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ScienceDirect
Defence Technology xx (2015) 1e10
www.elsevier.com/locate/dt

Stress corrosion cracking behaviour of gas tungsten arc welded super

austenitic stainless steel joints
M. VINOTH KUMAR a,*, V. BALASUBRAMANIAN b,1, S. RAJAKUMAR b,
SHAJU K. ALBERT c
a

Department of Manufacturing Engineering, Annamalai University, Annamalai Nagar, Tamil Nadu 608002, India
Center for Materials Joining and Research (CEMAJOR), Department of Manufacturing Engineering, Annamalai Nagar, Tamil Nadu 608002, India
c
Materials Technology Division, Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam, Tamilnadu 603102, India
Received 13 May 2015; accepted 15 May 2015
Available online

Abstract
Super 304H austenitic stainless steel with 3% of copper posses excellent creep strength and corrosion resistance, which is mainly used in heat
exchanger tubing of the boiler. Heat exchangers are used in nuclear power plants and marine vehicles which are intended to operate in chloride
rich offshore environment. Chloride stress corrosion cracking is the most likely life limiting failure with austenitic stainless steel tubing. Welding
may worsen the stress corrosion cracking susceptibility of the material. Stress corrosion cracking susceptibility of Super 304H parent metal and
gas tungsten arc (GTA) welded joints were studied by constant load tests in 45% boiling MgCl2 solution. Stress corrosion cracking resistance of
Super 304H stainless steel was deteriorated by GTA welding due to the formation of susceptible microstructure in the HAZ of the weld joint and
the residual stresses. The mechanism of cracking was found to be anodic path cracking, with transgranular nature of crack propagation. Linear
relationships were derived to predict the time to failure by extrapolating the rate of steady state elongation.
Copyright 2015, China Ordnance Society. Production and hosting by Elsevier B.V. All rights reserved.

Keywords: Super 304H; Chloride stress corrosion cracking; Constant load test; Gas tungsten arc welding

1. Introduction
Austenitic stainless steels are the desired material for use in
high temperatures under highly corrosive environment. Heat
exchangers are used in nuclear power plants and marine vehicles which are intended to operate in chloride rich offshore
environment. The efficiency of the power cycle is function of
the operating temperature and pressure. Development and
selection of materials with required high temperature strength
and corrosion resistance is vital in further improvement in
* Corresponding author. Tel.: 91 9751014430 (mobile).
E-mail addresses: vinothmecho@gmail.com (M. VINOTH KUMAR),
visvabalu@yahoo.com (V. BALASUBRAMANIAN), srkcemajor@gmail.
com (S. RAJAKUMAR), shaju@igcar.gov.in (S.K. ALBERT).
Peer review under responsibility of China Ordnance Society.
1
Tel.: 91 9443412249 (mobile).

efficiency of the power cycle [1,2]. Recently developed Super

304H austenitic stainless steel with excellent creep strength
and corrosion resistance is mainly used in heat exchanger
tubing of the boiler. The addition of 3 wt.% Cu to Super 304H
enhances the precipitation strengthening of the alloy by
precipitating out fine, stable and coherent Cu rich particles at
elevated temperatures [3].
Stainless steels resist general corrosion but are susceptible
to localized corrosion such as pitting, and stress corrosion
cracking (SCC) in chloride environments [4]. SCC is the most
likely life limiting failure in boilers with austenitic stainless
steel tubing [5]. SCC is caused by the synergic and simultaneous action of tensile stress, environment and susceptible
microstructure [6]. The microstructure depends on the chemical composition and manufacturing methods. Welding is
considered as the major manufacturing method for pressure
equipments in power plants [7]. Welding may alter the

http://dx.doi.org/10.1016/j.dt.2015.05.009
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Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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Table 1
Chemical composition (wt.%) of parent metal (PM) and filler metal (FM).

PM
FM

Si

Mn

Cr

Ni

Cu

Nb

Mo

0.086
0.1

0.23
0.3

0.81
3.3

0.021
<0.01

0.0003
<0.01

18.18
18.3

9.06
15.7

0.095
0.16

3.080
2.9

0.045
0.5

e
0.7

0.0039
e

Table 2
Tensile properties of parent metal and weld joint.

