ISIJ International, Vol. 41 (2001), No. 3, pp.

262–267

Effects of Nitrogen, Niobium and Molybdenum on Strengthening

of Austenitic Stainless Steel Produced by Thermo-Mechanical
Control Process

Masayuki TENDO, Yutaka TADOKORO,1) Kazuhiro SUETSUGU2) and Takanori NAKAZAWA3)

Steel Research Laboratories, Nippon Steel Corporation, Shintomi, Futtsu, Chiba 293-8511 Japan.
1) Yawata Laboratory, Nippon Steel Corporation, Tobihata-cho, Tobata-ku, Kitakyusyu, Fukuoka 804-8501 Japan.
2) Stainless Steels Division, Nippon Steel Corporation, Otemachi, Chiyoda-ku, Tokyo 100-8071 Japan.
3) Department of Mechanical System Engineer, Gunma University, Tenjin-cho, Kiryu, Gunma 376-0052 Japan.
(Received on July 25, 2000; accepted in final form on November 24, 2000 )

Thermo-mechanical control process (TMCP) applied to high nitrogen austenitic stainless steels could pro-
duce high-strength thick plates with a 0.2 % proof stress of higher than 600 MPa. The effects of nitrogen,
niobium and molybdenum on the strengthening have been examined by hot compression tests around
1 223 K. The hardness of the compressed specimens linearly increased with increasing the nitrogen con-
tent, and the increment in hardness was larger than that of the specimens in a recrystallized state. This
could be explained in terms of enhanced work-hardening by nitrogen addition during hot compression. In
fact, the flow stress linearly increased with increasing the nitrogen content. The planar dislocation structure
observed in the specimens with high nitrogen contents also gave evidence that nitrogen affected the work-
hardening behavior. Although it was not clear that nitrogen affected dislocation glide or dynamic recovery, it
could be predicted that nitrogen addition was effective in increasing the dislocation density. Since niobium
(0.1 mass%) had a marked effect on retarding the static recrystallization, probably owing to the fine pre-
cipitates of NbN, niobium addition is an effective way to prevent softening before accelerated cooling in
TMCP.
KEY WORDS: austenitic stainless steel; nitrogen; niobium; molybdenum; strengthening; hot compression
test; work hardening; thermo mechanical control process.

from this amount of nitrogen content is up to about 450

1. Introduction
MPa. Controlled hot rolling carried out below the recrystal-
Austenitic stainless steels are widely used for structural lization temperature is also effective in increasing yield
members in corrosive environments because of their superi- strength.2–6) Figure 1 shows a thermo-mechanical control
or corrosion resistance and excellent mechanical properties. process (TMCP) for austenitic stainless steel plates, which
The strengthening methods of austenitic stainless steels, consists of controlled hot rolling and accelerated cooling.
which have relatively low yield strength, include solid-solu- Although lower finish-rolling temperature leads to higher
tion hardening, work hardening, precipitation hardening 0.2% proof stress, it enhances the precipitation of chromi-
and grain refinement.1,2) Precipitation hardening involves um carbides impairing the corrosion resistance. Higher de-
problems with fabricability, including aging heat treatment formation stress also makes hot rolling difficult. Since ni-
after welding. Sufficient grain-size refinement to raise the trogen addition and controlled hot rolling are effective in
yield strength is difficult to achieve by a hot rolling process
because of the absence of g /a transformation. Recrystal-
lization after hot rolling is insufficient for the grain-size re-
finement to raise the yield strength. Two methods, i.e. solid-
solution hardening by nitrogen addition and work hardening
by controlled hot rolling, are effective in increasing the
strength of hot-rolled thick plates for structural applica-
tions. Since nitrogen is the most effective and economical
solid-solution strengthener, there are many types of nitro-
gen-alloyed austenitic stainless steels. However, nitrogen
addition to stainless steels in a conventional melting and Fig. 1. Schematic representation of thermo mechanical control
casting process has been limited to approximately 0.4 process (TMCP) for production of austenitic stainless
mass%. The yield strength (0.2% proof stress) achieved steel plates.

