Journal of Nuclear Materials 423 (2012) 28–39

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Journal of Nuclear Materials

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Synergistic effects of local strain-hardening and dissolved oxygen on stress

corrosion cracking of 316NG weld heat-affected zones in simulated BWR
environments
Zhanpeng Lu, Tetsuo Shoji ⇑, He Xue, Fanjiang Meng, Chaoyang Fu, Yoichi Takeda, Koji Negishi
Fracture and Reliability Research Institute, Faculty of Engineering, Tohoku University, 6-6-10, Sendai 980-8579, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Stress corrosion cracking growth during long-term test in high temperature water was monitored in two
Received 5 April 2011 316NG weld heat-affected zones representing highly hardened and medially hardened regions. Cracking
Accepted 26 December 2011 near the weld fusion line exhibited both macroscopic bifurcation and extensive microscopic branching,
Available online 11 January 2012
which was faster than that in the medially hardened region where crack kinking was observed. There
is an interaction between material hardening and dissolved oxygen on crack growth. The effect of a single
overloading on crack growth in 316NG heat-affected zones is less significant than that in a cold worked
316NG stainless steel.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction hardened non-sensitized stainless steels exhibited high crack

There have been some cases of cracking in boiling water reactor
(BWR) pressure boundary components, such as primary loop
re-circulation (PLR) pipes made with 304 stainless steel (SS), where
the cracking was caused by typical weld sensitization in heat af-
fected zones due to Cr depletion along grain boundaries [1–4].
Non-sensitized stainless steels are used to replace the previously
used 304 SS for mitigating SCC. However, recently cracking was
found in PLR pipes and core internals in BWR plants [4–9]. Extensive
analyses on these cracked components from BWR plants have been
performed and reported. Cracking of these PLR pipes generally
occurred in the HAZ where significantly high hardness due to weld
shrinkage was observed. Also, a hardened surface layer due to sur-
face treatment was observed. Analyses showed that cracking initi-
ated in the surface hardened layer as transgranular SCC (TGSCC)
and then propagated as intergranular SCC (IGSCC) [4,5,7,9]. Several
types of crack growth behavior were categorized: growing in HAZ,
type T-I; stopping at fusion boundary, type T-II; penetrating into
weld metal, type T-III, and changing the growing direction in the
HAZ along fusion line, type T-IV. In some cases, cracks grew into
the weld metal region. The majority of cracks arrested before reach-
ing a critical depth of about 10 mm for A600 PLR piping. Microstruc-
tural analyses show that most low carbon stainless steels were not
thermally sensitized [4,5,10]. Increased hardness or strength due to
weld shrinkage has been identified to be crucial for the high crack
growth rates observed in BWR plants. Recent results showed that
⇑ Corresponding author. Tel.: +81 22 7957517.
E-mail address: tshoji@rift.mech.tohoku.ac.jp (T. Shoji).
growth rates in oxygenated pure water [4,11–21], which provided
the supporting evidence that hardening in HAZ might play an
important role in promoting SCC growth. Besides the hardening of
materials, changes in crack tip mechanical fields due to local
stress–strain distribution may also affect the crack growth behavior
such as the crack arrest phenomenon [5,9,22,23]. Understanding
and quantifying the crack growth behavior in the HAZ near the
fusion line and related influencing factors is important in the
prediction of the service time of real components [4,5,23–26].
Overloading effects on subsequent material degradation can be re-
lated to pressure–tolerance tests or earthquake [27]. In the present
research, two 316NG HAZ specimens were tested in simulated
boiling water reactor water environments for about 4605 h under
various test conditions. The objectives are to investigate the effect
of the locations in the HAZ with two levels of hardness, the
effect of dissolved oxygen, the effect of single overloading, and
the effect of test interruption on stress corrosion cracking growth.
2. Experimental details
2.1. Materials and specimen preparation
Type 316NG pipe (600 mm diameter, 41.27 mm wall thickness)
was welded using two heats of Type 316L weld wire [28]. The
chemical compositions of 316NG PLR pipe are shown in Table 1.
The high ferrite content wire composition in wt.% was 0.015 C,
1.75 Mn, 0.35 Si, 0.014 S, 0.017 P, 19.2 Cr, 12.3 Ni. 2.61 Mo, and
0.05 Cu, which yields a Cr(eq) of 22.33% and a Ni(eq) of 13.62%.
The low ferrite content wire content composition was: 0.022 C,

