Corrosion Science 42 (2000) 10051021

Stress corrosion cracking of a low alloy steel

to stainless steel transition weld in PWR
primary waters at 2928C
G.F. Li, J. Congleton*
Department of Mechanical, Materials and Manufacturing Engineering, Materials Division, The University
of Newcastle upon Tyne, NE1 7RU, UK
Received 19 April 1999; accepted 16 September 1999

Abstract
The eects of electrode potential and sulphate SO2
4 content in the water on the stress
corrosion cracking (SCC) of a low alloy steel austenitic stainless steel transition weld,
A508-309L/308L, in pressurised water reactor (PWR) primary side waters at 2928C have
been studied using slow strain rate testing (SSRT). The weld was post-weld-heat-treated at
6208C for 20 h before testing. Results showed that the transition zone in the weld had a
higher susceptibility to SCC than either the bulk stainless steel or the bulk low alloy steel.
The SCC in the transition zone was mainly intergranular in the austenitic layer, but
transgranular cracking occurred at the interface and in the low alloy steel. The minimum
potential for SCC, Ec , in each water used was higher than the free corrosion potential
range of 880 to 660 mV (SHE) and the susceptibility to SCC increased with increasing
electrode potential. In sulphate doped waters, crack growth rates >2  106 mm/s occurred
at high applied potentials in the low alloy steel and/or in the austenitic layer but some less
severe cracking occurred at the interface. Contamination of the water with SO2
4 increased
the SCC susceptibility by both decreasing the minimum potentials for cracking and
increasing the crack growth rate. However, the data suggest that transition welds should be
immune from SCC in typical PWR primary side coolant water at 2928C even in the
unlikely event that a break in the stainless steel cladding allowed access of the cooling
water to the transition joint area. # 2000 Elsevier Science Ltd. All rights reserved.

* Corresponding author. 24 Eppleton Close, Langley Park, Durham, DH7 9UX, UK. Tel.: +440191-373-5187.
0010-938X/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 9 9 ) 0 0 1 3 1 - 6

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

Keywords: Dissimilar metal weld; Stress corrosion cracking; High temperature water; Electrode potential; Water chemistry; Pressurised water reactor

1. Introduction
Degradation of components in light water reactor nuclear power plants plus
the desire for high plant integrity have stimulated many investigations on
environment-assisted cracking of low alloy and stainless steels in high
temperature water [1,2]. Both electrode potential and sulphate SO2
4 content
in water are important environmental parameters controlling the SCC
susceptibility of these materials [36]. However, little attention has been paid
to the SCC of dissimilar metal welds used to connect stainless steel piping to
the low alloy steel vessel, although recently Hurst et al. [7]. found that SCC
can occur in the transition zone of such welds at high potentials (125 and
+75 mV) but not at the free corrosion potential (about 725 mV) in PWR
primary water. All potentials are quoted with respect to the Standard
Hydrogen Electrode scale.
The dissimilar metal welds constitute both material and structural
discontinuities in reactors. Between the bulk low alloy steel parent material and
the bulk high alloy weld metal there exists a transition zone that has complicated
microstructure and varying chemical composition. In addition to stress from the
working load, thermally induced stresses will be present because the thermal
conductivities and expansion coecients of the austenitic and ferritic steels are
dierent [8]. Two dierent types of transition weld are in common use, one using
austenitic stainless steels such as 309L/308L as ller metals and the other using
nickel alloys such as I-82 and I-182 as llers. The present research is related only
to the former type of weld.
Environmental degradation at low alloy steelstainless steel welds have been
reported in PWRs in the USA and France [9,10]. These defects reported were
all nucleated from the outside surface and attributed to high stresses plus
either the presence of contaminants from the insulation and protective
materials [9] or atmospheric corrosion [10]. The inner surfaces of the
transition welds in a reactor are protected with austenitic stainless steel
cladding. In the unlikely occurrence of a break in the cladding, say due to a
welding defect or fatigue or thermal ageing embrittlement, and the remote
possibility that such a break would lie above a transition weld, direct contact
between the water coolant and the weld would result with a risk of
environment-assisted-cracking.
The present research is concerned with the SCC susceptibility of such welds in
high temperature water at 2928C. The eects of electrode potential and
SO2
4 content in water on the SCC behaviour are reported here.