© 2001 ISIJ 262

 ISIJ International, Vol. 41 (2001), No. 3
Table 1. Chemical compositions of steels used for hot compression tests.
increasing the strength, it can be easily predicted that the
combination of the two methods brings about much higher
yield strength. We reported the mechanical properties of
high-nitrogen stainless steel plates manufactured by TMCP
in an industrial scale.7) The 0.2% proof stresses of
SUS304N2 (18%Cr–9%Ni–0.2%N–0.1%Nb) TMCP plates
and SUS317J2 (25%Cr–13%Ni–0.8%Mo–0.35%N) TMCP
plates were 600–650 MPa and 750–850 MPa, respectively.
These high proof stresses are hardly achieved for TMCP
plates with low nitrogen content. There have been some
studies2,3,8–10) on the application of controlled hot rolling
and forging to high nitrogen alloyed austenitic stainless
steels. According to the experimental results in these stud-
ies, solid-solution hardening by nitrogen seems to be re-
tained in a work-hardened steel by hot deformation. This
can be supported by the result that 0.2% proof stress was
linearly increased with nitrogen content under constant hot
deformation conditions.10) Nevertheless, it is not clear if the
strengthening mechanism of TMCP plates is the same as
that of solution-annealed plates, in which nitrogen atoms
act as effective solid-solution hardeners. On the other hand,
nitrogen may affect the work-hardening behavior during hot
rolling. Although this will lead the change of the substruc-
tures and yield strength, there has been little study of the ni-
trogen effects on the deformation behavior around hot-
rolling temperature. In addition, the presence of niobium
and molybdenum can be expected to enhance work-harden-
ing, because these elements tend to retard dynamic recov-
ery during hot rolling and to retard static recrystallization
after hot rolling. In this study, the effects of nitrogen, niobi-
um and molybdenum on strengthening have been examined
by hot compression tests around 1 223 K. The strengthening
mechanisms of nitrogen addition under work-hardening
conditions are mainly discussed.
2. Experimental Procedure
In order to understand the effects of chemical composi-
tions, hot compression tests were carried out for two types
of samples, A and B, having chemical compositions listed
in Table 1. In the A series, the nitrogen content was varied
from 0.05 to 0.25 mass% with a basic composition of
18%Cr–9%Ni, and 0.2 mass% niobium alloyed samples
were also prepared for each nitrogen content. In the B se-
ries, molybdenum was alloyed up to 1.5 mass% with a basic
composition of 24.5%Cr–13.5%Ni–0.35%N. These steels
were melted in a 25 kg high frequency induction furnace,
and hot rolled to 15 mm thick plates. Cylindrical specimens
with a diameter of 8 mm and a length of 12 mm were ma-
chined from the plates in the thickness direction. Figure 2
shows a schematic representation of the hot compression
test conditions. After heating at 1 473 K for 60 s, specimens
were compressed from 12 to 8.4 mm at a temperature rang-
ing from 1 123 to 1 223 K (mainly 1 223 K). Strain rate for
263
Fig. 2. Schematic representation of hot compression test condi-
tions.
hot-compression tests was varied from 0.05 to 5 s1 (mainly
5 s1). The specimens were held isothermally at the same
temperature for various periods of time from 1 to 500 s, fol-
lowed by rapid cooling at a rate of faster than 50 K/s.
Metallographic observation was performed at the central
position of the deformed specimens. Vickers hardness was
also measured at the same position with an indentation load
of 10 N.
3. Results
3.1. Effects of Nitrogen Addition
Figure 3 shows the changes of Vickers hardness with
holding time after hot compression at 1 223 K for the speci-
mens with various nitrogen contents. Softening behavior
due to static recrystallization was almost unchanged by the
nitrogen content for the 18%Cr–9%Ni steel. The softening
of the 24.5%Cr–13.5%Ni–0.35%N steel was slightly de-
layed because of its higher chromium and nickel contents.
It is obvious from this figure that nitrogen increased hard-
ness at every period of holding time. This means that
strengthening by nitrogen addition is effective not only in
the recrystallized state but also in the deformed state.
Figure 4 shows the effects of the nitrogen content on the
Vickers hardness of the 18%Cr–9%Ni specimens quenched
immediately after compression (holding time: 1 s) and