Parent metal
Weld joint

0.2% yield
strength YS/MPa

Ultimate tensile
strength UTS/MPa

Elongation in 25 mm
gauge length/%

Joint efficiency /%

284.2
349.6

575.8
614.6

71.8
52.3

e
106.7

favorable parent metal microstructure and induce residual

stresses in the joints. In some cases the residual stress may
exceed the tensile stress of the material, resulting in worsening
of SCC susceptibility of the material [4,8]. The addition of Nb
to the steel and weld metal is beneficial for stabilizing C in the
matrix to avoid sensitization, while the effect of nitrogen on
SCC in parent metal is considered beneficial, and for the welds
it remains complicated due to their inhomogenous dendritic
cast structure [9].
In the absence of analytical approaches to predict SCC,
testing becomes vital. In actual conditions, SCC tends occur
over long periods of time; hence the SCC tests are accelerated
by using highly aggressive environments, constantly
increasing the load/strain. The results of accelerated tests can
be extrapolated to predict the long term service life of the
structure [10]. The test methods for SCC are classified as
constant load tests, constant strain tests and slow strain rate
tests based on mode of specimen loading [11]. Recent works
in Refs. [12,13] on SCC of Super 304H using constant strain
method revealed the SCC susceptibility of the Super 304H
under larger strain and improper heat treatment conditions.
In this present work, the SCC susceptibility of Super 304H
parent metal and gas tungsten arc welded (GTA) joints were
studied by recording the corrosioneelongation curves during constant load tests in boiling MgCl2 solution.
2. Experimental details
The parent metal used in this investigation was Super 304H
austenitic stainless steel with distinct addition of 3 wt% of
copper. Super 304H was received in annealed condition
(1145  C), in the form of tubes with outer diameter of

57.1 mm and wall thickness of 3.5 mm. For GTA welding, the
joints with single V butt configuration were welded with
addition of filler metal. Filler metal composition was suitably
modified to achieve delta ferrite free weld metal by increasing
the Ni content; the resultant weld metal microstructure was
fully austenitic, as preferred in high temperature applications
[9]. Mo was added to avoid the risk of hot cracking in the fully
austenitic weld metal by modifying the S inclusions and
enhance the resistance to pitting corrosion [14,15]. The
chemical compositions of the parent metal and filler metal are
presented in Table 1. The welding was carried out with
average heat input of 0.68 kJ/mm, in which argon was used as
the shielding and purging gas.
The specimens for transverse tensile test and SCC tests
were extracted from the parent metal and weld joints using
wire-cut electric discharge machining. The tensile properties
of as-received parent metal and weld joints are listed in Table
2. In order to reveal the susceptibility of Super 304H parent
metal and weld joint to intergranular corrosion (IGC), the
specimens were subjected to oxalic acid etch test as per ASTM
A262 practice A. The specimens were probed under light
microscope to reveal the level of Super 304H's susceptibility to
IGC before and after welding.
The SCC test was carried out using the smooth tensile
specimen (shown in Fig. 1) in a custom-built constant load
setup with maximum loading capacity of 10 kN. The applied
loads are measured using a load cell with an accuracy of
10 N. The strain measurements were done using an LVDT
with measurable range of 5 mm and an accuracy of <1 mm.
The schematic representation of the SCC constant load setup
is shown in Fig. 2. The environment for SCC testing of Super
304H was chosen as 45% MgCl2 boiling at 155  C, and the

Fig. 1. Schematic representation of the SCC constant load setup.

Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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M. VINOTH KUMAR et al. / Defence Technology xx (2015) 1e10

tests were conducted in accordance with ASTM G36. The

constant load SCC tests were conducted for parent metal and
weld joints of Super 304H at stress levels of 100%, 80%, 60%
and 40% of the parent metal's yield strength. The specimens
for microstructure analysis were polished and etched using
Glyceregia. The fracture surfaces of the SCC specimens were
ultrasonically cleaned and analyzed using scanning electron
microscopy (SEM) to reveal the modes of failure. Energy
dispersive spectroscopy (EDS) attached with SEM was used to
reveal the elemental composition of interested spots in fracture
surface.
3. Results
3.1. Microstructure

Fig. 2. Schematic representation of the SCC constant load setup with boiling
MgCl2.

