Materials Science and Engineering A 528 (2011) 22772281

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Effect of Ni content on the tensile properties and strain-induced martensite

transformation for 304 stainless steel
Do-Yeal Ryoo a , Namhyun Kang b , Chung-Yun Kang b,
a
b

Technical Research Laboratories, POSCO, 1 Goedong-dong, Nam-gu, Pohang, Gyeongbuk 790-785, Republic of Korea
Department of Materials Science and Engineering, Pusan National University, San 30, Jangjeon-dong, Geumjeong-gu, Busan 609-735, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 31 March 2010
Received in revised form 27 October 2010
Accepted 8 December 2010
Available online 15 December 2010
Keywords:
Austenitic 304 stainless steel
Ni content
Tensile strength
Elongation
Strain-induced martensite transformation
Strain hardening

a b s t r a c t
The effect of Ni content (8.312 wt.%) on the tensile properties and strain hardening behavior was studied on type 304 stainless steels (STS) used for the membrane of LNG storage tanks. The tensile test
temperature was varied from 25 C to 196 C. At room temperature, the hardening and ductility indices
(tensile strength, strain hardening exponent and elongation) increased with decreasing Ni content. For
the 8.39.0 wt.% Ni STS, a lower yield point was observed at temperatures below 60 C. It was due to
the dynamic strain softening and/or transformation-induced plasticity (TRIP) that accompanied the rapid
increase in the amount of strain-induced martensite ( ) at low strains. Neither dynamic strain softening
nor TRIP was observed for the 12 wt.% Ni STS because only the -martensite transformation was produced
at the low strains.
2010 Elsevier B.V. All rights reserved.

1. Introduction
The storage tanks for large volumes of liqueed natural gas
(LNG) are constructed from 304 stainless steel (STS). The LNG
should be stored and transported at 162 C. Some parts of the LNG
storage tanks are subjected to bending fatigue or tensile fatigue due
to an abrupt temporal change in the charging and discharging of the
gas and due to repetitive deformation induced by variations of LNG
level and pressure [1].
Type 304 STS (Fe18Cr8.4Ni) consists of -austenite, which is
a metastable phase at room temperature (RT). The stability of the
austenite phase varies with respect to the Ni content. In addition,
the strains applied at a temperature less than the martensite transformation temperature (Md ) transform the metastable austenite to
 -martensite, which is termed strain-induced martensite transformation. The factors affecting the phase transformation are Ni
content, strain-rate and temperature. The amount of the transformed phase inuences the tensile and fatigue properties.
Many studies on the mechanical properties have been conducted for austenitic STS at RT and lower temperatures [27].
However, very few studies have focused on the effect of Ni content
on the mechanical properties for 304 STS [810]. Therefore, this
study investigated the effect of Ni content on the tensile properties

Corresponding author. Fax: +82 51 514 4457.

E-mail address: kangcy@pusan.ac.kr (C.-Y. Kang).
0921-5093/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.12.022

and phase transformation for 304 STS at RT and lower temperatures.

2. Experimental procedure
The specimen was typical 304 STS with a Ni content varying from
8.3 wt.% to 12 wt.%. A 50 kg ingot with the designed composition
was produced in a high-frequency induction furnace and its thickness reduced to 2 mm by hot rolling and subsequent cold rolling.
Regardless of the Ni content, the grain size for the all specimens
remained mostly constant as specied in ASTM No. 6.87.0.
The JIS 13B specimen was used for the tensile test at RT. The
low temperature tensile test was performed by using the cryogenic
sub-size specimen at a strain rate of 1 mm/min. After completion of
the tensile experiment, the amount of strain-induced  -martensite
was measured by using a ferritescope (Fischer Co.). The ferritescope
uses an eddy current probe to measure ferrite content since ferrite is ferromagnetism. A vibration sample magnetometer VSM
has a same principle with the ferritescope. The ferritescope is
useful specically in the eld since it is portable and can success small specimens. For quantitative analysis of the  -amount,
standard samples were produced by changing the temperature
during the cold rolling. Therefore, the amount of produced  martensite ranged from 4.6 vol.% to 98 vol.%, and was measured
with the (VSM). The amount of  -martensite measured from the
VSM was applied to the ferritescope for the correction. The paramagnetic -martensite was observed by using X-ray diffraction

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Fig. 3. Effect of Ni content on the strain hardening exponent (n) at room temperature.