0022-3115/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnucmat.2011.12.030
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39
Table 1
Chemical composition (wt.%) of 316NG SS base metal used in fabrication of pipe
welds.
C Si Mn P S Ni Cr Mo N Fe
0.01 0.48 1.42 0.023 0.003 11.64 17.50 2.08 0.116 Bal.
1.85 Mn, 0.44 Si, 0.001 S, 0.021 P, 19.34 Cr, 12.68 Ni. 2.51 Mo, and
0.26 Cu, which yields a Cr(eq) of 22.51% and a Ni(eq) of 14.26%. The
nominal ferrite content for the two welds was 10% and 8%, respec-
tively. The ferrite compositions correspond to ferrite numbers
(FNs) of approximately 13 and 10, respectively. The welds were
prepared in accordance with nuclear specification by Gas Tungsten
Arc welding. The weld-hardening behavior in two weld HAZs pre-
pared by two weld filler metals is similar, as indicated by previous
measurements [26].
Two contoured double cantilever beam (CDCB) specimens were
fabricated by electron-beam welding of the blocks with weld heat-
affected zones to support blocks to have enough size for preparing
crack growth rate specimens. Specimen HTH4 was prepared from a
weld prepared with a high ferrite content wire, and specimen
WOH3 was prepared from a weld prepared with a low ferrite con-
tent wire. The design of the CDCB specimen has been described in
previous publications [17,20]. The distribution of Vickers hardness
(HV1) in the HAZ was measured with Shimazu Vickers hardness
tester with a loading of 9.8 N and a holding time of 15s on an as-
welded HAZ block prepared by a high ferrite content wire
[18,29]. The mapping of Vickers hardness (HV1) is shown in
Fig. 1, which is also assumed approximately applicable to both
HTH4 and WOH3 HAZ specimens.
Based on the HV distribution, the locations of the notches in
specimens WOH3 and HTH4 were determined to test SCC behavior
at different regions with different degree of strain-hardening pro-
duced by welding process. The crack growth in the region near
the fusion line was emphasized for its engineering application to
evaluation of the plant component performance. The size of the
CDCB specimens is shown in Fig. 2a. The notch of specimen
WOH3 was located in the heavily hardened (due to weld shrink-
age) region near the fusion line, where the HV is around 220. The
notch of specimen HTH4 was located in the medially hardened
region where the HV is around 190. The locations of the notches
of specimens WHO3 and HTH4 are shown in Fig. 2b and c. The
detailed locations of notches are shown in the experimental result.
Fig. 1. Hardness distribution in the 316NG weld heat-affected zone.
29
The grain boundary microstructures were observed by electron-
back scattering diffraction (EBSD) technique on separate blocks
taken from the same pipe weld mockup. EBSD was measured with
Hitachi S-4300 FE-SEM, TSL solutions camera control system
VIT1000, image processing system DSP 2000, and interface control-
ler MSC 2000. The EBSD pattern was analyzed using OIM-Analysis
software provided by TSL, Co. Ltd. [30]. Acceleration voltage of SEM
beam for the EBSD measurement is 25 kV and the beam current is
15 lA. The surface for EBSD measurements was finally finished by
polishing with 0.3 lm deagglomerated alpha alumina powder/
water mixture followed by electropolishing using HClO4 + C2H5OH
electrolyte in order to get relatively smooth surface free from sur-
face hardening caused by the mechanical polishing.
2.2. Stress corrosion cracking tests
The thickness of the specimens is 12.5 mm. The specimen was
first air-fatigued at 15 Hz at a Kmax of about 15 MPa m0.5 and a
load ratio (R = Kmin/Kmax) R = 0.2. Locations of the notches in CDCB
specimens after the precracking in air have been shown in Fig. 2a
and b. After precracking in air, the specimen was side-grooved
5% on each side. The in situ precracking and SCC growth test was
performed in high temperature pure water at 288 °C. Pressure
was 8.9 MPa, and the flow rate was 5 L/h. The outlet conductivity
was less than 0.20 ls/cm. The triangle (Tri.) wave loading mode
used for in situ precracking is: f  0.01 Hz, Kmax  20 MPa m0.5:
R = 0.3 (288 cycles), R = 0.5 (576 cycles), and R = 0.7 (864 cycles),
respectively. SCC tests were performed under a constant loading
condition at a nominal K of about 20 MPa m0.5. The actual values
of stress intensity factor at the crack tips in two specimens were
calculated by finite element methods. The effects of dissolved oxy-
gen (DO) and single overloading on crack growth of two specimens
were investigated. Crack growth was monitored by using an Alter-
nating Current Potential Drop (ACPD) machine. During SCC tests,
electrochemical corrosion potential of the specimen was measured
against a pressure-balanced external Ag–AgCl (0.1 mol/L KCl) ref-
erence electrode. The measured ECP for 316L SS HAZ specimens
in 288 °C pure water is about 0.05 V (SHE) at DO = 0.2 ppm, about
0.1 V (SHE) at DO = 2 ppm, and about 0.13 V (SHE) at DO = 7 ppm.
The average SCC crack length measured on the fracture surface
after the test was used to calibrate the ACPD data. The test matrix
and conditions are shown in Table 2. During shutdown interrup-
tion, the temperature was decreased to room temperature and
the load was removed. The duration of shutdown is about 2 days.
3. Results and discussion
3.1. SCC paths and morphologies
The side surface of specimen WOH3 after removing the side
groove is shown in Fig. 3a. There are two main crack branches,
branches H3L and H3R. Branch H3L was at an angle of about 40°
against the notch direction, which was going toward to (almost
perpendicular to) the weld fusion line. The crack tip region of
H3L is nearby the weld fusion line and appeared to be confined
in the HAZ from the side surface observation. Branch H3R was at
an angle of about 15° against the notch direction. Both branches
H3L and H3R exhibit intergranular feature and small secondary
branches. Branch H3L is significantly longer than branch H3R,
which is treated as the main SCC crack in specimen WOH3. The
side surface of specimen HTH4 after removing the side groove is
shown in Fig. 3b. The stress corrosion crack is at an angle of about
15° against the notch direction, showing a kinking feature toward
the weld fusion line. The values of stress intensity factor at the
branched crack tips in specimens WOH3 and HTH4 were calculated
30 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39

(a) Drawing of CDCB specimens

(b) Specimen HTH4 (c) Specimen WOH3

Fig. 2. (a) Drawing of CDCB specimens, and photos of, (b) specimen HTH4 and (c) specimen WOH3 after the precracking in air. The thickness of specimens is 12.5 mm.

Table 2
Test conditions and sequences for two 316L HAZ specimens in simulated BWR water at 288 °C.

Specimen and step no. DO (ppm) Loading mode Cycles or time

Specimen HTH4 (medium HV) Specimen WOH3 (high HV)
HTH4P1 WOH3P1 2 Tri. loading*, R = 0.3, 0.01 Hz 288 cycles
HTH4P2 WOH3P2 2 Tri. loading, R = 0.5, 0.01 Hz 576 cycles
HTH4P3 WOH3P3 2 Tri. loading, R = 0.7, 0.01 Hz 864 cycles
HTH4S1 WOH3S1 2 Constant loading (CL) 987 h
HTH4S2 WOH3S2 0.2 CL 813 h
HTH4S3 WOH3S3 7 CL 477.2 h
HTH4S3a WOH3S3a 1st shutdown and restart
HTH4S4 WOH3S4 7 CL 358 h
HTH4S4a WOH3S4a 2nd shutdown and restart
HTH4S5 WOH3S5 7 CL 582.9 h
HTH4S5a WOH3S5a 7 Single overloading, 1.2KCL Total 855 s
HTH4S6 WOH3S6 7 CL 530.1 h
HTH4S6a WOH3S6a 7 Single overloading, 1.3KCL Total 1060 s
HTH4S7 WOH3S7 7 CL 856.9 h
*
Tri. loading: triangular loading.

