Science and Engineering, A103,
pp.167183, 1988.
4. F.P. Ford, D.F. Taylor, P.L. Andresen and R.G. Ballinger,
Corrosion Assisted Cracking of Stainless and Low Alloy
Steels in LWR Environments, EPRI Contract RP2006-6,
Report NP5064M, 1987.
5. P.L. Andresen, Perspective and Direction of Stress
Corrosion Cracking in Hot Water, Proc. Tenth Int. Symp.
on Env. Degradation of Materials in Nuclear Power Systems
- Water Reactors, NACE, 2001.
6. P.L. Andresen, Conceptual Similarities and Common
Predictive Approaches for SCC in High Temperature Water
Systems, Paper 96258, Corrosion/96, NACE, 1996.
7. P.L. Andresen, F.P. Ford, S.M. Murphy, J.M. Perks, State
of Knowledge of Radiation Effects on Environmental
Cracking in Light Water Reactor Core Materials, Proc. 4
th
Int. Symp. on Environmental Degradation of Materials in
Nuclear Power Systems Water Reactors, NACE, pp. 183
to 1121, 1990.
8. P.L. Andresen and L.M. Young, Characterization of the
Roles of Electrochemistry, Convection and Crack Chemistry
in Stress Corrosion Cracking, Proc. 7
th
Int. Symp. on
Environmental Degradation of Materials in Nuclear Power
Systems Water Reactors, NACE, p.579596, 1995.
9. P.L. Andresen and F.P. Ford, Response to On the Modeling
of Stress Corrosion Cracking of Iron and Nickel Base Alloys
992
in High Temperature Aqueous Environments , Corrosion
Science Vol 38, p.10111016, 1996.
22. L.W. Niedrach, A New Membrane Type pH Sensor for Use
in High Temperature High Pressure Water, J. Electrochem.
Soc. 127, p. 2122, 1980. 10. Y.J. Kim, L.W. Niedrach, M.E. Indig and P.L. Andresen,
Applications of Noble Metals in Coatings and Alloys for
Light Water Reactors, J. of Metals , Vol. 44, No. 2, p. 14-
18, April 1992. See also, P.L. Andresen, Application of
Noble Metal Technology for Mitigation of Stress Corrosion
Cracking in BWRs, Proc. 7
th
Int. Symp. on Env.
Degradation of Materials in Nuclear Power Systems Water
Reactors, NACE, p.563-578, 1995.
23. P.L. Andresen, L.M. Young, P.W. Emigh and R.M. Horn,
Stress Corrosion Crack Growth Rate Behavior of Ni Alloys
182 and 600 in High Temperature Water, Corrosion/02,
Paper 02510, NACE, 2002.
24. P.L. Andresen, Fracture Mechanics Data and Modeling of
Environmental Cracking of Nickel-Base Alloys in High
Temperature Water, Corrosion 47, Dec.1991, p. 917-938.
11. S. Hettiarachchi, G.P. Wozadlo, T.P. Diaz, P.L. Andresen
and R.L Cowan, The Concept of Noble Metal Addition
Technology for IGSCC Mitigation of Nuclear Materials,
Proc. 7
th
Int. Symp. on Environmental Degradation of
Materials in Nuclear Power Systems Water Reactors,
NACE, p.735-746, 1995.
25. P.L. Andresen, unpublished data, GE Global Research,
Schenectady, NY, 2003.
26. P.L. Andresen, P.W. Emigh, M.M. Morra, SCC of High
Strength Ni-base Alloys in High Temperature Water, Paper
#04675, Corrosion/04, NACE, 2004.
27. Y.J. Kim and P.L. Andresen, Data Quality, Issues and
Guidelines for ECP Measurements in High Temperature
Water, Corrosion/2001, Paper 01137, NACE, 2001.
12. P.L. Andresen, P.W. Emigh, M.M. Morra and R.M. Horn,
Effects of Yield Strength, Corrosion Potential, Stress
Intensity Factor, Silicon and Grain Boundary Character on
the SCC of Stainless Steels, Proc. of 11th Int. Symp. on
Environmental Degradation of Materials in Nuclear Power
Systems - Water Reactors, ANS, 2003.
28. Y.J. Kim, Effect of Variation in BWR Water Chemistry on
Type 304 SS ECP, Corrosion Vol. 58, p. 208-215, March
2002.
29. D.S. Morton and M. Hansen, The Effect of pH on Nickel
Alloy SCC and Corrosion Performance, Paper 03675,
Corrosion/03, NACE, 2003.
13. P.L. Andresen, T.M. Angeliu, L.M. Young, W.R. Catlin, and
R.M. Horn, Mechanisms and Kinetics of SCC in Stainless
Steels, Proc. Tenth Int. Symp. on Environmental
Degradation of Materials in Nuclear Power Systems Water
Reactors, NACE, 2001.
30. H-P. Seifert, Environmentally Assisted Cracking of Low-
Alloy RPV and Piping Steels under LWR Conditions, Proc.
11
th
Int. Symp on Environmental Degradation of Materials in
