JMEPEG (2013) 22:17831789 ASM International

DOI: 10.1007/s11665-012-0461-3 1059-9495/$19.00

Effect of Strain Rate on Stress Corrosion Cracking of 316L

Austenitic Stainless Steel in Boiling MgCl2 Environment
A. Hassani, A. Habibolahzadeh, A.H. Javadi, and S.M. Hosseini

(Submitted May 1, 2012; in revised form November 22, 2012; published online December 27, 2012)

Stress corrosion cracking behaviors of AISI 316L austenitic stainless steel at slow strain rates in two
environments of air and MgCl2 at ambient temperature and 154 C were investigated. The results revealed
that a decrease in strain rate, during testing in boiling MgCl2 environment, led to a rigorous deterioration
of the mechanical properties of the material, causing brittleness of the steel. The results obtained from
fractography indicated that the samples tested in air had typical ductile fracture surface appearances, while
the fracture surfaces of the samples tested in a corrosive environment showed a combination of inter-
granular and transgranular fracture modes, having a brittle macroscopic appearance. The transgranular
mode became predominant as strain rate decreased. The results suggested that the presence of deformation
bands in front of crack tips were responsible for transgranular cracking caused by stress corrosion.

Keywords corrosion, ferrous metals and alloys, scanning electron
microscopy
1. Introduction
Stress corrosion cracking (SCC) is one of the most
important phenomena, which causes many engineering failures
in stainless steel pipes, ttings, and equipments at chemical and
petrochemical industries. This phenomenon, which is almost
unpredictable, occurs even at very low stresses like residual
stresses due to welding or machining leading to catastrophic
failures in industries (Ref 1-3). The total SCC damage can be
divided into two steps of induction time: the time necessary for
a crack to initiate on an apparently smooth surface, and crack
propagation time. The most important factors that affect SCC
are metallurgical (or internal) and environmental (or external)
factors. Although signicant investigations have been con-
ducted on this issue, still there is no comprehensive theory to
completely explain SCC phenomenon in alloys (Ref 4-6).
Among the common alloys employed in chemical indus-
tries, austenitic stainless steels are probably the most important
class of corrosion-resistant metallic materials. Their high Cr
content is responsible for formation of protective oxide lm
layers, and high Ni content enables the steel to remain
austenitic (Ref 7). Common austenitic grades of Ni-Cr and
Ni-Cr-Mo stainless steels are usually sensitive to SCC. This
type of cracking affects mostly the steels containing Ni, with
the greatest damage occurring in the most common range of Ni
content (Ref 8). SCC in stainless steels mainly occurs at
temperatures above 50 C in chloride environments (Ref 9).
The effect of Mo on SCC resistance of stainless steels depends
A. Hassani, A. Habibolahzadeh, A.H. Javadi, and S.M. Hosseini,
Faculty of Materials Science and Engineering, Semnan University,
35131-19111 Semnan, Iran. Contact e-mail: irsangestan@yahoo.com.
on the test environment (Ref 9). The MgCl2 data suggest that
Mo addition beyond 1.5% increases the SCC resistance of
stainless steel. No such pattern is in evidence in NaCl tests
(Ref 8). In addition, low carbon contents of stainless steels
decrease the susceptibility of the alloy to SCC due to lowering
the possibility of precipitation of chromium carbides in the
matrix. It has been suggested that the minimum resistance to
chloride SCC in austenitic stainless steel occurs when carbon
content is between 0.06 and 0.1% (Ref 8). Then, the 316L
austenitic stainless steel, which is a low-carbon-containing steel
and containing appropriate amount of Mo, has a noticeable
resistance to SCC compared to those with higher carbon
content.
In this paper, the effect of strain rate on SCC resistance of
316L austenitic stainless steel has been investigated.
2. Experimental Procedure
AISI 316L austenitic stainless steel specimens, with the
composition as shown in Table 1, were received for the
experimental investigation. Slow strain rate tensile test (SSRT)
was carried out to evaluate susceptibility of the steel to SCC in
boiling MgCl2 bath, according to NACE TM0198-98 standard
(Fig. 1) using INSTRON universal testing machine, model
6027. The specimens were machined according to ASTM E8
standard (Fig. 2). Strain rates were measured based on velocity
of cross-head displacement. To relax stresses and stabilize
dimensions of the specimens, the specimens were solution
treated at 1085 5 C for 120 min and then air cooled,
followed by heating at 300 C for 90 min. Surfaces of the
specimens were ground and polished by 0.25 lm diamond
paste and then rinsed. Two samples, as the reference samples,
were tested in air at ambient temperature and at 154 C,
respectively, at a strain rate of 1.1 9 10 4 s 1. The strain rates
of 1.1 9 10 4 s 1, 1.1 9 10 5 s 1, and 1.1 9 10 6 s 1 were
selected to evaluate effect of strain rate on SCC behavior of
the alloy in boiling MgCl2. Table 2 demonstrates the test