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1007

2. Experimental
The low alloy steelstainless steel weld, A508-309L/308L, was made at The
Welding Institute (UK) by manual-metal-arc-welding a butter layer of 309L
stainless steel followed by 15 layers of 308L stainless steel to a block of A508 low
alloy steel. Table 1 lists the chemical compositions of the materials used. The
material was post-weld-heat-treated at 6208C for 20 h prior to manufacturing the
SSRT specimens.
The microstructure and chemical composition prole of the weld was
determined by optical microscopy, scanning electron microscopy (SEM) and
energy dispersion X-ray (EDX) analysis. The low alloy steel part was etched in
3% Nital. The high alloy part was electrolytically etched at 6 V for 510 s, either
in a mixed acid solution (H3PO3: 55 ml, H2SO4: 12 ml, pure water: 33 ml) or in
10% oxalic acid solution, both of which dissolved carbides preferentially from
polished sections and revealed the d-ferrite. The micro-hardness distribution was
measured using a pyramidal diamond and a 50 g load.
Dumb-bell shaped tensile specimens, as shown in Fig. 1, designed to localise
stress to zones of interest were used for the SCC testing. The specimens were
machined after chemical etching the blanks so that the interface could be
accurately positioned at the minimum diameter and perpendicular to the loading
axis of the specimen. The oset stress, Soff , that indicated the onset of yield and
the maximum stress, Smax , were calculated by dividing the appropriate loads by
the original minimum cross sectional area of the specimen.
Three simulated PWR primary waters with dierent SO2
4 contents were used.
The `good water' was made up by adding 2.2 ppm lithium (from LiOH
H2O) and
1200 ppm boron (from H3BO3) to deionised water. It had a pH value of 6.3 and a
conductivity of 18 mS/cm at room temperature. The deionised water had an
estimated SO2
4 impurity content of <10 ppb [11]. The two contaminated waters
were made by doping the good water with 60 and 150 ppb SO2
4 (from Li2SO4)
respectively. No obvious dierences in pH and conductivity were found among
the three waters. The various waters were purged with hydrogen gas to ensure a
low dissolved oxygen level (<5 ppb) during tests and an overpressure of 0.034
MPa hydrogen was maintained in the feed tank. The pH, conductivity and
dissolved oxygen were measured before and after every test to verify good water
quality.
Table 1
Chemical compositions of the materials used for making the weld (wt%)
Steel

Mn

Si

Mo

Ni

Cr

Cu

Co

A508
309La
308La

0.005
< 0.020
< 0.020

0.15
< 0.03
< 0.03

1.27
1.75
0.9

0.006
< 0.020
< 0.020

0.19
0.38
0.35

0.53

0.74
13.5
11

0.23
23
20

0.05

0.01

Average nominal values.

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

Slow strain rate tests were conducted using a refreshed autoclave rig. The
autoclave was made of Type 316 stainless steel, had a 14.3 mm internal diameter
by 135 mm long bore and gave a 16 ml free internal volume after the specimen
was inserted for testing. The specimens were polished to 1200 grit and rinsed with
methylated spirit and deionised water before loading, following the ASTM G49-85
[12] recommendations. The electrode potentials of the specimens were measured
using an Andresen-type external silversilver chloride (SSC) reference electrode
lled with deaerated 0.025 M KCl solution and a measuring instrument with
r1000 MO input impedance. The measured potentials were then converted to the
standard hydrogen electrode (SHE) scale. After the free corrosion potential of the
tested specimen became stable (rate of change <3 mV/h), an applied potential
was imposed if the specimen was to be tested under potentiostatic control. Almost
all of the tests were performed at a constant cross-head speed of 3.6  106 mm/s.
(Strain rates can not be calculated due to the specimen shape and the non-uniform
deformation of the dissimilar weld). The water ow rate was 56 ml/min.
After test, the fractured specimens were observed by both optical microscopy
and scanning electron microscopy. The depths of the largest stress corrosion
cracks present in each part of the specimen, i.e. the low alloy steel, at the interface
and in the stainless steel regions, were measured either from the fracture surface
or from a section cut on the diametric plane through the largest visible crack. For
some small cracks, the depths were estimated from the surface length by assuming
an aspect ratio for the crack of 0.5. Maximum crack growth rate was obtained by
dividing the largest crack depth by the total test time. Such values provide a
useful parameter for relative SCC susceptibility but do not necessarily indicative
magnitudes for crack growth rate that may occur in operating plant.