Nuclear Power Systems Water Reactors, ANS, 2003. 14. P.L. Andresen, T.M. Angeliu, W.R. Catlin, L.M. Young and
R.M. Horn, Effect of Deformation on SCC of Unsensitized
Stainless Steel, Corrosion/2000, Paper 00203, NACE, 2000.
31. S.A. Attanasio and D.S. Morton, Measurement of the
Ni/NiO Transition in Ni-Cr-Fe Alloys and Updated Data and
Correlation to Quantify the Effect of Aqueous Hydrogen on
Primary Water SCC, Proc. 11th Int. Symp. on
Environmental Degradation of Materials in Nuclear Power
Systems Water Reactors, ANS, 2003.
15. P.L. Andresen, T.M. Angeliu and L.M. Young, Effect of
Martensite and Hydrogen on SCC of Stainless Steels, Paper
#01228, Corrosion/01, NACE, 2001.
16. P.L. Andresen, Similarity of Cold Work and Radiation
Hardening in Enhancing Yield Strength and SCC Growth of
Stainless Steel in Hot Water, Corrosion/02, Paper 02509,
NACE, 2002.
32. S.A. Attanasio, D.S. Morton, M.A. Ando, N.F. Panayotou
and C.D. Thompson, Measurement of the Ni / NiO Phase
Transition in High Temperature Hydrogenated Water Using
the Contact Electrical Resistance (CER) Technique, Proc.
10th Int. Symp. on Environmental Degradation of Materials
in Nuclear Power Systems Water Reactors, NACE, 2001.
17. T. Shoji, Progress in the Mechanistic Understanding of
BWR SCC and Its Implications to the Prediction of SCC
Growth Behavior in Plants, Proc. 11
th
Int. Symp. on
Environmental Degradation of Materials in Nuclear Power
Systems Water Reactors, ANS, 2003.
33. D.S. Morton, S.A. Attanasio and G.A. Young, Primary
Water SCC Understanding and Characterization Through
Fundamental Understanding in the Vicinity of the Ni / NiO
Phase Transition, Proc. 10th Int. Symp. on Environmental
Degradation of Materials in Nuclear Power Systems Water
Reactors, NACE, 2001.
18. P.L. Andresen and C.L. Briant, Environmentally Assisted
Cracking of Types 304L/316L/316NG Stainless Steel in 288
C Water, Corrosion, Vol. 45, pp. 448463, 1989.
19. P.L. Andresen and C.L. Briant, Role of S, P and N
Segregation on Intergranular Environmental Cracking of
Stainless Steels in High Temperature Water, Proc. 3rd Int.
Symp. on Environmental Degradation of Materials in
Nuclear Power Systems Water Reactors, AIME, pp. 371
382, 1988.
34. S. Attanasio, J. Mullen, J. Wuthrich, W. Wilkening, D.
Morton, SCC Growth Rates of Alloy 182 and 82 Welds,
NRC Conference on PWR Vessel Penetration Inspection,
Cracking and Repair, Gaithersburg, MD, September 2003.
35. T.M. Angeliu, P.L. Andresen, and M.L. Pollick,
Repassivation and Crack Propagation of Alloy 600 in 288C
Water, Corrosion 53, p.114, 1997.
20. P.L. Andresen, Environmentally Assisted Growth Rate
Response of Nonsensitized AISI 316 Grade Stainless Steels
in High Temperature Water, Corrosion 44, 7, p. 450, 1988. 36. D.S. Morton, S.A. Attanasio, J.S. Fish, and M.K. Schurman,
Influence of Dissolved Hydrogen on Nickel Alloy SCC in
High Temperature Water, Corrosion/99, Paper 99447,
NACE, 1999.
21. P.L. Andresen, The Effects of Aqueous Impurities on
Intergranular Stress Corrosion Cracking of Sensitized Type
304 Stainless Steel, Final Report NP3384 Contract T115-3,
EPRI, 1983. See also, Innovations in Experimental
Techniques for Testing in High Temperature Aqueous
Environments, Report No. 81CRD088, GE CRD,
Schenectady, New York, 1981.
37. C.D. Thompson, D.M. Carey, and N.L. Perazzo, Effects of
Hydrogen on Electropotential Monitoring of Stress Corrosion
Crack Growth, Eighth Int. Symp. on Environmental
Degradation of Materials in Nuclear Power Systems Water
Reactors, ANS, p. 366, 1997.
993
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4
Corrosion Potential, Vshe
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
Sensitized 304 Stainless Steel
30 MPa\m, 288C Water
0.06-0.4 S/cm, 0-25 ppb SO
4
filled triangle = constant load
open squares = "gentle" cyclic
Screened Round Robin data
- highest quality data
- corrected corr. potential
- growth rates corrected
to 30 MPa\m 42.5
28.3
14.2
in/h
GE PLEDGE
Predictions
30 MPa\m 0.5
0.25
0.1
0.06 S/cm
0.06 S/cm
Industry Mean
30 MPa\m