with finite element methods. There are K = 21.2 MPa m0.5 at SCC tip
H3L and K = 12.71 MPa m0.5 at SCC tip H3R in specimen WOH3, and
K = 21.1 MPa m0.5 at the SCC tip H4t in specimen HTH4, as shown
in Fig. 3.
The typical fracture surfaces of specimens HTH4 and WOH3 are
shown in Figs. 4 and 5. Typical intergranular SCC features are
identified on both specimens. The averaged crack lengths mea-
sured on the fracture surfaces are used to obtain the average crack
lengths at each test step based on the ACPD monitoring results.
The observation of typical intergranular stress corrosion
cracking in the weld HAZ specimens HTH4 and WHO3 are consis-
tent with reported results of SCC in low-carbon stainless steel
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39 31

(a) Specimen HTH4 (b) Specimen WOH3

Fig. 3. The side surface of (a) HTH4 specimen and (b) WOH3 specimen after the SCC test (after removing of the side groove). The distance between the notch tip H4f and the
fusion line is about 6 mm in specimen HTH4, and the distance between the notch tip H3 and the fusion line is about 2.5 mm.

Fig. 5. The fracture surface of specimen WOH3 (high HV) after the SCC test.
(a) Fracture surface
HAZ specimens and the results of BWR components [4,5,7–
9,25,26,31,32]. The role of strain hardening in promoting intergran-
ular SCC in the HAZ has been confirmed by the observation of IGSCC
in cold-worked or warm-worked austenitic alloys in high tempera-
ture water. It is proposed that locally high stress at the grain bound-
aries in the strain-hardened austenitic alloys with high yield
strengths promotes the grain boundary oxidation and the resultant
stress corrosion cracking growth rate [33]. The role of dislocation
distribution is also proposed as one of the factor for the enhanced
SCC growth in prior-deformed austenitic alloys in high temperature
water [16].
Crack branching in low-carbon stainless steel weld HAZs near the
weld fusion line has been observed in other laboratory samples fab-
ricated with BWR PLR mockups [23,24,26]. Generally the main SCC
crack in the HAZ exhibits a tendency going toward the weld fusion
line [23–26]. Several underlying factors such as microstructural
(b) Typical IGSCC region heterogeneity, residual stress and residual strain are proposed for
the occurrence of SCC branching or kinking in the HAZ. The EBSD
Fig. 4. The fracture surface of specimen HTH4 (medium HV) after the SCC test. results in terms of inverse pole figure (IPF), types of boundaries
32 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39
(a) Locations for the EBSD measurements
(b) EBSD results obtained in the region shown in Fig. a.
Fig. 6. A 316NG HAZ block. Step size = 4 lm
and kernel average misorientation (KAM) of the region near the
weld fusion line in a 316NG HAZ are shown in Fig. 6. Significant den-
drite structure in the weld metal is observed. Heterogeneity in crys-
talline microstructure in the HAZ is observed, such as the grain size
and the orientation, as shown in Fig. 6b. More details of EBSD results
of other regions adjacent to the weld fusion line are shown in Figs. 7
and 8, showing types of boundaries and distribution of KAM. It has
been reported that the fraction of high angle boundaries in the
HAZ increases with the distance from the weld fusion line [26]. High
fraction of high angle boundaries and locally high KAZ near the high
angle boundaries are observed in the regions near the weld fusion
line, Figs. 7 and 8. If the applied stress is not very high, these high an-
gle boundaries with locally high KAM would act as active SCC paths
thus causes crack branching in the HAZ rather than the penetration
into the weld metal.
It is thought that residual stress would play an important role in
promoting SCC and crack branching/kinking in the weld HAZ. The
change of SCC growth direction toward the weld fusion line in
specimen HTH4 implied the effect of residual stress, as shown in
Fig. 3b. For a SCC branching system, it is expected the crack branch-
ing would be more significant if the SCC growth is only weakly K
dependent. A simple correlation between CGR and overall stress
intensity factor Kov is assumed in Eq. (1), where Kov is the overall
K. The stress intensity factor imposed by applied loading, Kap, is
the function of the crack geometry and the applied stress (rap).
The stress intensity factor imposed by residual stress, Kres, is the
function of crack geometry and the residual stress (rres) that is
dependent on the welding process.
CGRðK ov Þ ¼ C K  ðK ov Þnk ð1Þ
where CGR(Kov) is CGR at stress intensity factor Kov, CK is a constant,
nk is an exponent in the CGR-K correlation. Eq. (2) shows that the
overall stress intensity factor Kov is the combined result of applied
stress and residual stress.
K ov ¼ K ap þ K res ð2Þ
A crack branching system is schematically shown in Fig. 9. FEM
calculation shows that Kap is sensitive to the lengths of crack
branches. Kres is related to the crack geometry and also the residual
stress that is highly dependent on the location in the HAZ [9]. Kap at
branching crack tip B1 can be significantly higher than that at
branching crack tip B1 if LB1 is significantly longer than LB2, as de-
scribed in the results of the stress intensity factor for branching
crack tip H3L and H3R, as shown in Fig. 3. Analysis of several types
of crack branching systems has been reported previously [34,35].
Suzuki et al. [32] reported the results of residual stress distribu-
tion on inner surface of mockup of 316L PLR pipe 600A. The axial
residual stress near the fusion line is tensile and can be as high
as 400 MPa. The results of principal stress direction near the weld
root of PLR pipe weld joint by FEM are also reported for a 600A PLR
mockup. Crack generally follows the path that is perpendicular to
the main stress direction, which is generally going toward the weld
fusion line. Arai et al. [23] has measured the residual stress in a
316L SS HAZ mockup by XRD. Biaxial tensile stresses were detected
in the HAZ region near the fusion line. The main stress is perpen-
dicular to the weld fusion line, which varies from about 600–
800 MPa, and the secondary stress parallel to the weld fusion line
varies from about 200–400 MPa at a distance of about 0.1 mm
away from the weld fusion line. These results show significantly
high values of residual stress and the existence of bi-axial stress
in the weld HAZ. If the stress intensity factor imposed by residual
stress, Kres, constitutes a significant portion of the overall stress
intensity factor, Kres, CGR is expected to be less sensitive to Kap in
the HAZ than that in the cold worked stainless steels. Such a sup-
position is verified by the experimental SCC growth rate data for
cold worked stainless steels and HAZ specimens, as shown in
Fig. 10. Analyses of reported CGR data show that the dependence
of CGR on K in low-C stainless steel HAZ tends to be less significant
than that in as-solution annealed low-C stainless steel or cold-
worked low-carbon stainless steel [8,12,15,36–39]. Andresen et
al. have reported that nk in Eq. (1) is about 2.3 for CGR of non-
sensitized cold-worked stainless steels in oxygenated pure water
at 288 °C. However, only weak dependence of CGR on applied
stress intensity factor for high HV HAZ is observed, which is possi-
bly caused by the presence of residual stress in the HAZ. If the
effect of K on CGR is weak, the difference between branching crack
tips of different lengths is not significant thus, the crack growth at
two tips can be maintained. The existence of bi-axial stress would
affect crack branching, which needs more systematic investigation.
Fig. 3 shows that crack branching tends to become less significant
with increasing the distance from the fusion line, which
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39 33