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Table 1 Chemical composition (wt.%) of AISI 316L
austenitic stainless steel
C S Si Mn Cr Ni Mo Cu V W Co

0.01 0.02 0.35 1.68 16.5 10.25 2.02 0.5 0.16 0.11 0.1

conditions of ve different experiments. Work hardening

exponent, n, was calculated from stress-strain curves using
the Hollomon equation, r = Ken (Ref 10). Macro- and
microfractography analyses of fracture surfaces were performed
using scanning electron microscope (SEM) make Camscan,
model MV2300. Samples of optical microscopy were prepared
by cutting cross-sectional proles out of the specimens,
grinding, and then polishing them by 0.25 lm diamond paste.
Longitudinal sections of the failed specimens were also
prepared for metallographic examinations. Samples were
cleaned by ultrasonic cleaner using 5% ethanol solution before
SEM examinations.

3. Results and Discussion

3.1 Slow Strain Rate Tensile Tests (SSRTs)

Figure 3 shows the engineering stress-strain curves. The
graphs shown in Fig. 4 are the resulting mechanical properties
of all samples, examined at low strain rate tensile tests. As seen
in Fig. 3, the graphs for all samples, except for the one tested at
room temperature, have serrated appearances. The serration
may implicate the occurrence of dynamic strain aging during
the tests. This behavior is usually observed at higher work
hardening rates and negative strain-rate dependence of ow
stress (Ref 10). Dynamic strain aging implies that a solute atom
must be able to make at least one diffusive jump while the alloy
is being deformed, and therefore the process is sensitive to
temperature and to strain rate (Ref 10). Accordingly, it is
evident from Fig. 4(a) that the work hardening exponent
increases when the temperature increases to 154 C in air.
Comparison between work hardening exponents of the samples
tested at 1.1 9 10 4 s 1 and 154 C, but in different environ-
ments of air and boiling MgCl2 (Fig. 4a), reveals that the
exponent increases slightly when the test was carried out in the
boiling MgCl2 environment. While comparing the results
obtained in boiling MgCl2 environment with different strain
rate values, it is obvious that the exponent would increase when
the strain rate decreases. This discrepancy might be due to the
domination of the corrosion phenomenon at lower strain rates.
Therefore, there is a competition between increasing work
hardening exponent due to decreasing strain rate (resulting from
activation of dynamic strain aging at 154 C) and decreasing
the exponent due to the progress of SCC. The latter has a
predominant effect at lower strain rates and reduces the
resulting work hardening exponent as strain rate decreases.
Strength and ductility of the alloy decreases appreciably at
154 C and in boiling MgCl2 environment (Fig. 4b, d, e). As
seen, at strain rate of 1.1 9 10 4 s 1, the ultimate tensile
strength, elongation, and reduction of cross-sectional area for
the samples tested in boiling MgCl2 are respectively 5, 20, and
10% less than those tested in air at 154 C (sample No. 2 in
Table 2). Upon decreasing the strain rate from 1.1 9 10 4 s 1
to 1.1 9 10 6 s 1 for the specimens tested in boiling MgCl2,
Fig. 1 Test setup for SSRT experiments
the amounts of UTS, elongation to failure, and reduction of
cross-sectional area are recorded to be about 57, 88, and 82%,
respectively. The results indicate that this type of chemical
environment employed has a detrimental effect on ductility of
the steel in low strain rates. However, yield stress is not
signicantly affected by strain rate during the test in MgCl2
boiling environment (Fig. 4c). In this study, the yield stress of
the steel decreased signicantly as the temperature increased
from room temperature to 154 C at air.
3.2 Fractography
Figure 5 illustrates the macrofractography of the samples. It
is evident that the fracture of austenitic stainless steel in air is
completely ductile. The brous appearance of the fracture
surface which represents ductile fracture becomes granular as
the testing environment changes from air to boiling MgCl2
representing brittle fracture. Granular appearance becomes
more distinct as strain rate decreases (samples No.4 and 5 in
Fig. 5). These observations are in accordance with the decreas-
ing ductility of the steel when tested in MgCl2 environment
(Fig. 4d). Necking and formation of cracks on peripheral
surfaces of the samples observed in the other fracture features
are absent. At high strain rates, peripheral surface cracks are
small, shallow, and straggly, but they are larger, deeper, and
localized at low strain rates.
Micrographs of the fracture surfaces are shown in Fig. 6.
The fracture surface of the sample tested in air is rather ductile
and subtends small dimples (Fig. 6a), while the fracture
surfaces of the samples tested in boiling MgCl2 (Fig. 6b, c)
show both the intergranular (IG) and transgranular (TG)
fracture modes; the latter becomes predominant on fracture
surface as strain rate decreases to 1.1 9 10 6 s 1 (Fig. 6c). It
should be noted that although TG has normally been introduced
as fracture mode of austenitic stainless steels in boiling
magnesium chloride, depending on the sensitization condition,