Fig. 1. Effect of Ni content on the tensile properties at room temperature: (a) tensile
and yield strength and (b) total and uniform elongation.

(XRD). The CuK characteristic X-ray (50 kV, 150 mA) was used for
the XRD.
3. Results and discussion
3.1. Tensile properties at room temperature (RT)
Fig. 1 shows the tensile strength, yield strength (0.2% offset), total elongation and uniform elongation as a function of the
Ni content. The tensile strength, total elongation and uniform
elongation decreased with increasing Ni content, while the yield
strength remained mostly constant. This was coincident with a previous study nding that the 0.2% offset yield strength at RT was
independent of the Ni content if it was larger than some limits
[8].
The effect of Ni content on the strain hardening behavior was
examined for the 304 STS. Fig. 2 shows the true stresstrue strain
curve at RT as a function of the Ni content. For the true strain above
0.15, the increment slope of the true stress decreased with increasing Ni content. Fig. 3 indicates the behavior of the strain-hardening
exponents (n) for the strain regimes of 2030% and 3040%. The nvalue decreased with increasing the strain. The n-value decreased

Fig. 2. Effect of Ni content on the true stresstrue strain curves at room temperature.

for both strain regimes with increasing Ni content, which suggested

deterioration in formability.
Type 304 STS has transition temperatures of Md 293 K and
Ms 4 K [11]. The Md value is very similar to RT. The specimen
compositions of the present study, specically 8.39.0 wt.% Ni, differed slightly from that of the previous study [11]. Therefore, the
study specimen can undergo a strain-induced martensitic transformation at RT, i.e., the metastable austenite () transforms to the
 -martensite under straining.
The tensile test specimens were subjected to various strains
from 20% to 50%, and the amount of  -martensite was measured
from the ferritescope. Fig. 4 shows the volume fraction of the  phase at RT as a function of Ni content and tensile strain. No. 4 steel
(12 wt.% Ni) did not produce the  -phase, even up to an applied tensile strain of 50%. The nickel element is the austenite stabilizer, and
the largest Ni content of 12 wt.% stabilized the austenite phase and
suppressed the phase transformation to the  -martensite at RT.
The Md for the 12 wt.% Ni steel should be signicantly lower than
RT. This result coincided with the previous report from Fujikura
et al. [9].
For the 8.39.0 wt.% Ni STS, the amount of the  -martensite
increased with increasing strain and decreasing Ni content. Therefore, the tensile strength and strain hardening exponent (n)
increased due to the  transformation, as indicated in Fig. 3. The
transformation-induced plasticity (TRIP) effect restrained the local
necking more signicantly with increasing Ni content, and nally
increased the elongation [12].

Fig. 4. Volume fraction of the strain-induced  -martensite as a function of Ni content and tensile strain at room temperature.

D.-Y. Ryoo et al. / Materials Science and Engineering A 528 (2011) 22772281

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Fig. 5. Effects of Ni content on the tensile properties at various test temperatures: (a) strength and (b) elongation.