(a) IPF

(b) Types of boundaries

(c) KAM distribution

Fig. 7. EBSD results of one region near the fusion boundary in a 316NG.

corresponds to the reported results on the decay of residual stress
in the weld HAZ. In summary, the SCC branching in the HAZ near
the weld fusion line is the combined result under the effects of
local hardening at the grain boundaries, heterogeneous
microstructure, and the residual stress.
3.2. SCC growth kinetics and influencing factors
The values of crack length vs. test time are shown in Fig. 11a for
specimen HTH4 and Fig. 11b for specimen WOH3 under various
test conditions. Well-behaved crack growth during the entire SCC
34 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39

(a) IPF

(b) Types of boundaries

(c) KAM
Fig. 8. EBSD (step size = 3 lm) results of one region near the fusion boundary in a 316NG weld.

3.2.1. The effect of strain hardening

Fig. 9. Schematic of a crack branching system. Where point A is the starting
position of SCC, B1 and B2 are two SCC branches with lengths of LB1 and LB2, and
branching angles of hB1 and hB2 respectively.
test period was observed based on the ACPD monitoring for both
specimens.
SCC incubation in the test step just after the in situ precracking
is more significant in medium HV specimen HTH4 than that in
specimen WOH3. Higher degree of strain hardening in the high
HV specimen would lead to high SCC sensitivity thus facilitates
the transition from TG cracking to IGSCC easier [20,25]. The com-
parison of the crack growth behavior in high HV HAZ and medium
HV HAZ is shown in Fig. 12. The steady state CGR for specimen
WOH3 during test step WOHS1 is 1.52  1010 m/s, which is
4.0  1011 m/s for specimen HTH4 during the test step HTH4S1.
The CGR in high HV specimen WOH3 is 3.8 times of that in medium
HV specimen HTH4. The results are consistent with the reported
data on the effect of HV on CGR in 316L HAZ and the data on the
effect of yield strength on CGR of low-carbon stainless steels in
simulated BWR environments.
Increasing of SCC growth rates of austenitic alloys with increas-
ing yield strength could be caused by several factors such as locally
high stress region at the crack tip that would enhance the mass
transport processes at the crack tip interface, and steep strain-
gradient that would localize the crack tip oxidation or degradation
of crack tip oxide film. The role of stress-enhanced oxidation on
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39 35

o
Andresen et al, CW316L, YS(288 C)=558 MPa, 2 ppm DO 0.7
FRI data, CW 316L, YS(RT)=760 MPa, 2 ppm DO
FRI data, CW 316L, YS(RT)=760 MPa, 7.5 ppm DO
316NG weld HAZ specimens
Crack growth rate, CGR (m/s)

1E-9
Itow et al., 304L SA, 15-20 ppm
Itow et al., 316 NG SA, 18-27 ppm 0.6 288 C water,2 ppm DO, constant loading

Crack length, da (mm)

Itow et al., 316 L SA, DO=18-33 ppm
Tsubota et al., 316L SA, 8ppm DO
JNES 316L, SA, high ECP
JNES HAZ, 316L HAZ, medium HV: 182~197, high ECP
0.5
WOH3(high HV)
JNES HAZ, 316L HAZ, high HV: 200~255, high ECP
step WOH3S1
1E-10 0.4

0.3

1E-11 0.2
HTH4(medium HV)
step HTH4S1
0.1
Constant K or constant loading,
0
pure water, 288 C
1E-12 0.0
0 10 20 30 40 0 200 400 600 800 1000 1200
Stress intensity factor, K (MPa m0.5) Test time, t (h)

Fig. 10. Crack growth rate vs. stress intensity factor for non-sensitized stainless Fig. 12. Comparison of crack length vs. time curves for specimens HTH4 and WHO3
steels in oxygenated pure water at 288 °C. The reported data [8,12,15,36–39] are in 288 °C pure water with 2 ppm DO.
also plotted.

ing DO from 0.2 ppm DO to 7 ppm DO significantly increases crack

growth rates, as shown in Fig. 13. The calculated steady state CGRs
are calculated and the CGR ratio (Rcgr) for two specimens tested
under the same condition is calculated according to Eq. (3). The re-
sults are shown in Fig. 14. The results clearly show that SCC growth
rates in specimen WOH3 are higher than those in specimen HTH4
at each DO concentration in high temperature pure water. The ef-
fect of yield strength appears to be more significant at low DO, as
shown in Fig. 14. Fig. 13 show that CGR(HTH4) at 7 ppm DO is sig-
nificantly higher than that at 2 ppm DO, while CGR(WOH3) exhibit
similar values at 2 ppm DO and 7 ppm DO. There is an interaction
between environmental conditions and strain hardening of mate-
rial on SCC growth in high temperature water environments. A
moderate decrease of CGR in non-sensitized austenitic stainless
steel with decreasing DO from 2 ppm to 0.2 ppm in high tempera-
ture pure water has been reported by Andresen et al. [11].