The SEM micrograph of parent metal is shown in Fig. 3,

which cons(a)ists of equiaxed austenitic grains with annealing
twins and precipitates (marked by arrows). The precipitates in
parent metal were chemically extracted from the austenite

Fig. 3. SEM micrograph of parent metal and weld joint.

Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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Fig. 4. Oxalic acid etched structure of weld metal and HAZ.

Fig. 5. Typical corrosion elongation curve of Super 304H and its parameters in
boiling MgCl2 solution.

shows grain coarsening due to the weld thermal cycles, however no liquation of grain boundaries nor sensitization is
observed from SEM micrograph.
The fusion zone of the weld next to fusion line is shown in
Fig. 3(e) which shows the mixed morphology (cellular and
dendritic) of the austenite in this zone. The white dotted line
marks the transition of the austenitic weld from dendrite near
the fusion line to cell morphology towards the weld enter. The
magnified image of the area marked in Fig. 3(e) is shown in
Fig. 3(f). The marked arrow indicates the primary ferrite
dendritic core formed by F-A solidification mode and subsequently transformed to secondary austenite by solid state
diffusion. This confirms that both A type (cellular) and F-A
type of solidification have prevailed in the fusion zone next to
fusion line [16].
3.2. Oxalic acid etch structure

matrix, and their XRD pattern is shown in Fig. 3(b). The XRD
pattern confirmed the presence of Nb(C,N), M23C6 carbides in
the parent metal. The SEM micrograph of weldmetal in the
center of the joint is shown in Fig. 3(c), which reveals fully
austenitic grains with cellular morphology and carbides (NbC,
M23C6) precipitated along the boundaries. The fusion line (FL)
of the weld joint shown in Fig. 3(d) reveals the epitaxial grain
growth. The heat affected zone (HAZ) next to the fusion line

The oxalic acid etch structure of weld metal is shown in

Fig. 4(a), which reveals the end grain pits in austenitic weld
metal. The etch structure of HAZ shown in Fig. 4(b) reveals
the step structure among the grains (marked as 1), few deep
end grain pits (marked as 2) and dual structure in which a
single grain is not completely surrounded by the ditches
(marked as 3). The etch structures of both weld metal and
HAZ were acceptable as per ASTM A262 and show no

Fig. 6. Corrosion elongation curves for parent metal and weld joints of Super 304H in boiling MgCl2 at 100%, 80%, 60% and 40% of the yield strength.
Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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susceptibility to intergranular attack associated with chromium

carbide precipitation.
3.3. Corrosion elongation curves
The corrosion elongation curve for unwelded parent metal
tested at 80% of its yield strength in boiling MgCl2 is shown in
Fig. 5, and the parameters such as iss, tss and tf were derived
from this curve. The slope of the curve in the secondary region
before the time to transition (tss) from secondary region to
tertiary region represents the rate of steady state elongation
(iss), where the tf represents the time to complete fracture. The
corrosion elongation curves of parent metal and weld joint for
all test conditions are shown in Fig. 6, and the evaluated parameters are listed in Table 3. The corrosion elongation curves
provide information about the SCC cracking mechanisms
involved in the parent metal and weld joint of Super 304H
austenitic stainless steel [17].
The relationship between the applied stress and the tf for
parent metal and weld joint of Super 304H is shown in Fig. 7,
which reveals the significant degradation in SCC resistance of
Super 304H subjected to welding, as the tf of weld joint is
lower than that of parent metal at their respective stress level.
The ratio of tss to tf shown in Table 3 is used to determine the
most prominent mode of degradation (corrosive or mechanical) active in their respective test conditions. The typical
values of tss/tf for 316 stainless steels in stress corrosion range
was reported to be ~0.6 [18]. In the case of Super 304H parent
metal and weld joint, the value of tss/tf tends to increase with
the decrease in applied stress typical of N alloyed steels, as
reported elsewhere for 0.25% N alloyed austenitic stainless
steels [17]. This implies that the time in the tertiary region, i.e.
the time for fracture after crack initiation, decreases steadily
with the decrease in applied stress level, whereas the steady
state elongation rate (iss) decreases with the increase in tf and
the decrease in applied stress. Puiggali et al. [18] described the
crack growth rate (Vc) as,
Vc

Fig. 7. Relationship between applied stress and time to failure.