2
0
0


p
p
b

O
2

5
0
0


p
p
b

O
2

2
0
0
0

p
p
b

O
2
2000 ppb O2
Ann. 304SS
200 ppb O2
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4
Corrosion Potential, Vshe
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
Sensitized 304 Stainless Steel
30 MPa\m, 288C Water
0.06-0.4 S/cm, 0-25 ppb SO
4
SKI Round Robin Data
filled triangle = constant load
open squares = "gentle" cyclic
42.5
28.3
14.2
in/h
GE PLEDGE
Predictions
30 MPa\m 0.5
Sens SS
0.25
0.1
0.06 S/cm

2
0
0


p
p
b

O
2

5
0
0


p
p
b

O
2

2
0
0
0

p
p
b

O
2
2000 ppb O2
Ann. 304SS
200 ppb O2
316L (A14128, square)
304L (Grand Gulf, circle )
non-sensitized SS
50%RA 140 C (black )
10%RA 140C (grey)
CWA600
CW A600
GE PLEDGE Predictions for Unsensitized
Stainless Steel (upper curve for 20% CW)
(a) (b) (c)
Figure 1. SCC growth rate vs. corrosion potential for stainless steels tested in 288 C high purity water containing 2000 ppb O
2
and 95
3000 ppb H
2
.
12.15
12.25
12.35
12.45
12.55
12.65
12.75
1000 1200 1400 1600 1800 2000 2200 2400
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
CT Potential
316L SS 20% Cold Work
25 ksi\in, 2000 ppb O
2
, Pure Water
Outlet Conductivity
1.9 x 10
-8
mm/s
T
o

s
t
a
t
i
c

l
o
a
d

@
3
6
7
h
T
o

6
%

H
2

i
n

A
r

@
1
2
4
5
h
2.7 x 10
-7
mm/s
1.8 x 10
-7
mm/s
T
o

2
0
0
0

p
p
b

O
2

@
2
1
0
8
h
Figure 2. SCC response in 288 C water for a 0.5TCT of unsensitized Type 316L SS with 20% CW at 55 C.
994
11.25
11.3
11.35
11.4
11.45
11.5
11.55
11.6
11.65
11.7
11.75
0 200 400 600 800 1000 1200 1400 1600 1800
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
CT Potential
316L SS 20% Cool Work
25 ksi\in, 1.58 ppm H
2
, 320C Pure Water
Outlet Conductivity
1.6 x 10
-7
mm/s
T
o

R
=
0
.
7
,

0
.
0
0
1

H
z

@

6
3
h
T
o

R
=
0
.
7
,

0
.
0
0
1

H
z
+
9
0
0
0
s

h
o
l
d

@
1
8
5
h
Elevated conductivity
from soluble iron
Pt Potential
5 x 10
-8
mm/s
T
o

s
t
a
t
i
c

l
o
a
d

@

5
2
1
h
4.5 x 10
-8
mm/s
T
o

3
4
0
C

@

8
3
2
h
7.6 x 10
-8
mm/s
9.0 x 10
-8
mm/s
Figure 3. SCC reponse in 288 C water for a 0.5TCT of unsensitized Type 316L SS with 20% CW at 140 C.
SCC#5 of c129 - Annealed + 20%CW Alloy 600, heat 67167
23.5
23.55
23.6
23.65
23.7
23.75
4700 4800 4900 5000 5100 5200 5300
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

u
S
/
c
m
c129 - 1T CT of Annealed + 20%CW Alloy 600
30 MPa\m, 2000 ppb O
2
, Pure Water
Outlet Conductivity
CT Potential
2.1 x 10
-7
mm/s
T
o

c
o
n
s
t

3
1
.
1

M
P
a
\
m
@

3
4
4
9
h
3.2 x 10
-8
mm/s
Pt Potential
T
o

2
0
0

p
p
b

O
2
@

4
1
7
4

h
T
o

9
5

p
p
b

H
2
@

4
8
1
6

h
T
o

2
0
0
0

p
p
b

O
2
@

5
1
0
7

h
2.0 x 10
-7
mm/s
Figure 4. Crack length vs. time for solution annealed alloy 600 cold worked by 20% CW by forging.
SCC#3a - c227 - Annealed Alloy X750 + 20% CW, 50FOX
11.8
11.9
12
12.1
12.2
12.3
12.4
12.5
12.6
1300 1400 1500 1600 1700 1800
Test Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m

o
r

P
o
t
e
n
t
i
a
l
,

V
s
h
e
Outlet conductivity
CT potential
Pt potential
1 x 10
-6
mm/s
c227 - 0.5TCT of X750 20%CW
25 ksi\in, 2 ppm O
2
, 30 ppb SO
4
T
o