(a) Specimen HTH4 Rcgr ¼ CGRðWOH3Þ=CGRðHTH4Þ ð3Þ

Crack growth rate of various alloys in high temperature water
can be expressed by a general equation:

da
¼ ja  ðe_ct Þm ð4Þ
dt

td ¼ ed =e_ct ð5Þ

where da/dt or CGR is crack growth rate, ja is the crack tip oxidation
rate constant in the crack growth rate equation, m is the slope of the
oxidation rate decay curve, td is the period of crack tip film degrada-
tion, e_ct is the crack tip strain rate, ed is the threshold strain for deg-
radation of the protective film. The definition of ja depends on the
rate-determining step for the crack tip oxidation process. Several
SCC mechanisms have been proposed concerning the element pro-
cesses and rate-controlling laws, such as slip-dissolution/oxidation,
(b) Specimen WOH3 internal oxidation, or deformation/oxidation laws [3,4,42–44].
For slip-dissolution/oxidation mechanism, there are
Fig. 11. SCC crack advance vs. test time for 316NG HAZ specimens.
   m
SCC growth has been proposed for primary water SCC (PWSCC) of
Ma  i0 t0
ka ¼ ð6Þ
nickel-base alloys, which would also apply to SCC in BWR environ- z  q  F  ð1  mÞ ef
ments [33]. The effects of local deformation on IASCC and SCC have
  m
been investigated [40,41]. da M a  i0 t0
¼ fe_ct gm ð7Þ
dt z  q  F  ð1  mÞ ef
3.2.2. Effects of dissolved oxygen in high temperature water on crack
growth where Ma is the (normalized) atomic weight, i0 active surface oxida-
In both specimens HTH4 and WOH3, decreasing DO from 2 ppm tion current density, z in valence due to oxidation of alloy, q is
to 0.2 ppm significantly decreases crack growth rates, and increas- density of alloy, F is Faraday’s constant, t0 is time for the onset of
36 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39

Oxidation rate parameters k1, m1 and m are defined in the fol-

lowing equations:

Lm1 ¼ k1 t ð10Þ
 
1
m¼ 1 ð11Þ
m1
where L is the oxide film thickness and t is time.
Values of m1 and m take different values for different kinds of
oxidation rate law. For example, there are m1 = 1 for linear growth
law, m1 = 2 for parabolic growth law, and m1 = 3 for cubic growth
law. A larger m1 corresponds to higher tendency to form protective
oxide film. There are m1 = 2 and m = 0.5 for the parabolic oxidation
kinetics that follows Wagner’s theory of oxidation [45].
Oxidation rate constants ja is strongly dependent on the envi-
ronmental parameters that affect bulk and local chemistry and
(a) specimen HTH4
electrochemistry. The chemistry and electrochemistry are crucial
in modeling of environmentally assisted cracking. A schematic of
a SCC systems with different interface is shown in Fig. 15. A more
complete description of the interfaces and related mass transport-
ing processes have been proposed [44,46,47]. The crack chemistry
has been theoretically investigated by Turnbull [48,49,51], Turn-
bull and Ferriss [50], Psaila-Dombrowski et al. [52], and Macdonald
and Urquidimacdonald [53], Macdonald et al. [54], and Engelhardt
et al. [55]. Turnbull [51] reported that the crack tip potential is not
independent of the external potential in BWR water, and the reac-
tions on the crack walls cannot be ignored in predicting the chem-
istry and potential in a crack. Engelhardt et al. [55] reported that
the potential and concentrations reach plateau values at a suffi-
ciently large distance from the crack mouth, and the plateau only
occurs for sufficiently low corrosion potential at the crack mouth.
The distribution of the crack anions and cations in the crack en-
clave is also numerically calculated. Andresen and Morra [15]
(b) specimen WOH3 pointed out the importance of crack chemistry evolution and re-
lated ionic current flow within cracks in SCC process. It is reported
Fig. 13. Details of the crack length vs. time curves for (a) specimen HTH4 and (b)
specimen WOH3 in 288 °C pure water at various DO concentrations.
that the entire gradient in oxidant concentration, corrosion poten-
tial and resulted chemistry exists over a comparatively short dis-
tance near the crack mouth [15]. There are some remaining
o
288 C pure water, CL issues in the modeling of crack chemistry and electrochemistry.
2.0x10-10 5 Turnbull [51] proposed the general equation for the mass trans-
Specimen HTH4 port in a SCC crack, Eq. (12). In this equation, the convective mass
Crack growth rate, CGR (m/s)

Crack growth rate ratio, Rcgr

Specimen WOH3 transport in the crack is neglected which implicitly assumes that
1.5x10
-10 4 the external flow direction is across the narrow mouth opening
so that through-thickness convection can be neglected.
  X X Ri;j;hetero
@C i @ 2 C i zi D i F @ @u
-10 3 ¼ Di 2 þ Ci þ Ri;j;homo þ ð12Þ
1.0x10 @t @x RT @x @x j j
dx

where Ri,j,hom represents homogeneous equilibrium reaction process

5.0x10
-11 2 that can occur in the solution in the crack, Ri,j,hetero represents

Rcgr=CGR(WOH3)/CGR(HTH4)
0.0 1
0 1 2 3 4 5 6 7 8
Dissolved oxygen concentration, DO (ppm)

Fig. 14. SCC growth rate vs. dissolved oxygen concentration for specimens HTH4
and WOH3 in 288 °C pure water during the test steps shown in Fig. 9.

current decay, ef is the threshold strain for the rupture of the protec-
tive film.
For solid state oxidation mechanism, there are
ka ¼ ½ðk1 Þð1mÞ  ðed ÞðmÞ  ð8Þ

da
¼ ½ðk1 Þð1mÞ  ðed ÞðmÞ fe_ct gm ð9Þ
dt Fig. 15. Schematic of a stress corrosion cracking system with different interfaces.
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39 37

heterogeneous reactions processes that can occur on the walls of

the crack (including redox reactions and interfacial precipitation
reactions), dx is a half of the crack width at a distance x from the
crack mouth.
The general mass transport Eq. [51] considers the role of con-
vection, diffusion and potential driven ion migration:

@C i ðxÞ zi F @ uðxÞ
J i ðxÞ ¼ Di  Di C i þ ci v ðxÞ ð13Þ
@x RT @x

where Ji (mol/(s m2)) is the flux of species i, Ci is the concentration of

species i at distance x, m (in m/s) is the fluid velocity at location x, Di
is the diffusion coefficient of species i in water, oCi/ox is the concen-
tration gradient, zi is charge of species i, R is the gas constant, T is
the absolute temperature (K), F is Faraday’s constant, u is the differ-
ence in potential between the value at the crack mouth (Emouth or
ECM) and that at a position with distance x from the crack mouth.
In a simplified condition considering diffusion is the only rate (a) Specimen HTH4
limiting process for the mass transport, non-steady diffusion of
oxygen from the bulk solution to the crack enclave can be ex-
pressed by Ficker’s second law.