quenched after recrystallization (holding time: 200 s). For
both conditions, the hardness increased linearly with the in-
crease of nitrogen content. The slope of the approximated
line of the deformed state, however, was larger than that of
the recrystallized one. This result indicates that nitrogen
strengthening in the deformed state is more effective than
that in the recrystallized state. The increment in hardness
for the recrystallized state is attributed to solid-solution
hardening by nitrogen, while the increment for the de-
formed state is the result of the combination of solid-solu-
tion hardening and work-hardening. Under the assumption
that the effect of solid-solution hardening is unchanged in
both states, nitrogen is considered to enhance work-harden-
ing during hot deformation.
© 2001 ISIJ
 ISIJ International, Vol. 41 (2001), No. 3
Fig. 3. Effect of nitrogen content on softening behavior during
isothermal holding after compression at 1 223 K.
Fig. 4. Effect of nitrogen content on hardness of specimens
quenched before (1 s holding) and after recrystallization
(200 s holding).
Fig. 5. Effect of nitrogen content on stress–strain curves of com-
pression at 1 223 K.
Figure 5 shows the true stress–strain curves obtained
from the hot compression tests at 1 223 K for the specimens
with 0.05 and 0.25 mass% nitrogen. It is obvious that the
nitrogen increased the flow stress at any strain values. From
the metallographic observation of specimens quenched im-
mediately after hot compression, the microstructure main-
tained the deformed state at any positions. No indication of
dynamic recrystallization was found. Consequently, nitro-
gen affected the work-hardening behavior during hot defor-
mation. Figure 6 shows transmission electron micrographs
© 2001 ISIJ
Fig. 6. Dislocation structures of specimens compressed at
1 223 K; a) 0.05 mass%, b) 0.25 mass%.
of the specimens quenched immediately after compression.
Although no evidence of precipitation was obtained in both
specimens, there was significant difference in the disloca-
tion structures. In the specimen with the low nitrogen con-
tent, a cell or subgrain structure was developed. On the
other hand, in the specimens with the high nitrogen content,
a well-defined planar structure was observed. The planar
dislocation structure could be observed in the nitrogen al-
loyed austenitic stainless steels deformed at low tempera-
tures.11–14) A marked planar structure was also observed in
18%Cr–14%Ni–0.13%N specimens, whereas a cell struc-
ture was observed in 18%Cr–14%Ni–0.001%N specimens
crept at room temperature.14) Figure 6 provides evidence
that nitrogen enhances the formation of the planar disloca-
tion structure even at high temperatures. The nitrogen ef-
fects during hot deformation will be discussed in a later
chapter.
3.2. Effects of Niobium and Molybdenum Addition
The effects of niobium and molybdenum addition were
investigated in the same way. Figure 7 shows the effect of
niobium on the softening behavior after compression at
1 223 K. Although a marked difference in hardness of the
specimens quenched after compression was not observed,
softening during isothermal annealing was significantly
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 ISIJ International, Vol. 41 (2001), No. 3
Fig. 7. Effect of niobium addition on softening behav-
ior during isothermal holding after compres-
sion at 1 223 K.
Fig. 8.
Fig. 9. Effect of molybdenum addition on softening
behavior during isothermal holding after com-
pression at 1 223 K.
suppressed by niobium addition. It was confirmed by opti-
cal microscope observations that static recrystallization in
the niobium alloyed specimens was entirely retarded after
200 s holding. Figure 8 shows the transmission electron
micrographs of the substructure and precipitates. Fine pre-
cipitates, which were found to be NbN from the electron
diffraction pattern and the EDX spectra, were observed
along dislocations. These fine particles were densely pre-
cipitated before recrystallization and probably retarded the
static recrystallization after the deformation. Niobium addi-
tion, thus, is an effective way to prevent a controlled-rolled
plate from softening before accelerated cooling.
Figure 9 shows the effect of molybdenum addition on
the softening behavior after compression at 1 223 K. From