Fig. 8. Prediction of time to failure of Super 304H parent metal and weld joint
by SCC in boiling MgCl2.

sr is ultimate tensile strength. The crack growth rate in terms

of mm2/h was calculated for all the test conditions and listed in
Table 3. It was found that, for both parent metal and weld
joint, Vc was higher in the stress dominant region (1.0  YS),
while Vc decreased at 0.8  YS indicating the transition point
to SCC dominant region and continues to increase from
thereof, till the corrosion dominant region (0.4  YS), where
the highest value of Vc was recorded.



Cracking surface S0
s

1
Propogation time tp
sr

where So is initial cross section; tp is time for crack propagation after crack initiation (tss); s is initial applied stress; and

Table 3
Corrosion elongation curve parameters for Super 304H in boiling MgCl2 solution.
Material

Applied tensile
stress/MPa

% of applied
tensile stress

Parent metal

280
230
170
110
280
230
170
110

1.0
0.8
0.6
0.4
1.0
0.8
0.6
0.4

Weld joint










YS
YS
YS
YS
YS
YS
YS
YS

Time to
failure tf/h

Time to
transition tss/h

tss/tf

Elongation
rate iss/(mm$s1)

Crack growth
rate Vc/(mm2$h1)

6.75
12.17
22.17
25.92
4.17
9.75
10.08
11.00

2.75
5.32
14.80
19.65
1.25
2.50
6.10
7.97

0.48
0.5
0.67
0.75
0.3
0.26
0.6
0.72

2.70E-06
6.15E-07
2.01E-07
1.66E-07
1.32E-03
5.33E-06
1.98E-07
2.42E-08

1.57
1.07
1.17
1.58
1.81
0.92
2.03
3.12

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3.4. Prediction of time to failure

The calculated corrosion elongation curve parameters
shown in Table 3 can be used for prediction of time to failure
by extrapolation of time scale. The logarithmic relationship
between iss and tf is always linear and independent of pH,
concentration of ion, temperature and material [17,19]. The
Fig. 8 reveals that such a linear relationship also exists between the iss and tf of parent metal and weld joints of Super

304H. The mathematically expressed linear relationships

iss 2.08 tf  2.11 (for parent metal) and
iss 40.66 tf 36.37 (for weld joint) can be used for prediction of time to failure.
3.5. Fracture surfaces
The SCC characteristics in the directions parallel and
normal to loading, for the parent metal and weld joint are

Fig. 9. Fracture characteristics of Super 304H parent metal SCC specimens tested in boiling MgCl2 solution at different stress levels.
Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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Fig. 10. Fracture characteristics of Super 304H GTAW joints SCC specimens tested in boiling MgCl2 solution at different stress levels.

shown in Figs. 9 and 10 respectively. The cracks are oriented

normal to the loading direction, and the number of cracks and
crack width decreases with the decrease in applied stress for
both parent metal (refer Fig. 9(a)) and weld joint (refer
Fig. 10(a)). The fracture surfaces of the parent metal and weld
joint at low magnification (refer Figs. 9(b) and 10(b)) reveal
brittle mode of failure, with no reduction in cross sectional
area. The Figs. 9(c) and 10(c) confirms the transgranular mode
of crack propagation for both parent metal and weld joint at all
stress levels, with de-cohesion of grains at the grain
boundaries.

The microstructural characteristic features of SCC in parent

metal and weld joint are shown in Fig. 11. In parent metal, the
interface between the matrix and coarse carbides are identified as
the source of crack initiation, as indicated by arrow in Fig. 11(a).
The other crack initiation sites are the high number of slip steps at
the edges of the specimen, which promotes the formation and
growth of corrosion pits in large numbers by anodic dissolution,
as shown in Fig. 11(c). The parent metal with lesser applied stress
level provides lesser crack initiation sites by slips at the edges and
hence the crack propagates by branching and interconnecting
other probable cracks (Fig. 11(e)).

Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
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Fig. 11. Crack propagation characteristics in SCC specimen tested in boiling MgCl2 solution at different applied stress levels.

In the weld joint the cracks initiate and propagate in the

HAZ and fusion line/HAZ region, which are more susceptible
to SCC, as shown in Fig. 11(b). The weld metal posses better
resistance to SCC (refer Fig. 11(e) and (f)), however the
presence of carbides results in initiation of the crack and these
cracks gets interconnected to the main crack propagating in to
the weld metal, as shown in Fig. 11(d).