@ci ðx; tÞ @ 2 ci ðx; tÞ

¼D ð14Þ
@t @x2
With increasing dissolved oxygen concentration in high tem-
perature water, electrode potential of the bulk surface or at the
crack mouth increases, and the potential gradient between the

(b) Specimen WOH3

Fig. 17. Details of the crack length vs. time curves for (a) specimen HTH4 and (b)
specimen WOH3 in 288 °C pure water before and after single cycle overloading
operations.

crack mouth and the crack tip increases if a relatively constant

crack tip potential is assumed [3,15]. With increasing the potential
gradient between the crack mouth and the crack tip, the migration
of aggressive ions toward the crack tip is enhanced, which could
accelerate the oxidation rate at the crack tip. The active surface
(a) Specimen HTH4 oxidation current i0 or solid-state oxidation rate constant k1 would
be affected by changing DO concentrations through the changing of
the potential gradient, the changing of surface vacancy concentra-
tion and other related processes. The dependence of CGR on
electrochemical potential in a wide range has been summarized
for various austenitic stainless steels in 288 °C pure water
[15,18]. Some details for element processes and rate-controlling
laws for SCC in high temperature has been discussed [3,4,42–44]
and further investigation is still necessary for SCC systems under
various combined effects of material, mechanical and environmen-
tal parameters.