0
.
2
6
7

u
S
/
c
m

H
2
S
O
4

@

1
1
0
8
h
T
o

C
o
n
s
t
a
n
t

K

@

1
3
4
1
h
1 x 10
-7
mm/s
T
o

6
%

H
2

@

1
4
3
7
h
T
o

2

p
p
m

O
2
2
0

p
p
b

S
O
4

@

1
7
4
9
h
1 x 10
-6
mm/s
Figure 5. Crack length vs. time for solution annealed alloy X750 cold worked by 20% CW by forging.
995
Figure 6. Intergranular SCC fracture morphology in annealed (or as-deposited) (a) Type 304L SS + 20% cold work at 55 C, (b)
annealed alloy 600 + 20% cold work, and (c) alloy 182 weld metal.
Figure 7. Schematic of the crack tip when oxidants (like O
2
) are present. Oxidants affect the corrosion potential of the free surface, but as
they diffuse into the tight crack they are consumed by corrosion and reaction with H
2
. This produces a potential gradient, which
concentrates anions in the crack and shifts the pH.
996
0
5
10
15
20
25
30
35
40
45
50
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Li, ppm
C
o
n
d
u
c
t
i
v
i
t
y

a
t

2
5
C
,

u
S
/
c
m
100 ppm B as H
3
BO
3
1000 ppmB as H
3
BO
3
Figure 8. Effect of Li as LiOH on solution conductivity at 25 C in 100 and 1000 ppm B as H
3
BO
3
showing that conductivity (and pH) is
controlled primarily by the Li concentration.
-600
-400
-200
0
200
400
600
800
1000
0.01 0.1 1 10 100 1000
CURRENT DENSITY, A/cm
2
E
L
E
C
T
R
O
D
E

P
O
T
E
N
T
I
A
L
,

m
V
(
S
H
E
)
304 SS polarization measurement was done in
deaerated, high purity water (< 2 ppb O
2
) at 288
o
C and
150 cc/min
After preoxidation
in deaerated water
for 3 weeks
After preoxidation
in 150 ppb H
2
for 3 weeks
After preoxidation
in 1 ppm H
2
O
2
for 3 weeks
After preoxidation
in 200 ppb O
2
for 3 weeks
-600
-400
-200
0
200
400
600
800
1000
0.01 0.1 1 10 100 1000
CURRENT DENSITY, A/ cm
2
E
L
E
C
T
R
O
D
E

P
O
T
E
N
T
I
A
L
,

m
V
(
S
H
E
)
Aft er
pr eoxidat ion
in 200ppb O
2
for 3 weeks After preoxidation
in 150ppb H
2
for 3 weeks
Aft er
pr eoxidat ion
in deaer at ed
t
Alloy 600 polarization measurement was done in
deaerated, high purity water (< 2 ppb O
2
) at 288
o
C and
150 cc/min
Figure 9. Polarization curves for type 304 stainless steel and alloy 600 obtained in N
2
deaerated, 288C water after several weeks exposure
to the water chemistries shown in the graph.
Figure 10. Crack length vs. time for sensitized type 304 stainless tested in 288 C water. At low corrosion potential, the addition of 100
ppb sulfate (0.863 S/cm H
2
SO
4
) has no effect, but once the potential is increased at about 6120 hours, a very marked effect on crack
growth is observed.
997
Figure 11. The effect of H
2
SO
4
additions to deaerated water on SCC growth rate in SSRT of sensitized type 304 stainless steel. Despite
the low corrosion potential, sufficient H
2
SO
4
can produce a dramatic increase in growth rate.
SCC#1a - c113 - Alloy 600, NX8844
22.82
22.84
22.86
22.88
22.9
22.92
22.94
22.96
22.98
23
400 500 600 700 800 900 1000 1100
Time, hours
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
1.2 x 10
-7
mm/s
6.0 x 10
-8
mm/s
c113, Alloy 600, NX8844, 325C
25 ksi
\
in, 3M NaCl, pH325C = 4.9
CT vs. CuO
Raw potentials -- Conversions are:
Cu/Cu2O @ pH 4.9 = -245 mVshe
@ pH 7.0 = -495 mVshe
@ pH 8.0 = -614 mVshe
Ext. 3N Ag/AgCl ~ -226 mVshe
Figure 12. SCC growth rate of alloy 600 under constant K conditions in 325 C, 3M NaCl.
SCC#1c - c261 - Alloy 600, CRDM Tube, 93510
11.08
11.1
11.12
11.14
11.16
11.18
11.2
1000 1100 1200 1300 1400 1500 1600 1700
Test Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m

o
r

P
o
t
e
n
t
i
a
l
,

V
s
h
e
CT potential Pt potential
c261 - 0.5TCT of A600 CRDM, 325C
27.5 MPa\m, 20 cc/kg H
2
, 600 B / 2.2 Li
4 x 10
-8
mm/s
T
o

C
o
n
s
t
a
n
t

K

@

1
0
4
0
h
D
e
m
i
n

c
a
u
s
e
s

s
l
o
w
|

i
n

L
i
!