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Fig. 2 Geometries and dimensions of tensile test specimens according to ASTM E8 standard, used for SCC tests

Table 2 Applied conditions during slow strain tensile tests of AISI 316L austenitic stainless steel
Sample no

Conditions 1 2 3 4 5

Strain rate, s 1 1.1 9 10 4

1.1 9 10 4
1.1 9 10 4 1.1 9 10 5 1.1 9 10 6
Environment air air Boiling MgCl2 Boiling MgCl2 Boiling MgCl2
Temperature, C 20 154 154 154 154

Fig. 3 Engineering stress-strain curves of different samples from 316L austenitic stainless steel

a mixture of TG and IG has also been observed for this grade of IGSCC (Ref 11-13). To clarify the details, some cases should be
stainless steel during fracture (Ref 11). pointed out. First, sensitization can be caused by the formation
Many reasons have been summarized in the literature to of chromium carbides (e.g., M23C6) on grain boundaries and a
explain the sensitization of stainless steels and the occurrence of concomitant reduction of chromium in the adjacent grains. The

Journal of Materials Engineering and Performance Volume 22(6) June 20131785

Fig. 4 Effects of strain rate, environment, and temperature on mechanical properties (a-e) of 316L austenitic stainless steel
depletion in chromium concentration adjacent to the grain
boundaries gives rise to a reduction in passivity relative to the
grains themselves and susceptibility to IGSCC. However,
thermal sensitization is not taken place in low carbon grades
(L-grades; rd type 304L or 316L), in which the bulk carbon
content is limited to C 0.03%. Second, for stabilized grades
of stainless steel, IGSCC can occur clearly not in a sensitized
condition. It has been shown that their susceptibility to IGSCC
is due to the cold work induced during fabrication. The
mechanism by which cold work renders austenitic alloys
susceptible to IGSCC can be ascribed to an unfavourable
interaction between deformation-induced martensite, high resid-
ual stresses, and localized deformation. Third, other environ-
mental conditions such as ow conditions, temperature, and the
presence of impurities such as sulphate and chloride also
inuence the occurrence of IGSCC (Ref 12, 13). Finally, the
simultaneous occurrence of IG and TG fracture modes would be
assisted by formation of shear bands consisting of stacking fault
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bundles around the cracks, which are propagated from fracture
surfaces as evidenced by Fig. 7 (high strain rate). These areas
even consist of strain-induced e-martensite. The occurrence of
strain-induced transformation (SIT) in austenitic stainless steels
is frequently reported (Ref 14, 15). It is postulated that the
product of SIT leads to formation of e- and/or a -martensites in
austenitic stainless steels. In support of these statements,
Staudhammer et al. (Ref 13) suggested that high strain rate
may promote more irregular shear band arrays compared with
the low strain rate. This led to a greater number of shear band
intersections and higher volume fraction of a-martensite at the
early stages of tensile deformation.
Furthermore, microhardness of these areas prove that these
deformation bands are harder (327 HV0.1) than adjacent austen-
itic matrix (260 HV0.1) developing a low-ductility zone in front of
the crack tips. Low-ductility bands would assist propagation of
cracks through the grains (transgranular fracture). Branching
behavior of the propagating crack is also noticeable in Fig. 7.
Journal of Materials Engineering and Performance
Fig. 5 Fracture surfaces of different samples form 316L austenitic stainless steel: (a) top view; (b) side view, with sample numbers correspond-
ing to Table 2