Fig. 1. Geometry of the dumb-bell shaped specimen.

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1009

3. Results
3.1. Weld characterisation
The microstructure of the LAS-309L/308 transition weld is shown in Fig. 2. The
bulk stainless steel consisted of austenite, about 4% d-ferrite and some carbides,
with the microstructure being similar from the 309L layer to the 308L layers due
to weld dilution. The bulk low alloy steel had an upper-bainitic microstructure
consisting of ferrite laths and inter-lath carbides, with the heat aected zone being
about 23 mm thick. A transition zone existed between the bulk materials. The
stainless steel part of the transition zone was austenite with carbide precipitation
at the grain boundaries, hereafter referred to as `the austenitic layer', which varied
in width from 10 to 200 mm along its length in the specimen. The grain
boundaries were easily etched in the oxalic acid solution, indicating that this layer
was sensitised. The low alloy steel part of the zone was an 0.30.4 mm thick
decarburization zone. A martensite-like layer was usually found at the interface
between the austenitic layer and the decarburized zone. The interface and the
austenitic layer had the highest microhardness in the weld and had Cr and Ni
concentrations intermediate between the bulk stainless steel and the low alloy
steel, as shown in Fig. 3.
3.2. Results of slow strain rate tests (SSRTs)
During SSRTs in the high temperature waters, some specimens failed either by
ductile failure in the bulk stainless steel about 12 mm away from the interface,
even though some stress corrosion cracks could be found at the interface, in the
low alloy steel part of the transition zone and in the bulk stainless steel of the
specimens, as shown in Fig. 4. Other specimens failed by SCC initially in the
transition zone and then mechanical shearing in the ligament of the bulk stainless
steel, Fig. 5. On all the specimens, numerous but shallow transgranular cracks
could be found at the slip steps in the bulk stainless steel in the necked region,
Fig. 6, which is not classied as SCC here. This is because it has been well
documented that such cracking is a characteristic of slow strain rate tests on
stainless steels in high temperature water. It occurs only at high strain values
during SSRTs and is of no practical signicance [1316].
Table 2 lists the test results. The maximum crack growth rates in the two
specimens tested at 100 mV in `good water' but at the dierent cross head
speeds of 1  106 and 3.6  106 mm/s were similar. Fig. 7 shows the maximum
crack growth rate versus electrode potential for individual specimens, irrespective
of location of cracking, and Fig. 8 shows the data for each of the three regions of
the joint. The crack growth rates increased with increasing electrode potential.
The minimum potential for SCC, Ec , was in the range 200 to 100 mV in the
good water, in the range 600 to 450 mV in the water doped with 60 ppb SO2
4
and in the range 300 to 200 mV in the water doped with 150 ppb SO2
4 : These

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

Fig. 2. A scheme and a photo showing the microstructure of the weld after post weld heat treatment at
6208C for 20 h.

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1011

Ec values were all anodic to the free corrosion potential range for specimens
(880 to 660 mV) for the weld in any of the waters.
Test results indicated that in sulphate doped waters, fast cracking, i.e.
cracking at a rate greater than 2  106 mm/s, occurs above a potential that can
be called Efc , the minimum potential for fast SCC. Efc values were between 200
to 100 mV in the 150 ppb SO2
4 water and between 0 to +100 mV in the 60 ppb
:
At
potentials
between
E
and Efc , SCC occurred at relatively low cracking
SO2
c
4
velocities (all <3  107 mm/s) and only in the low alloy steel part of the
transition zone, as shown in Fig. 4, and/or at the interface. Examination showed
that the cracks in the low alloy steel nucleated at sulphide inclusions. When the
electrode potential was increased above Efc , fast cracking (>2  106 mm/s)

Fig. 3. Chemical composition and micro-hardness (DHP) distributions of the weld.

