Materials Transactions, Vol. 50, No. 4 (2009) pp.

926 to 929
#2009 The Japan Institute of Metals RAPID PUBLICATION

Hardening Behavior of a 304 Stainless Steel Containing

Deformation-Induced Martensite during Static Strain Aging
Sang Hun Lee1; * , Jeom Yong Choi2 and Won Jong Nam1
1
School of Advanced Material Engineering, Kookmin University, Seoul 136-702, Korea
2
Stainless Steel Research Group, POSCO Technical Research Laboratories, POSCO, Pohang P.O. Box 36, 790-785, Korea

The hardening behavior of a 304 stainless steel containing deformation-induced martensite during static strain ageing was investigated.
Tensile strength increased with the increase of aging temperature. The results of DSC measurements showed that the aging mechanisms would
be related to carbon diffusion to dislocations in
0 -martensite and carbon diffusion in austenite. It is found that the increase of strength during
strain aging would be attributed to hardening of austenite as well as
0 -martensite. [doi:10.2320/matertrans.MRP2008416]

(Received November 7, 2008; Accepted January 19, 2009; Published March 4, 2009)
Keywords: strain aging, austenitic stainless steel, mechanical property, kinetics

1. Introduction of aging temperature on strength and the amount of
0 -

martensite was examined in the present work. Additionally,
Static strain aging (SSA) is well-known phenomenon to investigate the dominant mechanism of hardening during
frequently observed in bcc metals and alloys. This SSA is a strain aging, the changes of mechanical properties, the
consequence of the combined effect of temperatures and amount of
0 -martensite, and the kinetic data from DSC
plastic strains associated with the deformation process.1) It (differential scanning calorimetry) were discussed.
seems well established that the main mechanism of SSA is
closely related to the locking effect on dislocations caused by 2. Experimental Procedure
the formation of atmospheres of interstitial carbon (C) and
nitrogen (N) solute atoms dissolved in ferrite.2) The chemical composition of a 304 austenitic stainless
Metastable austenitic stainless steels are strengthened by steel used in this study was 0.057C, 0.376Si, 1.08Mn,
the formation of dislocation structure and/or the deforma- 18.14Cr, 8.14Ni, 0.305Cu, 0.146Mo and 0.033N (in mass%).
tion-induced martensitic transformation during cold work- An austenite grain size of the hot rolled and annealed sheet
ing.3) Furthermore, strain aging at the temperature of was 36.8 mm. To produce the deformation-induced marten-
200
400 C would result in the further increase of strength site, samples were cold rolled by 40% (with 16% reduction
in cold worked metastable austenitic stainless steels.4–6) per pass). An aging treatment was performed on cold rolled
Proposed mechanisms are (1) the formation of additional stainless steel sheets in a heated salt bath in the temperature
martensite after aging5–7) and (2) hardening of
0 -marten- range of 200
700 C for an hour. Small rectangular speci-
site.4,8) Mangonon and Thomas6) have shown that strength mens were cut from cold rolled and aged samples for X-ray
increases through the formation of thermal nucleation of diffraction analysis using Cu Ka radiation. To assess the

0 -martensite during aging up to 400 C. According to effect of surface constraint on the transformation response,
Mukhopadhyay, et al.,7) the further formation of
0 -marten- diffraction patterns were obtained on samples chemically
site during strain aging is attributed to a local increase of thinned to remove specific fractions of the sheet thickness.
the Ms temperature caused by a depletion of chromium and The solution used for surface removal was a mixture of
carbon in the surrounding matrix due to the precipitation hydrochloric acid, nitric acid and distilled water in 1 : 1 : 1
of fine carbides. However, Rathbun, et al.4) reported that proportion. The amount of
0 -martensite was also measured
strength would increase without the change in the volume using Ferritescope. Ferritescope readings were converted into
fraction of
0 -martensite during strain aging. Since no aging the amount of
0 -martensite by multiplying with the factor of
occurs in deformed austenite, the increase of strength must be 1.7 according to Talonen’s work.9)
associated with strengthening of
0 -martensite containing
The amount of
0 -martensite
high density of dislocations. Thus, the increase of strength ð1Þ
would be closely related to the diffusion of interstitial solute ¼ 1.71  Ferritescope reading
atoms and the interaction of the solutes with dislocations Tensile tests were performed at room temperature with a
during aging in the temperature range of 100
400 C. constant displacement speed. The initial strain rate was
However, the hardening behavior of cold worked metastable 6:7  104 s1 . Thermal analysis was performed with a
austenitic stainless steels during strain aging can’t be fully differential scanning calorimeter under a flowing Ar atmo-
understood yet with the above mechanisms. sphere. As the DSC peak position depends on the heating
Thus, to investigate the hardening behavior of a cold rate,10) the measured data of the peak positions for different
worked 304 stainless steel during strain aging, the effect heating rates of 2
16 C/min were used. To obtain the
activation energy, both the Kissinger11) and Chen and
*Graduate Student, Kookmin University Spaepen12) methods were applied in this work. To understand
 Hardening Behavior of a 304 Stainless Steel Containing Deformation-Induced Martensite during Static Strain Aging 927