3.2. Tensile properties at lower temperature

Fig. 5 shows the tensile properties measured at temperatures
lower than RT. The tensile strength increased with decreasing Ni
content, in the same trend as that evident at RT, and with decreasing test temperature. However, the 0.2% offset yield strengths were
mostly independent of the test temperature and Ni content. The
8.39.0 wt.% Ni STS exhibited a decreased elongation with decreasing test temperature. Specically, the elongation sharply decreased
when the test temperature was decreased from 25 C to 60 C.
However, the 12 wt.% Ni STS showed the largest elongation at
60 C rather than that at 196 C and 25 C.
The strength and elongation of the metastable austenitic STS
were closely related with the strain-induced martensite deformation [1315]. Fig. 6 shows the volume fraction of  -martensite as
a function of the Ni content and test temperature, which was measured from the tensile-fractured specimens. The volume fraction
of the  -martensite increased with decreasing test temperature
and Ni-content. The 8.39.0 wt.% Ni STS exhibited a sharp increase
of the  formation as the test temperature decreased from 25 C
to 60 C. Further decrease of the test temperature from 60 C
to 196 C indicated that the slope of the  formation decreased
with respect to the test temperature. The volume fraction of the
 -martensite was almost unaffected by the Ni content between
60 C and 196 C. However, the 12 wt.% Ni STS showed a constant
slope of the  formation from 25 C to 196 C. Most signicantly,

Fig. 6. Volume fraction of the  -martensite produced in the tensile-fractured specimens as a function of the Ni content and test temperature.

the  amount of the 12 wt.% Ni STS was signicantly smaller than

that of the 8.39.0 wt.% Ni STS for the entire test temperature range
(25 C and 196 C).
For the 12 wt.% Ni STS, the largest elongation at 60 C (213 K)
could be explained by the temperature from which the straininduced martensitic deformation was initiated. The  -martensite
was not produced during the tensile test at RT, but was at 60 C.
For this reason, the test temperature (60 C) should be main-

Fig. 7. Effect of the tensile test temperature on the true stressstrain curves for (a) 8.3 wt.% Ni stainless steel (STS) and (b) 12.0 wt.% Ni STS.

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Fig. 8. Lower yield strength as a function of Ni content and the tensile test temperature.

tained between Ms (4 K) and Md (<293 K). The low Md temperature

induced a slow increase of the  formation and maintained a large
strain-hardening until the deformation was completed. The straininduced martensite transformation occurred continuously at the
stress-concentrated region, which reduced the stress concentration, delayed the necking and cracking phenomena, and nally
increased the elongation.
For the 8.39.0 wt.% Ni STS, the Md temperatures should be very
close to 25 C. As the test temperature decreased from 25 C to
60 C, they indicated a sharp increase of the  formation (Fig. 6)
and strain-hardening (Fig. 5a). Therefore, the tensile specimens
were fractured easily and the elongation decreased signicantly,
as shown in Fig. 5b. As the test temperature was decreased further
from 60 C to 196 C, the rate of  formation slowed and the
decrement of the elongation was reduced.
Fig. 7 shows the true stressstrain curve to compare the strain
hardening behavior as a function of the Ni content and the tensile
test temperature. The 8.3 wt.% Ni STS (No. 1) exhibited a sigmoidshaped tensile stressstrain curve with a lower yield point from
60 C to 196 C. Fig. 8 shows the lower yield strength as a
function of the Ni content and the tensile test temperature. The
lower yield strength increased with decreasing temperature for the
8.39.0 wt.% Ni STS (No. 13). However, the 12 wt.% Ni STS (No. 4)
exhibited a parabolic-shaped tensile stressstrain curve with no
lower yield point from 60 C to 162 C. The lower yield point
was observed at the lowest temperature, i.e., 196 C, and the lower
yield strength of the 12 wt.% Ni STS was smaller than those for the
8.39.0 wt.% Ni STS. For the entire Ni content range (8.312 wt.%),
the serration phenomenon was not observed for the temperature
range (60 to 196 C).