L
i
,
!

p
H

b
y

~
0
.
3

@

1
3
3
5
h
Outlet conductivity 100
Figure 13. Crack length vs. time for alloy 600 and tested in 325 C water containing 20 cc/kg (1785 ppb) H
2
under constant K conditions.
The change from 600 ppm B and 4.3 ppm Li to 600 ppm B and 2.2 ppm Li at 1335 hours produces a change in conductivity and pH (from
pH
325C
of 7.5 to 7.2), but no change in crack growth rate.
998
SCC#1c - c262 - Alloy 600, CRDM Tube, 93510
11.11
11.13
11.15
11.17
11.19
11.21
11.23
11.25
1000 1100 1200 1300 1400 1500 1600 1700
Test Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m

o
r

P
o
t
e
n
t
i
a
l
,

V
s
h
e
CT potential Pt potential
c262 - 0.5TCT of A600 CRDM, 325C
27.5 MPa\m, 20 cc/kg H
2
, 600 B / 2.2 Li
5.3 x 10
-8
mm/s
T
o

C
o
n
s
t
a
n
t

K

@

1
0
4
0
h
Outlet conductivity 100
D
e
m
i
n

c
a
u
s
e
s

s
l
o
w
|

i
n

L
i
!

L
i
,
!

p
H

b
y

~
0
.
3

@

1
3
3
5
h
Figure 14. Crack length vs. time for alloy 600 and tested in 325 C water containing 20 cc/kg (1785 ppb) H
2
under constant K conditions.
The change from 600 ppm B and 4.3 ppm Li to 600 ppm B and 2.2 ppm Li at 1335 hours produces a change in conductivity and in pH
(from pH3
25C
of 7.5 to 7.2), but no change in crack growth rate.
c163 SCC #6a - 750MPa Cool Work 304L SS, TSh
12.83
12.85
12.87
12.89
12.91
12.93
12.95
12.97
3500 3700 3900 4100 4300 4500 4700
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
P
o
t
e
n
t
i
a
l
,

V
s
h
e


o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
Pt Potential
Outlet Conductivity
CT Potential
c163 - 750MPa Cool Work 304L
27.5 MPa\m, Pure Water
T
o

3
1
6
0

p
p
b

H
2
@

7
4
8
h
T
o

3
4
0
C
@

2
2
5
5
h
R
e
p
l
a
c
e
d

h
i
g
h

P
p
u
m
p

@

4
2
3
9
h
T
o

R
=
0
.
7
,

0
.
0
0
1

H
z

+
8
5
,
4
0
0
s

a
t

K
m
a
x

@

3
3
7
8
h
T
o

1
0
0
0

p
p
m

B
1

p
p
m

L
i

@

4
1
6
7
h
3 x 10
-8
mm/s
Figure 15. Crack length vs. time for type 304L stainless steel cold worked to 750 MPa yield strength and tested in 288 C water. The
change from H
2
deaerated water (17.7 cc/kg, or 1580 ppb H
2
) to 1000 ppm B and 1 ppm Li at 4167 hours produces a massive change in
conductivity, and moderate change in pH (from pH
288C
of 5.6 to 6.7).
999
27.5
27.6
27.7
27.8
27.9
28
28.1
28.2
28.3
2200 2250 2300 2350 2400 2450
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1

P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
CT Corrosion Potential
c85 - 1TCTof Sens. SS - AJ9139
95 ppbH
2
, 1200 ppm B, 2.2 ppm Li, 288C
30/21 ks\in,
0.01 Hz + 900 s hold
3.5 x 10
-6
mm/s
2.5 x 10
-8
mm/s
T
o

2
0
0

p
p
b

O
2

@
2
2
7
9
h
T
o

9
5

p
p
b

H
2

@
2
3
5
4
h
6 x 10
-8
mm/s
pH
288C
~ 6.79
Figure 16. SCC crack length vs. time of sensitized stainless steel in 288 C showing that the presence of 1200 ppm B as H
3
BO
3
and 2.2
ppm Li as LiOH results in a low growth rate until the corrosion potential becomes elevated at 2279 hours by the addition of 200 ppb O
2
.
28.15
28.25
28.35
28.45
28.55
28.65
28.75
2400 2450 2500 2550 2600 2650 2700 2750 2800
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1