500 0.0070
1500
Temperature

Volume Fraction of α -martensite, %

45 Dilatation
0.0068
450
1200

Temperature, °C
Strength, MPa

Delatation, µm
30 0.0066

400
900
0.0064
15

350
Tensile Strength
0.0062
Yield Strength
600
Volume Fraction of α -martensite
0

300 0.0060
0 200 400 600 0 500 1000 1500 2000 2500 3000 3500
Aging Temperature, °C Time, sec

Fig. 1 Effect of aging temperature on mechanical properties and the Fig. 2 Dilatation curves, showing the increase of the amount of
0 -
amount of
0 -martensite in cold rolled 304 stainless steels received 40% martensite with annealing time during heating at 450 C.
reduction. Samples were aged for an hour.

Fig. 3 TEM micrographs of a 304 austenitic stainless steel deformed at room temperature with 40% reduction.

the kinetics during heating, stainless steel sheets were heated calculated from Ferritescope readings increases from 45.5%
to the desired temperatures at a rate of 4 C/min and then for a cold rolled sample to 50% for a sample aged at 450 C.
rapidly cooled in water. According to the methods,11,12) the Additionally, the occurrence of the dilatation during aging at
heating rate (B), the apparent activation energy of the process 450 C in Fig. 2 also supports the increase in the amount of
(Q), and the maximum temperature of the peak Tp are related
0 -martensite with aging. This increase in the amount of
0 -
by the equation martensite with aging provides the evidence for the addi-
Q tional formation of
0 -martensite during aging.5–7) However,
lnð
Þ ¼  þC ð2Þ it is difficult to conclude that only the increased amount of
0 -
kB T p
martensite contributes to the increase of tensile strength in
where kB is the Boltzmann’s constant and C is an integration aged samples. Assuming that the increased amount of
0 -
constant. martensite, 4.5%, causes the increment of tensile strength,
140 MPa, during aging at 450 C, the calculated contribution
3. Results and Discussion of aged austenite to tensile strength would become ignored.
Thus, there must be other factors on tensile strength of aged
3.1 Mechanical properties samples.
Figure 1 shows the effect of aging temperature on tensile Figure 3 shows the typical microstructure of the 40%
strength, yield strength and the amount of
0 -martensite in deformed 304 austenitic stainless steel, revealing micro-
304 stainless steels cold rolled and aged for 1 h. The variation structures of
0 -martensite with high density of dislocations
of yield strength with aging temperature is similar to that of (Fig. 3(a)) and deformed austenite with micro-twins
tensile strength, except for the peak temperature of 300 C. (Fig. 3(b)). The closer examination of the XRD patterns of
Tensile strength increases continuously up to the aging a 304 stainless steel deformed 40% and aged at various
temperature of 450 C, and then decreases rapidly due to the temperatures reveals that phase transformation does not
reverse transformation of
0 -martensite to austenite.13) The occur during strain aging up to 450 C. To understand the
similar shapes of tensile strength and the amount of
0 - behavior of austenite and
0 -martensite during aging, hard-
martensite in Fig. 1 indicates that the increment of tensile ness of each phase was measured using a nano-indenter
strength during aging must be closely related to the variation (Fig. 4). Hardness of
0 -martensite increases from 4.6 GPa
in the amount of
0 -martensite. The amount of
0 -martensite (cold rolled) to 5.4 GPa (aged at 450 C) by 17.4%, while that
928 S. H. Lee, J. Y. Choi and W. J. Nam

6
γ -Austenite 1.2 2
a=b/ Tp
α -Martensite

1.0

-1
kln(α), 10 eVk
4
Hardness, GPa

5.28eV 1.38eV 0.69eV

0.8

3
510 kJ/mol 133 kJ/mol 67 kJ/mol

0.6 a=b/ Tp

2
0.4
5.34eV 1.43eV 0.73eV
0.2 516 kJ/mol 138 kJ/mol 70 kJ/mol

0 1.5 1.8 2.1 2.4 2.7

40% red. 40% red. & Aged(450 °C, 1hr) -1
1000/ T, k
Fig. 4 Effect of static strain aging on hardness of austenite and
0 -
martensite in cold rolled 304 stainless steels received 40% reduction. Fig. 6 Calculated apparent activation energy using Kissinger plot of the
maximum peak temperatures in the DSC curves.