this result, it was confirmed that molybdenum addition up
to 1.5 mass% had little effect on the softening behavior.
4. Discussion
The effects of nitrogen on work-hardening behavior at el-
evated temperatures is discussed in detail. It is well known
that nitrogen addition has a marked effect on increasing
yield strength, and this effect is significant at lower temper-
atures.15,16) Thus, nitrogen alloyed austenitic stainless steels
are used for structural materials at cryogenic temperature.
Figure 10 shows the temperature dependence of the flow
stress at 0.2% plastic strain (0.2% proof stress) for various
nitrogen contents, with data quoted from published pa-
pers.16,17) The flow stresses increase rapidly with decreasing
265
TEM investigation of 0.1 mass% niobium alloyed specimens com-
pressed at 1 223 K and 200 s holding.
Fig. 10. Effect of nitrogen content on temperature dependence of
flow stress with data quoted from Nilson et al.17) (open
symbols) and Byrnes et al.16) (open symbols).
temperature below 500 K, and the slope (∂s 0.2 /∂T)XN also
increases with increasing nitrogen content, XN. Byrnes et al.
discussed the effects of nitrogen on the flow stress separat-
ed into thermal and athermal components.16) Assuming the
athermal, s A, and the thermally activated, s T, flow stress to
be linearly additive, as shown in Fig. 10, they demonstrated
that the thermally activated flow stress,s T, could be repre-
sented as a function of the square root of nitrogen content,
and that the slope (∂s T/∂XN1/2)T increases with decreasing
temperature. From the analysis of the activation volume ob-
tained from experimental results, they considered that ther-
mally activated flow stress was mainly increased by the in-
teraction resulting from modulus change in the immediate
vicinity of a nitrogen atom. Above 500 K, the variation of
the flow stress with temperature becomes very small, and
the flow stress can be assumed to be athermal. Byrnes et
al.16) explained that this small temperature dependence
(0.05 MPa/K) resulted from the decrease of shear modu-
lus. It is obvious that the athermal flow stress also increases
with increasing nitrogen content, XN. They also demonstrat-
ed that it can be represented by a linear function of XN.
© 2001 ISIJ
 ISIJ International, Vol. 41 (2001), No. 3
Fig. 11. Effect of nitrogen content on flow stress at 0.3 true strain for various deformation temperatures and strain rates.
At higher temperature, i.e. around the hot rolling temper-
ature, it was confirmed from Fig. 6 that the nitrogen effect
on flow stress remained. The TEM observation of the de-
formed specimens suggested that nitrogen affected disloca-
tion glide and work-hardening behavior. Byrnes et al. spec-
ulated that the short-range order due to the unusually strong
affinity between chromium and nitrogen, was primarily re-
sponsible for the increase in flow stress above 500 K,16,18)
where the flow stress was mainly made up of the athermal
component. They considered that this short-range order
needed excess stress for the disruption by dislocation glide.
On the other hand, it is obvious from Fig. 6 that nitrogen af-
fected the substructures formed during hot deformation.
The dislocation structure of the specimens with high nitro-
gen content was changed into more homogeneous distribu-
tion, namely, planar structure. It can be assumed that this
change of substructure affected the work-hardening behav-
ior and increased the flow stress. This means that the dislo-
cation density at the same strain increased with the nitrogen
content. It is well known that nitrogen enhances the planar
slip of dislocations and retards cell formation during defor-
mation at low temperature.11–14) Moreover, Nilsson et al. re-
ported that planar slip was observed in low-cycle fatigue at
600 K.19) The most plausible explanation was that short-
range order led to the predominance of planar slip because
the nitrogen had little effect on the stacking fault ener-
gy.12,18) Figure 6 provides evidence that the effect of nitro-
gen on the dislocation structure is valid around 1 223 K. At
this high temperature, where atom diffusion becomes sig-
nificant, dynamic recovery during hot deformation must be
taken into account. The flow stress measured was deter-
mined by the balance of work-hardening and dynamic re-
covery. The former acts as a positive factor for increasing