P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
CT Corrosion Potential
c85 - 1T CT of Sens. SS- AJ9139
95 ppb H
2
, 1200 ppmB, 2.2 ppm Li, 288C
30/21 ks\in,
0.01 Hz + 900 s hold
2.3 x 10
-6
mm/s
6 x 10
-8
mm/s
T
o

2
0
0

p
p
b

O
2

@
2
4
2
6
h
T
o

9
5

p
p
b

H
2

@
2
5
1
8
h
2 x 10
-8
mm/s
T
o

p
u
r
e

w
a
t
e
r
,

p
o
t
e
n
t
i
a
l

s
h
i
f
t
f
r
o
m

c
h
a
n
g
e

i
n

p
H

@
2
6
3
8
h
pH
288C
~ 6.79
Figure 17. SCC crack length vs. time of sensitized stainless steel in 288 C showing that the presence of 1200 ppm B as H
3
BO
3
and 2.2
ppm Li as LiOH results in a low growth rate until the corrosion potential becomes elevated at 2279 hours by the addition of 200 ppb O
2
. A
return to low corrosion potential at 2518 hours slows the growth rate, which is then not significantly affected by the switch to pure water at
2638 hours.
1000
SCC#3 of c85 - SensitizedStainless Steel
28.6
28.65
28.7
28.75
28.8
28.85
2600 2700 2800 2900 3000 3100 3200
Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
0.01
0.1
1
10
100

P
o
t
e
n
t
i
a
l
,

V
s
h
e

o
r

C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m
Outlet Conductivity
c85 - 1T CT of Sensitized Stainless Steel
Heat AJ9139 - 95 ppb H
2
Pure Water, 288C
K =30/21 ksi\in, 0.01 Hz +900 s hold at K
max
T
o

4
2

u
S
/
c
m

N
H
4
O
H
(
2
6
.
8

p
p
m

N
H
3
)

@
2
7
6
1
h
6.1 x 10
-7
mm/s
1.5 x 10
-8
mm/s
5 x 10
-9
mm/s
T
o

2
0
0

p
p
b

O
2

@
2
8
5
1
h
T
o

9
5

p
p
b

H
2

@
2
9
5
0
h
pH
288C
~ 6.61
Figure 18. SCC crack length vs. time of sensitized stainless steel in 288 C showing that the addition of 26.8 ppm NH
3
to deaerated water
has little effect on growth rate. However, the change to high corrosion potential at 2851 hours had a large effect.
Figure 19. Ni H
2
O Pourbaix diagram at 300 C.
1001
Figure 20. Effect of pH
360C
on the crack growth rate of alloy X750 (determined by destructive exam, DE, and electric potential drop, EPD,
in iso-condition tests) in 360 C water. Over the pH range of 6.2 to 8.8 the crack growth rate is essentially constant.
Effects of H
2
and Temperature on Ni/NiOPhase Boundary
1
10
100
200 220 240 260 280 300 320 340
Temperature, C
H
2

F
u
g
a
c
i
t
y

a
t

T
e
m
p
e
r
a
t
u
r
e
,

c
c
/
k
g
392 428 464 500 536 572 608 644
N
i

C
o
r
r
.

P
o
t
e
n
t
i
a
l
,

V
s
h
e
Ni
NiO
Ni
Lower curve represents boundary
defined by KAPL measurements
by CER and using Ni coupons
NiO
Temp, F
-789
-675
-732
Corrosion potential is linear with
the logarithm of the H
2
fugacity.
Shown for pH
T
~ 7.0 & 300C
Figure 21. Ni/NiO phase boundary as a function of H
2
fugacity and temperature. Corrosion potential is shown on the right Y-axis for the
conditions shown in the graph.
1002
0
1
2
3
-900 -850 -800 -750 -700
Corrosion Potential, mV
she
A
r
b
i
t
r
a
r
y

G
r
o
w
t
h

R
a
t
e
0.1 1.0 10.0 100.0 1000.0
H
2
Fugacity, cc/kg
75 mV Full Width
Half Max
Change in CGR:
20 > 40: 1.22X
40 > 80: 1.37X
20 > 80: 1.67X
20 >200: 2.38X
Change in Growth Rate
at Peak of ~13 cc/kg H
2
= 3X
For 325C where dependence is
118.7 mV per 10X change in H
2
Note that specific
corrosion potentials
depend on pH at 325C
Ni NiO
Phase Stability
0
1
2
3
4
5
6
7
8
9
-900 -850 -800 -750 -700
Corrosion Potential, mV
she
A
r
b
i
t
r
a
r
y