Fig. 6 SEM micrographs of fracture surfaces from different samples of 316L austenitic stainless steel which were tested at (a) ambient temper-
ature and air 1.1 9 10 4 s 1 strain rate, (b) boiling MgCl2 at 154 C 1.1 9 10 5 s 1 strain rate, and (c) boiling MgCl2 at 154 C 1.1 9 10 6 s 1
strain rate

Longitudinal sections of fracture surface are shown in Fig. 8
and 9. The presence of two crack paths in front of a crack tip in
Fig. 8b is also remarkable, which conrms the prevalence of a
lm-induced mechanism during the SCC process (Ref 1, 2).
Tiny holes on crack path and also dispersed holes in matrix are
the other appreciable features of both IG and TG cracks in the
samples (Fig. 8, 9). These corroded holes are apparently
localized and random. These tiny holes, or pits, can act as
points of cracks initiation, coalescence, and then propagation
due to mechanical loading. These pits are observable even
around inclusions as shown in Fig. 9. It is seen in Fig. 9 that
the crack path does not inevitably pass through inclusions or
MnS particles.
In this respect, initiation of TGSCC cracks in our experi-
ments is apparently assisted by establishment of low-ductility
deformation bands in austenitic matrix during plastic deforma-
tion of the steel. The discrepancy in ductility between
deformation bands and the matrix promotes propagation of

Journal of Materials Engineering and Performance Volume 22(6) June 20131787

Fig. 7 Micrographs of a propagated crack in matrix of 316L austenitic stainless steel tensioned under 1.1 9 10 5 s 1 strain rate in boiling
MgCl2 at 154 C. Branching behavior of the crack is assisted by deformation bands (in white circles) in fronts of crack tips

Fig. 8 SEM micrographs of a transgranular crack in sample no.5 (Table 2); (a, b) pits on the transgranular crack (BSE image); and (c) two
white crack paths in front of a crack tip (BSE image)

Fig. 9 SEM micrographs of (a) and (b) intergranular cracks passing beside inclusion and MnS particles, and (c) some pits on interface of an
inclusion (MnS particle) and matrix, in sample no.5 (Table 2)

cracks through the grain, inducing TG crack mode. In addition, zones in the matrix helps in crack propagation. These pits later
the presence of pits in the matrix which could be resulting from connect together under mechanical load, and the TG crack
the preferred corrosion in localized chemically heterogeneous propagates faster until it culminates in fracture (Ref 13, 16).

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4. Conclusions
It is revealed that boiling MgCl2 provides a highly
aggressive and corrosive medium which completely degrades
the mechanical properties of 316L austenitic stainless steel
because of the progression of SCC. The effect of boiling MgCl2
on mechanical properties of steel becomes more signicant as
strain rate during SSRT decreases. Lowering the strain rate in
the presence of boiling MgCl2 environment changes macro-
fracture mode from ductile to brittle, and microfracture
appearance becomes a mix of intergranular (IG) and transgran-
ular (TG) modes. The TG fracture mode becomes almost
predominant at the lowest strain rate of 1.1 9 10 6 as observed
in this study.
It appears that the promotion of TG fracture would be
assisted by the presence of low-ductile deformation bands in
front of the crack. The presence of tiny holes or pits on crack
path and dispersed pits in matrix would indicate that SCC in
316L austenitic steel can initiate from these random and
localized pits which then become interconnected and propagate
further in matrix.
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