3.2.3. The effect of test interruptions

Crack growth behavior of two specimens before and after test
interruptions is shown in Fig. 16. Test interruption here refers to
the shutdown of the autoclave system, including the decrease of
temperature to room temperature and the removal of the loading,
(b) Specimen WOH3 due to loss of power supply as the result of cable inspection or
Fig. 16. Details of the crack length vs. time curves for (a) specimen HTH4 and (b)
other operations. For specimen HTH4, after the test interruption
specimen WOH3 in 288 °C pure water before and after shutdown/restart HTH4S3a, the CGR at first did not change much but later decreased
interruptions. to a lower value. A similar change of CGR occurred after the test
38 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39
interruption WOH3S3a in specimen WOH3. After the second test
interruption (HTH4S4a), CGR decreased significantly in a short per-
iod and then changed to a steady value that is lower than that
before the test interruption. A similar change of CGR occurred after
the test interruption WOH3S4a, while showing a longer period for
the transition from low CGR to a new steady state growth period.
Even though the test interruptions would involved many aspects
of SCC processes, the general trend is that well-behaved SCC
growth at a lower CGR value could be achieved after a period of
transition growth.
3.2.4. Effects of single cycle overloading
Crack growth behavior of two specimens before and after single
overloading procedures is shown in Fig. 17. After the single
overloading of R = 1.2 for specimen HTH4, CGR initially seemed to
be unaffected and then decreased to a lower value. After the single
overloading of R = 1.2 for specimen WOH3, CGR initially decreased
and then soon changed to a steady value that is lower than that be-
fore the single overloading. After the single overloading of R = 1.3 for
specimen HTH4, it seemed that CGR initially was not affected but
later decreased to a lower value.. After the single overloading of
R = 1.3 for specimen WHO3, CGR initially decreased for a short per-
iod and then increased to a steady value that was still lower than that
before the single overloading. Generally single overloading proce-
dures leads to a lower CGR after a transition period that is dependent
on the material property and overload ratio. The effect of overload-
ing on SCC growth can be attributed to the effect of residual strain
field on the subsequent crack growth, which has been analyzed by
finite element analysis [56]. There appears to be a stronger effect
of single overloading on the transient SCC growth has been observed
in a
3-directionally cold worked 316NG stainless steel [18,56], showing
that the complex stress state in the weld HAZ would apparently off-
set to some extent the effect of applied single overload.
4. Conclusions
Long-term stress corrosion cracking growth in high temperature
water was monitored in two 316NG weld heat-affected zones near
the weld fusion line and at about 6 mm away from the fusion line,
representing crack growth in highly hardened area and medially
hardened area. Crack growth near the fusion line exhibited both
macroscopic bifurcation and extensive microscopic branching,
which was faster than that in the medially hardened region under
the same testing condition. Residual stress and microstructural het-
erogeneity are thought to contribute to the crack branching or kink-
ing in the HAZ. Crack growth rate increases with increasing DO from
0.2 ppm to 2 ppm or 7 ppm. CGR in the highly hardened region is
less sensitive to dissolved oxygen than that in the medially hard-
ened region. There is an interaction between material hardening
and dissolved oxygen on crack growth. Test interruption generally
results in a lower CGR. The effect of a single cycle overloading with
load ratio of 1.2 or 1.3 generally had a mild decreasing effect on
crack growth in the subsequent test period. The transient crack
growth behavior after the single cycle overloading varies with the
locations in the HAZ, which is less significant than that observed
in cold worked stainless steel under a similar test condition.
Acknowledgements
This work has been performed as a part of the PEACE-E program
jointly supported by EDF, EPRI, SSM, TEPCO, KEPCO, TohokuEPCO,
ChubuEPCO, JAPCO, HITACHI Ltd., MHI, TOSHIBA Co., and IHI. This
work has been also performed under the supports of Grant-in-Aid
for Scientific Research (S) 17106002, (C) 20560063 and (C)
23560078, Japan Society for the Promotion of Science, and the
support of the International Cooperative Program for Education
and Research, the Japanese Ministry of Education, Culture, Sports,
Science and Technology. Part of this work was performed as a part
of the contracted work on Enhancement of Ageing Management
and Maintenance of Nuclear Power Plants by Nuclear and
Industrial Safety Agency (NISA) in the Ministry of Economy, Trade
and Industry (METI) of Japan.
References
[1] R.L. Jones, G.M. Gordon, G.H. Neils, Environmental degradation of materials in
boiling water reactors, in: Proc. 4th International Conf. on Environmental
Degradation of Materials in Nuclear Power Systems-Water Reactors, NACE,
1989, pp. 1–10.
[2] H.T. Tang, R.S. Pathania, A.R. McIlree, Overview of environmentally assisted
cracking in LWR components, in: Proc. Corrosion’2002, NACE, 2002. Paper No.
507.
[3] P.L. Andresen, F.P. Ford, Mater. Sci. Eng. A 103 (1988) 167–184.
[4] T. Shoji, Progress in the mechanistic understanding of BWR SCC and its
implication to the prediction of SCC growth behavior in plants, in: Proc. 11th
International Conf. on Environmental Degradation of Materials in Nuclear
Power Systems-Water Reactors, ANS, 2003, pp. 588–598.
[5] S. Suzuki, K. Kumagayi, C. Shitara, J. Mizutani, A. Sakashita, H. Tohkuma, H.
Yamashita, Maintenology 3 (2004) 65–70.
[6] T.M. Angeliu, P.L. Andresen, E. Hall, J.A. Sutliff, S. Sitzman, R.M. Horn,
Intergranular stress corrosion cracking of unsensitized stainless steels in
BWR environments, in: Proc. 9th International Conf. on Environmental
Degradation of Materials in Nuclear Power Systems-Water Reactors, TMS,
1999, pp. 311–317.
[7] NISA, Documents Presented at 5th Structural Integrity Evaluation Committee,
NISA, February 18, 2003 (in Japanese).
[8] M. Ando, K. Nakata, M. Itow, N. Tanaka, M. Koshiishi, R. Obata, Y. Miwa, Y. Kaji,
M. Hayakawa, CGR behavior of low carbon stainless steel of heat affected zone
in PLR piping weld joints, in: Proc. 13th International Conf. on Environmental
Degradation of Materials in Nuclear Power Systems-Water Reactors, CNS,
2007. CDROM.
[9] S. Suzuki, K. Takamori, K. Kumagayi, A. Sakashita, N. Yamashita, C. Shitara, Y.
Okamura, E-J. Adv. Maintan. 1 (2009) 1–29.
[10] S. Ooki, Y. Tanaka, K. Takamori, S. Suzuki, S. Tanaka, Y. Saito, T. Nakamura, T.
Kato, K. Chatani, M. Kodama, Study on SCC growth behavior of BWR shroud, in:
Proc. 12th International Conf. on Environmental Degradation of Materials in