6.0

0.000
Heat Flow, mW/mg

peak 1 5.5
peak 2 peak 3 α -Martensite

-0.003
Hardness, GPa
5.0

-0.006
4.5 Austenite

-0.009 4.0
0 150 300 450 600
Temperature, °C
3.5
0 100 200 300 400 500
Fig. 5 DSC curves of a 40% cold rolled sample and a reheated sample,
with the heating rate of 4 C/min. Aging temperature, °C

Fig. 7 The hardness of austenite and
0 -martensite in 304 stainless steels

of austenite increases from 4.2 to 4.8 GPa by 14.3%. These cold rolled and heated to 180, 300 and 450 C with the heating rate of
results indicate that hardness values of both
0 -martensite and 2 C/min.
austenite obviously increase during static aging. It is also
noted that the increase of hardness is more pronounced in
0 - of 0:69
0:73 eV (67
70 kJ/mol) for the first peak,
martensite than austenite during aging at 450 C. This means 1:38
1:43 eV (133
138 kJ/mol) for the second peak and
that the age hardening operates more effectively in
0 - 5:28
5:34 eV (510
516 kJ/mol) for the third peak.
martensite rather than in deformed austenite. The apparent activation energy of the first peak, 67
70
kJ/mol, is close to the activation energy for the diffusion of
3.2 Kinetics of strain aging carbon atoms in ferrite, 66.9 kJ/mol.15) This confirms that the
The kinetics of strain aging was evaluated on the cold mechanism for the first peak of strain aging (100
150 C) is
rolled material using a differential scanning calorimeter closely related to the redistribution of interstitial solute
(DSC). The DSC curves in Fig. 5 reveal three exothermic carbon atoms to dislocations in
0 -martensite containing high
peaks, which represent the different stages occurred during density of dislocations. The interaction of carbon atoms with
aging of a 304 stainless steel deformed 40%. The temperature dislocations in
0 -martensite would result in the rapid
range is found as 100
150 C for the first peak, 180
270 C increase of hardness in
0 -martensite when heated to 180 C
for the second peak and 350
450 C for the third peak, (Fig. 7). Meanwhile, the apparent activation energy of the
respectively. Additionally, the presence of an endothermic second peak, 133
138 kJ/mol, coincides with the activation
peak around 500 C implies that the reversion of
0 -martensite energy for carbon diffusion in austenite, 134
136 kJ/mol.16)
to austenite begins at above ageing temperature of 450 C.14) According to Fujita, et al.,17) the segregation of solute atoms
The values of the parameter Q, can give important on the stacking fault known as the Suzuki effect can occur in
information concerning the mechanisms of aging. The a deformed and annealed 304 stainless steel. Thus, it is
apparent activation energy of DSC peaks obtained by expected that the presence of the second peak (180
270 C)
analyzing Kissinger plot (Fig. 6) would be useful for under- might be related to the segregation of solute carbon atoms to
standing the mechanisms of the each stage of static aging dislocations and micro-twins in deformed austenite during
more precisely. Figure 6 shows plots of lnð
Þ (where
¼ aging. Accordingly, in Fig. 7, hardness of austenite increase
B/T2 p 11) and
¼ B/Tp 12)) against 1/kB Tp and the resultant steadily up to 300 C and hardness of
0 -martensite increases
Q values calculated from each slope. The two methods show slightly due to the occurrence of carbide precipitation and the
a reasonable agreement with each other, yielding Q values progress of recovery in
0 -martensite.
 Hardening Behavior of a 304 Stainless Steel Containing Deformation-Induced Martensite during Static Strain Aging 929

The measured activation energy of the third peak, Acknowledgements

510
516 kJ/mol, seems considerably higher than the re-
ported Q values available for steels, such as Q Cr ¼ 405 kJ/ The authors would like to acknowledge the support of
mol, Q Cr ¼ 343 kJ/mol, Q Ni ¼ 280 kJ/mol and Q Ni ¼ POSCO.
358 kJ/mol.18) There has been no clear explanation regarding
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