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

occurred in the low alloy steel and/or in the austenitic layer and SCC could be
found in all the three regions of the weld, as shown in Figs. 5, 9 and 10. In the
low alloy steel part, SCC occurred not only in the decarburized zone but also in
the bulk zone less than 0.5 mm away from the interface, as shown in Fig. 9. The
crack nucleation was not only at sulphide-inclusions but also in the matrix.
The SCC cracks were transgranular in the low alloy steel and at the
interface but mainly intergranular in the austenitic layer.
Contamination of the good water with SO2
4 in the range from 60 to 150 ppb
raised the susceptibilities of the weld to SCC by decreasing the minimum
potentials for cracking for all of the three regions of the weld and increasing the
crack growth rates in all the three regions at a given potential. In the present
work, the minimum potential for SCC for the weld did not decrease systematically
content in the water but the addition of sulphate always
with increasing SO2
4
caused a reduction in the minimum potential for fast SCC.

Fig. 4. Fractograph of a specimen after SSRT at 2928C at an applied potential of 200 mV (SHE) in
water doped with 150 ppb SO2
4 :

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1013

4. Discussion
4.1. SCC of the transition zone in the weld
The data show that SCC occurred mainly in the transition zone of the
dissimilar weld, with the low alloy steel part being the most susceptible. The
greater susceptibility to SCC of the transition zone is not a consequence of the
specimen geometry generating higher stresses. The tensile stress dierence due to
initial diameter dierence is R2.5% in the region within 1 mm from the interface
and R9.4% in the region within 2 mm from the interface, but the transition zone
of the weld was contained within 0.4 mm from the interface.
The higher SCC susceptibility of the transition zone is due to both the
microstructure and chemical composition of that zone and the non-uniform
distributions in stress and strain across the weld during the slow strain rate test.
Compared with the bulk stainless steel, the austenitic layer in the transition zone
has low Cr% and Ni% and contains no d-ferrite. Each of these factors can
promote SCC. Lower Cr% will result in a looser and less protective oxide lm on
the surface [13]. Lower Ni% will lower the stacking fault energy and thereby give
a greater tendency for dislocation coplanar slip to form higher stress
concentration [18]. The absence of d-ferrite can increase the susceptibility of

Fig. 5. Fractograph of a specimen after SSRT at 2928C at an applied potential of100 mV (SHE) in
water doped with 150 ppb SO2
4 :

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

Fig. 6. Transgranular cracks at slip steps in the SS necked region of a specimen after SSRT at 2928C at
an applied potential of 600 mV (SHE) in water doped with 60 ppb SO2
4 :

Fig. 7. Maximum stress corrosion crack growth rate versus electrode potential for the weld during
SSRTs at 2928C in waters doped with dierent contents of SO2
4 :

G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

Table 2
Results of tests on the weld A508-309L/308L in the waters at 2928C

1015

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

austenitic stainless steels to intergranular SCC in high temperature water [19]. The
intergranular mode of SCC in the austenitic layer should result from the
sensitisation which can cause a signicant dierence in dissolution rate between
the matrix and the Cr-depleted grain boundaries [16]. The interface has a

Fig. 8. Maximum stress corrosion crack growth rate versus electrode potential for dierent regions of
the weld during SSRTs in waters at 2928C.

G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

1017

Fig. 9. Fractographs of a specimen after SSRT at 2928C at an applied potential of +100 mV (SHE) in
water doped with 60 ppb SO2
4 : (a) the low alloy steel side; (b) the stainless steel side.

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

complicated microstructure and a sharp change in Cr% from nearly 0 to about

14%, which may result in signicant dierences in electrochemistry between
adjacent areas in the waters and thereby cause SCC at the interface.
Austenitic stainless steels have lower yield strength but higher strain-hardening
exponent than low alloy steels. Therefore, the plastic deformations in the regions
near the interface of the weld will aect each other and non-uniform stress and
strain distributions will appear during the slow strain rate tensile test, which could
also contribute to the higher SCC susceptibility of the transition zone and nearby
low alloy steel. The strain distribution across a 316 stainless steel to A533B low
alloy steel joint with dumb-bell shaped specimen geometry has been calculated by
Feng [20] using a nite element analysis (FEA) procedure. He has shown that with
an applied stress of 450 MPa at the minimum section, which is beyond yield for
the specimen, the stress and strain in the low alloy steel are higher in the region
close to the interface than the remote to it, which should be an important reason
for the higher SCC susceptibility near the interface in the present tests. The
calculations also showed that the maximum strain appears in the stainless steel
about 12 mm from the interface, which is consistent with the site for the
mechanical failure by necking in experiments for specimens in which no SCC
occurred or for specimens in which the stress corrosion crack growth rate was too
low to prevent ductile overload failure in the stainless steel part of the specimen.