the flow stress, and the latter acts as a negative one. The ap-
parent dependence of flow stress on deformation tempera-
ture and strain rate is attributed to dynamic recovery at high
temperature, where the athermal component is predomi-
nant. Figure 11 demonstrates the effect of the nitrogen con-
tent on the flow stress at 0.3 true strain for various tempera-
tures and strain rates. It can be seen that the linear relation-
ship between the nitrogen concentration and the flow stress
was maintained at any temperatures and strain rate.
Furthermore, there is large temperature dependence (0.5
MPa/K), which can not be explained from the decrease of
shear modulus, and marked strain rate dependence. From
© 2001 ISIJ
Fig. 12. Relationship between flow stress measured in hot com-
pression tests and calibrated hardness of work-hardened
specimens.
these experimental results, two mechanisms can possibly
explain the effect of nitrogen on increasing the flow stress.
One is that work-hardening is enhanced by planar slip of
dislocations, and the other is that dynamic recovery is sup-
pressed by short-range order. Although it is difficult to de-
termine which is predominant from these data, it can be as-
sumed that increase in flow stress is attributed to increase in
dislocation density. It has been reported that the flow stress
at high temperature deformation could be represented as a
function of the square root of dislocation density.20) If the
dislocation density of a specimen deformed at the same
conditions increased with nitrogen content, the increment in
hardness with nitrogen content becomes larger than that ex-
pected from solid-solution hardening. Figure 12 shows the
relationship between the flow stress measured in hot com-
pression tests and the calibrated hardness of quenched spec-
imens. The calibrated hardness means the measured hard-
ness minus the estimated value of solid-solution hardening
by nitrogen, which was calculated from the following equa-
tion based on the result of Fig. 4.
Hv (calibrated)Hv (measured)203[mass% N]
Since the deformation at lower temperature or higher strain
rate increases the density of dislocations accumulated dur-
ing deformation, the flow stress and the calibrated hardness
are increased, and the linear relationship between them ap-
pears in Fig. 12. Moreover, it can been seen that the effect
of nitrogen on the flow stress and the calibrated hardness is
266
 ISIJ International, Vol. 41 (2001), No. 3
the same as that of deformation temperature and strain rate,
because the data obtained from the specimens with differ- 1)
ent nitrogen contents are involved in the same linear rela-
tionship with a certain scattering range. Thus, it can be pre-
dicted that the nitrogen effect of increasing the calibrated 2)
hardness is attributed to increase in dislocation density dur-
ing hot deformation. 3)
4)
5. Summary
5)
Thermo-mechanical control process (TMCP) applied to
high nitrogen austenitic stainless steels could produce high- 6)
strength thick plates with a 0.2% proof stress of higher than
600 MPa. The effects of nitrogen, niobium and molybde- 7)
num on the strengthening have been examined by hot com-
pression tests around 1 223 K. The hardness of the com-
8)
pressed specimens linearly increased with increasing the ni- 9)
trogen content, and the increment in hardness was larger
than that of the specimens in a recrystallized state. This 10)
could be explained in terms of enhanced work-hardening by 11)
12)
nitrogen addition during hot compression. In fact, the flow
stress linearly increased with increasing the nitrogen con- 13)
tent, as well as decreasing the deformation temperature or
increasing the strain rate. The planar dislocation structure 14)
observed in the specimens with high nitrogen contents also
15)
gave evidence that nitrogen affected the work-hardening be-
havior. Although it was not clear that nitrogen affected the 16)
dislocation glide or dynamic recovery, it could be predicted
that nitrogen addition was effective in increasing the dislo- 17)
cation density. Niobium (0.1 mass%) gave a marked ef- 18)
fect on suppressing static recrystallization after hot defor- 19)
mation, probably owing to the fine precipitates of NbN. 20)
Thus, niobium addition is an effective way to prevent soft-
ening before accelerated cooling in TMCP.
267
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