The crack propagation micrograph of weld joint tested at

lower applied stress is shown in Fig. 11(f), which reveals the
initiation of crack in HAZ region and its transgranular propagation into the weld metal. However, no crack is observed in
the weld metal of the joint tested at lower applied stress (refer
Fig. 11(f)). The EDS spectra of fracture surfaces of parent
metal and weld joint are shown in Fig. 12(a) and (b),

Fig. 12. EDS elemental analysis of fracture surface.

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respectively. The presence of chloride in the fracture surfaces

confirms the interaction of chloride environment with the test
specimens to cause SCC failure.
4. Discussion
The SCC was transgranular at all the stress levels i.e. SCCdominated and stress-dominated regions, in parent metal and
weld joint, which is characteristic of the higher steady elongation observed [20]. Out of the numerous mechanisms proposed to explain SCC behaviour the anodic path cracking
mechanism (APC) belongs to the cracking of austenitic
stainless steel in chloride environment [21]. The mechanism
proposed by Nishimura for transgranular SCC is also valid for
this work, where the entire cracking is based on a cyclic event
of passive film formation and rupture, dealt elsewhere in detail
[22,4]. The anodic metal dissolution and passive film formation at the crack tip result in dislocation pile-up at the crack
tip, resulting in an increase in local stresses higher than the
applied local stress at the vicinity of the crack tip. The film
ruptures when the local stress exceeds a critical value and a
crack propagates by exposing fresh metal to repeat the process. Such event of crack propagation was recorded as noise
peaks in corrosion elongation curves until tss, resulting in
steady state elongation (refer Fig. 13). The downward arrows
indicate the critical stress at which the film ruptures and the
upward arrows indicate the applied mean stress.
In weld joints, HAZ is the most susceptible region to SCC due
to the metallurgical changes caused by weld thermal cycles. The
oxalic acid etch test reveals a dual structure in the HAZ, confirming the deterioration in the corrosion resistance of the zone.
In the worst case, the welding residual stress can be superimposed
and may be as high as yield strength of the material [15,4]. The
microstructure examination of the SCC weld joints reveals that
the failure occurred between the weld interface and HAZ, indicating the susceptibility of the zone to SCC. At lower applied
stress (0.4  YS), the cracks are found to initiate in the HAZ and
propagate in to the weld metal. The crack initiation sites are not
observed in the weld metal at lower stress (refer Fig. 11(f)), which

Fig. 13. Magnified view of serrations observed in corrosion elongation curves

of constant load SCC specimens tested in boiling MgCl2 solution.

confirms the enhanced pitting resistance of weld metal by Mo

addition [15]. The cracks initiated in the weld metal at higher
stress (refer Fig. 11(d)) are attributed to the local strain field
around the interface of matrix and precipitates, caused by the
misfit between matrix and precipitates.
5. Conclusions
1) The SCC resistance of Super 304H stainless steel is
deteriorated by GTA welding due to the detrimental
microstructural changes in the HAZ of the joint and the
residual stresses caused by the weld thermal cycles.
2) Linear relationships are derived from the elongation rate
and time to failure, from which it is possible to extrapolate
and predict the time to failure from the corrosion elongation curves.
3) The stress corrosion cracking is transgranular in nature
under all the test conditions, and the cracking mechanism
is found to be anodic path cracking.
4) Molybdenum is found to improve the stress corrosion
cracking resistance of weldmetal due to its enhanced
resistance for pitting corrosion.

Acknowledgements
The authors wish to express their sincere thanks to M/s
Mailam India Ltd, Pondicherry, India for providing the funds
to carry out this research work through Mailam India Research
(MIR) Fellowship, M/s Salzgitter Mannesmann Stainless
Tubes Italia Srl, Italy for supplying the Super 304H tubes and
Department of Science and Technology (DST-SERB), Government of India, for providing the stress corrosion cracking
setup wide project no. SB/FTP/ETA-281/2012.
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Please cite this article in press as: VINOTH KUMAR M, et al., Stress corrosion cracking behaviour of gas tungsten arc welded super austenitic stainless steel
joints, Defence Technology (2015), http://dx.doi.org/10.1016/j.dt.2015.05.009