G
r
o
w
t
h

R
a
t
e
0.1 1.0 10.0 100.0 1000.0
H
2
Fugacity, cc/kg
75 mV Full Width
Half Max
Change in CGR:
20 > 40: 1.32X
40 > 80: 1.62X
20 > 80: 2.13X
20 >200: 4.35X
Change in Growth Rate
at Peak of ~13 cc/kg H
2
= 8X
For 325C where dependence is
118.7 mV per 10X change in H
2
Note that specific
corrosion potentials
depend on pH at 325C
Ni NiO
Phase Stability
Figure 22. Effect of H
2
fugacity (also shown as corrosion potential on the bottom X-axis) on the crack growth rate of nickel-base alloys in
high temperature water. The location of the peak depends on temperature, as shown in Figure 21. The width of the peak appears to
relatively constant, but the magnitude of the peak varies from about 2.5 3X for alloy 600 (top figure) to 7 10X for alloy 182 weld metal
or alloy X750 (bottom figure).
SCC#1c - c113 - Alloy 600, NX8844
23.25
23.3
23.35
23.4
23.45
23.5
23.55
23.6
23.65
1400 1800 2200 2600 3000 3400 3800
Time, hours
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
7.5 x 10
-8
mm/s
5.0 x 10
-8
mm/s
2.6 x 10
-8
mm/s
c113, Alloy 600, NX8844, 325C
25 ksi
\
in, 3M NaCl, pH325C = 4.9
CT vs. CuO
Raw potentials -- Conversions are:
Cu/Cu2O @ pH 4.9 = -245 mVshe
@ pH 7.0 = -495 mVshe
@ pH 8.0 = -614 mVshe
Ext. 3N Ag/AgCl ~ -226 mVshe
Figure 23. SCC growth rate of alloy 600 under constant K conditions in 325 C, 3M NaCl at various H
2
levels.
1003
SCC#3b - c260 - Alloy 600, CRDM Tube, 93510
11.12
11.17
11.22
11.27
11.32
11.37
11.42
1000 1200 1400 1600 1800 2000 2200
Test Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.92
-0.91
-0.9
-0.89
-0.88
-0.87
-0.86
C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m

o
r

P
o
t
e
n
t
i
a
l
,

V
s
h
e
CT potential Pt potential
c260 - 0.5TCT of A600 CRDM, 340C
25 ksi\in, 18 cc/kg H
2
, 550 B / 1 Li
9.0 x 10
-8
mm/s
T
o

C
o
n
s
t
a
n
t
K
@

1
0
3
5
h
3 x 10
-8
mm/s
At 340C, pH = 7.56. At 300C, pH = 6.89
and potential would be ~154 mV higher
T
o

4
0

c
c
/
k
g

H
2
G
e
t

t
h
e
r
m
o
d
y
n
a
m
i
c
s
h
i
f
t

i
n

E
C
P

@

1
6
7
9
h
T
o

8
0

c
c
/
k
g

H
2
G
e
t

t
h
e
r
m
o
d
y
n
a
m
i
c
s
h
i
f
t

i
n

E
C
P

@

2
1
6
0
h
6 x 10
-8
mm/s
2.4 x 10
-8
mm/s
Thermodynamic
change in potential for
2X change in H
2
is 18.3 mV
Figure 24. SCC growth rate of alloy 600 under constant K conditions in 325 C, 3M NaCl at various H
2
levels.
SCC#3d - c262 - Alloy 600
11.1
11.15
11.2
11.25
11.3
11.35
11.4
11.45
1000 1500 2000 2500 3000 3500
Test Time, hours
C
r
a
c
k

l
e
n
g
t
h
,

m
m
-0.9
-0.89
-0.88
-0.87
-0.86
-0.85
-0.84
-0.83
-0.82
C
o
n
d
u
c
t
i
v
i
t
y
,

S
/
c
m

o
r

P
o
t
e
n
t
i
a
l
,

V
s
h
e
CT potential
Pt potential
c262 - 0.5TCT of A600, 325C
25 ksi\in, 20 cc/kg H
2
, 600 B / 2.2 Li
5.3 x 10
-8
mm/s
T
o