Fig. 10. Micro-section through the fracture surface in Fig. 9(a), showing SCC in the low alloy steel (left
below), along the interface (left) and along the grain boundaries in the stainless steel.

G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

1019

4.2. Eect of electrode potential

The susceptibility to SCC of the transition joints increased with increasing
applied potential, which suggests that anodic dissolution at the crack tip is the
main cracking mechanism. There are characteristic potentials, i.e. minimum
potentials for SCC, for each region of the weld in each of the water chemistries
used. In the present experiments, the minimum potential for SCC to nucleate at
the sulphide-inclusions in the low alloy steel part was almost always the minimum
potential for SCC of the weld.
Each characteristic potential may represent that potential at which the
environment at the crack tip achieves an appropriate critically aggressive
composition, as suggested by Macdonald and Cragnolino [3], or where the
dierence in dissolution rate between adjacent areas at a special site becomes large
enough to sustain crack-like morphology, as suggested by Congleton and Yang
[16]. Alternatively, the nature of the oxide lm on the surface may change
abruptly at the minimum potential for cracking [17].
The present data indicates that SCC only occurs at transition joints (post-weldheat-treated at 6208C for 20 h in this study), at relatively high applied potentials,
specically at potentials >600 mV, whereas the free corrosion potential range
for the weld in the simulated PWR primary waters was (880 to 660 mV).
Thus, SCC failures should not occur at transition welds at normal operating
temperature in a PWR even if the weld is in contact with the water coolant.
Oxygen contamination or another fault condition would need to raise the free
corrosion potential into the range of 600 to 200 mV for SCC to occur in the
low alloy steel and/or at the interface. If the corrosion potential was raised to
>200 mV, fast SCC may occur in the low alloy steel part and/or in the
austenitic layer of the weld. Such high potentials are unlikely to be achieved at
2928C in a PWR.
4.3. Eect of sulphate content in the water
Contamination of the good water with SO2
4 increased the susceptibilities of all
the three regions of the transition zone to SCC by decreasing the minimum
potentials for both SCC and fast SCC and by raising the crack growth rate at the
same potential. This is consistent with published data that show that SO2
4 reduces
the SCC resistance of both low alloy steels and austenitic stainless steels in high
content promotes higher
temperature waters [46]. Presumably the higher SO2
4
SCC susceptibility in the low alloy steel of the weld by generating a higher content
of S-bearing anions within the crack enclave. Andresen and Young [21] have
shown that 0.5 ppm S in the crack tip solution was sucient to induce a high
environmental crack growth rate in A533B steel tested in pure water.
The necessary level of SO2
4 in PWR primary water to induce SCC in the weld
at the free corrosion potential has not been determined, but it is expected to be
much higher than 150 ppb. For instance, the work of Shoji et al. [6] has shown

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G.F. Li, J. Congleton / Corrosion Science 42 (2000) 10051021

that 20 ppm SO2

4 was necessary to induce SCC in an A533B steel (0.014% S) at
the free corrosion potential in a simulated PWR primary side water at 2888C.
5. Conclusions
1. The transition zone of a low alloy steel to stainless steel transition joint had a
higher susceptibility to SCC than both the bulk stainless steel and the bulk low
alloy steel. The SCC in the zone was mainly intergranular in the austenitic layer
but transgranular cracking occurred both at the interface and in the low alloy
steel part of the joint.
2. The SCC susceptibility of the weld increased with increasing electrode potential
but the minimum potential for SCC was higher (more anodic) than the free
corrosion potential.
3. Contamination of the water with SO2
4 increased the SCC susceptibility of the
weld by both decreasing the minimum potential for cracking and by increasing
crack growth rate at the same potential.

Acknowledgements
This work was funded by H.M. Nuclear Installations Inspectorate, Health and
Safety Executive and is published with their permission. The views expressed in
this paper are those of the authors and do not necessarily represent the views of
the Inspectorate.
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