Nuclear Power Systems-Water Reactors, TMS, 2005, pp. 365–376.
[11] P.L. Andresen, L.M. Young, W.R. Catlin, R.M. Horn, Stress corrosion crack
growth rate behavior of various grades of cold worked stainless steel in high
temperature water, in: Proc. Corrosion 2002’NACE, NACE, 2002. Paper No. 511.
[12] T. Shoji, G.F. Li, J.H. Kwon, S. Matsushima, Z.P. Lu, Quantification of yield
strength effects on IGSCC of austenitic stainless steels in high temperature
waters, in: Proc. 11th International Conf. on Environmental Degradation of
Materials in Nuclear Power Systems-Water Reactors, ANS, 2003, pp.
834–843.
[13] M.M.L. Castaño, R.M.S. Garcia, V.G.D. Diego, B.D. Gòmez, Crack growth rate of
hardened austenitic stainless steels in BWR and PWR environments, in: Proc.
11th International Conf. on Environmental Degradation of Materials in Nuclear
Power Systems-Water Reactors, ANS, 2003, pp. 845–854.
[14] P.L. Andresen, T.M. Angeliu, L.M. Young, Effect of martensite and hydrogen on
SCC of stainless steels and Alloy 600, in: Proc. Corrosion’2001, NACE, 2001.
Paper No. 228.
[15] P.L. Andresen, M.M. Morra, J. Nucl. Mater. 383 (2008) 97–111.
[16] Z.P. Lu, T. Shoji, Y. Takeda, Y. Ito, A. Kai, S. Yamazaki, Corros. Sci. 50 (2008) 561–
575.
[17] Z.P. Lu, T. Shoji, Y. Takeda, A. Kai, Y. Ito, Corrosion 63 (2007) 1021–1032.
[18] Z.P. Lu, T. Shoji, F.J. Meng, Y.B. Qiu, T.C. Dan, H. Xue, Corros. Sci. 53 (2011) 247–
262.
[19] Z.P. Lu, T. Shoji, T. Dan, Y.B. Qiu, T. Yonezawa, Corros. Sci. 52 (2010) 2547–
2555.
[20] Z.P. Lu, T. Shoji, Y. Takeda, Y. Ito, S. Yamazaki, Corros. Sci. 50 (2008) 698–712.
[21] S. Roychowdhury, V. Kain, M. Gupta, R.C. Prasad, Corros. Sci. 53 (2011) 1120–
1129.
[22] K. Kumagai, S. Suzuki, J. Mizutani, C. Shitara, K. Yonekura, M. Masuda, T.
Futami, Evaluation of IGSCC growth behavior of 316NG PLR piping in BWR, in:
2004 ASME Pressure Vessels and Piping Division Conference, ASME, 2004, pp.
217–223.
[23] T. Arai, K. Watanabe, K. Kako, Y. Miyahara, SCC growth behavior of stainless
steel in the region near the weld fusion boundary, in: 55th Material and
Corrosion Symposium, JSCE, 2008, pp. 35–38.
[24] M. Itow, S. Suzuki, SCC growth and retardation behavior of low carbon
stainless steel piping in the region near the weld fusion boundary, in: 55th
Material and Corrosion Symposium, JSCE, 2008, pp. 31–34.
[25] Z.P. Lu, T. Shoji, Y. Takeda, Y. Ito, A. Kai, N. Tsuchiya, Corros. Sci. 50 (2008) 625–
638.
[26] Z.P. Lu, T. Shoji, F.J. Meng, Y.B. Qiu, H. Xue, Y. Takeda, K. Negishi, Corros. Sci. 53
(2011) 1916–1932.
 Z. Lu et al. / Journal of Nuclear Materials 423 (2012) 28–39
[27] K. Watanabe, NISA’s Communication Activities for Intelligible Explanation,
JNES, 2010. <http://www.jnes.go.jp/seismic-symposium10/presentationdata/
15_sessionD/D-12E.pdf> (in Japanese).
[28] J.H. Kim, R.G. Ballinger, Corrosion 64 (2008) 645–656.
[29] K. Negishi, Evaluation of Stress Corrosion Cracking Characteristic of Weldment
of 316 l Stainless Steels Piping Mockups Influenced by Thermal Aging. Master
Thesis, Tohoku University, 2009.
[30] OIM, OIM Analysis for Windows 5.0, User Manual, Texsem Laboratories Inc.,
Utah, USA, 2005.
[31] U. Ehrnstén, P.A. Aaltonen, P. Nenonen, H.E. Hänninen, C. Jansson, T.M. Angeliu,
Intergranular cracking of AISI 316NG stainless steel in BWR environment, in:
Proc. 10th International Conf. on Environmental Degradation of Materials in
Nuclear Power Systems-Water Reactors, NACE, 2001. CDROM.
[32] S. Suzuki, K. Takamori, K. Kumagayi, S. Ooki, Y. Okamura, T. Fukuda, H.
Yamashita, T. Futami, JHPI (Pressure Technology) 42 (2004) 188–198 (in
Japanese).
[33] T. Shoji, Z.P. Lu, S. Yamazaki, The effect of strain-hardening on PWSCC of
nickel-base alloys 600 and 690, in: Proc. 14th International Conf. on
Environmental Degradation of Materials in Nuclear Power Systems-Water
Reactors, ANS, 2009, pp. 220–238.
[34] Z.P. Lu, H. Xue, T. Shoji, Crack branching and its effect on environmentally
assisted cracking in high temperature water environments, in: 2010 ASME
Pressure Vessels and Piping Division Conference, ASME, 2010. PVP2010-25818.
[35] T. Igarashi, Y. Miwa, Y. Kaji, T. Tsukada, J. Power Energy Syst. 2 (2009) 1188–
1196.
[36] JNES, Report for the Verification of Low Crack Growth Rate Region of Low
Carbon Stainless Steels, JNES, 2010 (in Japanese).
[37] JNES IGSCC Reports, 2005, 2006, and 2007, JNES. <http://www.jnes.go.jp> (in
Japanese).
[38] M. Itow, M. Kikuchi, N. Tanaka, J. Kuniya, M. Yamamoto, S. Suzuki, S.
Namatame, T. Futami, SCC growth rates and reference curves for low carbon
stainless steels in BWR environments, in: 2004 ASME Pressure Vessels and
Piping Division Conference, ASME, 2004, pp. 167–173.
[39] M. Tsubota, Y. Katayama, Y. Saito, T. Kaneko, Stress corrosion cracking growth
behavior of cold worked austenitic stainless steel in high temperature water,
39
in: Proc. 12th International Conf. on Environmental Degradation of Materials
in Nuclear Power Systems-Water Reactors, TMS, 2005, pp. 167–181.
[40] Z. Jiao, G.S. Was, J. Nuclear, J. Nucl. Mater. 382 (2008) 203–209.
[41] S. Lozano-Perez, T. Yamada, T. Terachi, M. Schroder, C.A. English, G.D.W. Smith,
C.R.M. Grovenor, B.L. Eyre, Acta Mater. 57 (2009) 5361–5381.
[42] F.P. Ford, Corrosion 52 (1996) 375–395.
[43] P.M. Scott, P. Combrade, On the mechanism of stress corrosion crack initiation
and growth in alloy 600 exposed to PWR primary water, in: Proc. 11th
International Conf. on Environmental Degradation of Materials in Nuclear
Power Systems-Water Reactors, ANS, 2003, pp. 29–38.
[44] T. Shoji, Z.P. Lu, H. Murakami, Corros. Sci. 52 (2010) 769–779.
[45] N. Birks, G.H. Meier, Introduction to High Temperature Oxidation of Metals,
Edward Arnold, 1983.
[46] T. Shoji, Localized and Accelerated Oxidation and Stress Corrosion Cracking-
Role of Stress, Strain, Hydrogen and Microstructures, Quantitative Micro-Nano
(QMN) Approach to Predicting Stress Corrosion Cracking in Water-Cooled
Nuclear Plants, CDROM, 2010.
[47] T. Shoji, Z.P. Lu, H. Xue, Y.B. Qiu, K. Sakaguchi, Quantifying crack tip oxidation
kinetics parameters and their contribution to stress corrosion cracking in high
temperature water, in: 2010 ASME Pressure Vessels and Piping Division
Conference, ASME, 2010. PVP2010-25238.
[48] A. Turnbull, Brit. Corros. J. 15 (1980) 162–171.
[49] A. Turnbull, Corros. Sci. 34 (1993) 921–960.
[50] A. Turnbull, D.H. Ferriss, Corros. Sci. 27 (1987) 1323–1350.
[51] A. Turnbull, Corros. Sci. 39 (1997) 789–805.
[52] M. Psaila-Dombrowski, A. Turnbull, R.G. Ballinger, Implication of Crevice
Chemistry for Cracking of BWR Recirculation Inlet Safe Ends. Life Prediction of
Corrodible Structures, NACE, 1994.
[53] D.D. Macdonald, M. Urquidimacdonald, Corros. Sci. 32 (1991) 51–81.
[54] D.D. Macdonald, P.C. Lu, M.U. Macdonald, T.K. Yeh, Corrosion 52 (1996) 768–
785.
[55] G.R. Engelhardt, D.D. Macdonald, M. Urquidi-Macdonald, Corros. Sci. 41 (1999)
2267–2302.
[56] H. Xue, Z.J. Li, Z.P. Lu, T. Shoji, Nucl. Eng. Des. 241 (2011) 731–738.