C
o
n
s
t
a
n
t
K

@

1
0
4
0
h
T
o

4
0

c
c
/
k
g
H
2

@

1
8
5
7
h
4 x 10
-8
mm/s
T
o

8
0

c
c
/
k
g
H
2

@

2
6
9
7
h
3.4 x 10
-8
mm/s
Figure 25. SCC growth rate of alloy 600 under constant K conditions in 325 C water containing 600 ppm B as H
3
BO
3
and 2.2 ppm Li as
LiOH at various H
2
levels.
1.E-08
1.E-07
1.E-06
0 5 10 15 20 25 30
Stress Intensity, ksi\in
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
SCC of 20% Cool Worked Stainless Steel
288 C, 2000 ppb O
2
, Pure Water
CGR K
2.3
Figure 26. Stress intensity factor, K, dependency for IGSCC of cold worked stainless steel in 288 C water with 2000 ppb O
2
.
1004
1.E-08
1.E-07
1.E-06
8 10 12 14 16 18 20 22 24
Stress Intensity Factor, ksi\in
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
K
2
Dependency
K
2.5
Dependency
Effect of Stress Intensity Factor (K) on
Crack Growth Rate of 20% Cold Worked
316L SS Tested in 288 C Water Using
A Very Slow Reduction in K Under
"Constant K" Conditions (No Cycling)
26
Figure 27. Stress intensity factor, K, dependency for IGSCC of cold worked stainless steel in 288 C water with 2000 ppb O
2
.
1.E-08
1.E-07
1.E-06
14 16 18 20 22 24 26 28 30
Stress IntensityFactor, MPa\m
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
K
2.0
K
2.5
Dependency
Effect of Stress Intensity Factor (K) on
Crack GrowthRate of 20% ColdWorked
Wrought Alloy182 Testedin288 C Water
Using AVery SlowReduction in K Under
"Constant K" Conditions (No Cycling)
Figure 28. Stress intensity factor, K, dependency for IGSCC of cold worked wrought alloy 182 in 288 C water with 2000 ppb O
2
.
1005
1.E-08
1.E-07
1.E-06
10 12 14 16 18 20 22 24 26 28 30
Stress IntensityFactor, MPa\m
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
K
2.5
K
3.5
Dependency
Effect of Stress Intensity Factor (K) on
Crack GrowthRate of 21% ColdWorked
304L SS + 1.5%Si Tested in 288 CWater
Using AVery SlowReduction in K Under
"Constant K" Conditions (No Cycling)
K
3.0
Figure 29. The stress intensity factor, K, dependency for IGSCC of cold worked stainless steel in H
2
deaerated 288 C water. A somewhat
higher K dependency is typically observed at low corrosion potential.
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
-1000 -500 0 500
Corrosion Potential, mVshe
N
o
r
m
a
l
i
z
e
d
C
r
a
c
k

G
r
o
w
t
h

R
a
t
e
,

m
m
/
s
R
2
= 0.07
Sens 304 Stainless Steel, 288C Water
1TCT Specimens, ~< 0.2 S/cm
Figure 30. Crack growth rate vs. corrosion potential for type 304 stainless steel. The large scatter in the data makes it effectively
impossible to determine effects of individual variables, and produces severe dilution in important trends (e.g., vs. corrosion potential) that
then become only weakly evident.
1006
Session Name: PWR Primary III
Session Day/Time: Monday 8/15, 1:30-5:30
Effects of PWR Water Chemistry on SCC Growth Rate
of Alloy 600
Presenter: Peter Andresen
Name of Person Asking Question: Jeff Gorman
Affiliation of Person Asking Question: DEI
Question: Can you explain why Jackos crack initiation tests show a strong pH/Cu
dependence, while your crack growth rate tests show essentially no effect?
Response: No, Li (or B) should have no difficulty penetrating fully into the crack.
The basis for our confidence in crack growth rate data is much higher than for
initiation data and there is a strong and growing body of such crack growth data.
My personal inclination is to doubt the effect on crack initiation because it is not
monotonic and there is a lot of noise and overlap in the raw data. This is in no
way criticism of Jackos efforts, because initiation is difficult to study and his test
design and execution seems as sound as anyones.
Name of Person Asking Question: Roger Staehle
Affiliation of Person Asking Question:
Question: Where is the clear definition of continuity of your S-shape curves with
the Morton type gauss shapes? How good is this correction? While I didnt ask
or point this out, there should be an effect as f(pH) in view of the enormous
change in solubility of NiO. Investigating this effect might usefully be used to
study the mechanistic aspects.
Response: We have not studied in a single specimen the range of potential
from oxidizing to deaerated, then with increasing H
2
to evaluate the Ni/NiO
peak. However, we have observed this continuity using multiple specimens and
its likely that similar observations have been performed by KAPL. Its clear that
SCC follows a well-behaved continuity from high potential (in O
2
water where the
crack tip is in the NiO stable region) to low potential and higher H
2
conditions
(where Ni is stable). Thus, its not obvious that there is a change in crack
advance mechanism and mechanisms that rely on Ni stability cant account for
the observed SCC response. We have examined pH explicitly in this paper,
1007
ranging from ~pH 5.7-5.9 (pure water at various temperatures) to pH ~8.0 using
B/Li. Dave Morton and colleagues have seen similar response (Paper 03675,
Corrosion 03, NACE) and Rich Jackos paper following this talk comes to similar
conclusions.
1008