Below RT, metastable austenitic STS produced the yielding and

serration phenomenon caused by the strain softening [3]. This was
because the types of the phase transformation varied when the
yielding occurred for the specic tensile test temperature. Straining
in the plastic deformation transforms the austenite to martensite, which is termed strain-induced martensite transformation,
whereas the martensite transformation in the elastic deformation
is dened as stress-induced martensite deformation [16]. For the
180 C tensile test, the transformation type of the high Ni content
STS was changed from  to  through the straininduced martensite transformation [9]. The  transformation
is also known as stress relaxation [17]. Reed and Pavlov et al. studied the tensile behavior at the low temperatures at which the strain
softening occurred to reduce the stress if the transformation
was generated at the low strain regime [18,19].
Therefore, the cause of the lower yield points at the low
temperature-tensile test was investigated in this study. The tensile test specimen at 60 C was deformed to the lower yield
point, after which the microstructural phase was measured by XRD.
Fig. 9 shows the XRD peaks as a function of the Ni content. The
8.3 wt.% Ni STS had  - and -martensite in the austenite matrix
(Fig. 9a). The amount of  -martensite was 10.1 vol.%, as measured
by using the ferritescope. However, the 12 wt.% Ni STS showed only
-martensite in the austenite matrix (Fig. 9b). The  -martensite
was not detected from the XRD pattern and the ferritescope.
The phase analysis results were used to discuss the yielding phenomenon as a function of the Ni content and the test temperature.
The unstable -austenite of the 8.3 wt.% Ni STS at low temperature
was transformed to -martensite in the beginning of the deformation stage. As the deformation proceeded, the  or 
transformations occurred instantly, which increased the strain rate
sensitivity continuously. The strain hardening exponent was minimized at the true strain (0.05), therefore producing the lower yield
point. As the strain increased further, the transformation slowed
down and the strain hardening decreased continuously. Finally, the
strain hardening exponent was maximized at the true strain (0.2),
and then decreased to exhibit an S shape of the true stressstrain
curve [6]. In the beginning of the deformation stage and at the low
temperature, the instant transformation to  -phase signicantly
increased the strain rate sensitivity and decreased the strain hardening. This was probably due to the TRIP and/or dynamic strain
softening caused by the strain-induced martensite transformation.
As the Ni content was increased to 12 wt.%, the -austenite was
stable in the beginning of the tensile deformation from 60 C
to 162 C, so that the dislocations became piled-up and a small
amount of -austenite was transformed to -martensite. The  transformation did not occur at the strain of the lower yield point.
Therefore, the tensile strength and strain hardening were increased

Fig. 9. X-ray diffraction (XRD) patterns of the tensile strained specimens to the lower yield point at 60 C for (a) 8.3 wt.% Ni stainless steel (STS) and (b) 12.0 wt.% Ni STS.

D.-Y. Ryoo et al. / Materials Science and Engineering A 528 (2011) 22772281

continuously to exhibit the parabolic shape of the true stressstrain

curve.
4. Conclusion

2281

ing the strain produced the  -transformation instantly and a

lower yield point. However, the 12 wt.% Ni STS produced the martensite with no  -martensite at 60 C, and no lower yield
point was observed.

For the 304 austenitic STS, the effects of Ni content

(8.312.0 wt.%) and tensile test temperature (196 to 25 C) on
the tensile properties were studied by using the concept of straininduced martensite deformation. The study results are summarized
as follows:

Acknowledgement

(1) With decreasing Ni content, the tensile strength, elongation and

strain hardening exponent all increased, although the 0.2% offset yield strength remained almost constant. The  -martensite
of the low Ni-content STS was increased by the strain-induced
martensite transformation, which induced TRIP and increased
the tensile strength and elongation.
(2) For the entire Ni-content range (8.312.0 wt.%), the tensile
strength was increased and the 0.2% offset yield strength
remained mostly constant as the tensile test temperature
was decreased from 25 C to 196 C. The 8.39.0 wt.% Ni STS
exhibited a decreasing elongation with decreasing tensile test
temperature. The lower yield point was observed at temperatures below 60 C. However, the elongation of the 12 wt.%
Ni STS was maximized at 60 C. The lower yield point was
observed only at 196 C.
(3) The variation of the elongation and the yielding phenomenon
was due to the different behavior of the phase transformation
with respect to the tensile test temperature and the Ni content.
The 8.39.0 wt.% Ni STS underwent the phase transformation
( ) in the beginning of the tensile deformation because
the metastable -austenite was unstable at 60 C. Increas-

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This work was supported by grants-in-aid for the National Core

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