Surface & Coatings Technology 296 (2016) 40–45

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Surface & Coatings Technology

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

Evaluation of nitrogen diffusion in thermo-mechanically nanostructured

and plasma nitrided stainless steel
M. Golzar Shahri a,⁎, S.R. Hosseini b, M. Salehi a, M. Naderi b
a
Department of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran
b
Department of Materials Engineering, Maleke-ashtar University of Technology, Isfahan 83145-115, Islamic Republic of Iran

a r t i c l e i n f o a b s t r a c t

Article history: The effect of grain size on diffusion depth of nitrogen in AISI 321 stainless steel during plasma nitriding was
Received 25 September 2015 investigated. The repetitive cold rolling and subsequent annealing were conducted to achieve nano/ultrafine
Revised 5 February 2016 grains in AISI 321 stainless steel. The grain size range of 130 nm up to 45 μm was obtained under these conditions.
Accepted in revised form 19 March 2016
Plasma nitriding was performed at temperatures of 400, 450 and 500 °C for duration of 5 h. Microstructural
Available online 21 March 2016
evolutions were conducted by OM, SEM and TEM. The microstructure and composition of the nitrided layer
Keywords:
were characterized by SEM and GDOES. Mechanical properties of the S phase were evaluated by micro-
Austenitic stainless steel hardness testing. Results indicated that nitrided layer of the nanostructured steel have uniform appearance
Plasma nitriding with no CrN precipitates, while CrN precipitations were formed in nitrided layer of the micro-grain one. The cor-
Nanostructured steel rosion resistance of the nitride layer was improved in nanostructured condition because of uniform appearance
Diffusion depth of nitrogen of the nitride layer. Furthermore, the hardness of the S phase improved by decreasing substrate grain size.
Increasing austenite grain size from 130 nm up to 45 μm, caused to increase surface nitrogen concentration in ni-
tride layer. Decreasing austenite grain size led to decreases the S phase thickness, while the nitrogen diffusion
mechanism is the same.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction mechanism of expanded austenite is still unknown and is the subject

Plasma nitriding (PN) is one of the thermochemical process used to
introduce nitrogen into austenitic stainless steel to improve the surface
hardness [1,2]. Since there is a deterioration of corrosion properties
when CrN forms, there is a great interest of introducing nitrogen into
the austenite matrix without CrN formation [3,4]. Thus, the nitrided
steels having high surface hardness and good corrosion properties can
be achieved by formation of the nitride layer which is formed at temper-
atures below 500 °C. Nitriding below 500 °C results in a thin layer that is
saturated with nitrogen atoms referred as S phase. In addition, forma-
tion of S-phase was observed in samples treated at 20% N2 atmosphere.
The compound layers thickness increases with increasing N2 content in
the atmospheric gas mixture up to approximately 80% N2 [5]. The S
phase was first reported by Zhang and Bell in 1985 [6]. In parallel
investigation, Ichii et al. obtain the S phase by low temperature nitriding
at 400 °C [7]. The term S phase was invented by Ichii et al. [7] and also
referred as expanded or supersaturated austenite by Leyland et al. [9,
10], the m phase by Marchev et al. [10,11], and the έ phase [12]. It is
also denoted as the Ś phase by Gontijo et al. [13]. Despite of many stud-
ies devoted to ion nitriding of austenitic stainless steel, the formation
⁎ Corresponding author.
E-mail address: m.golzar@ma.iut.ac.ir (M. Golzar Shahri).
of current investigations.
Pretreatment of austenitic stainless steel like heat treatment can
change its properties. Heat treatment influences the grain size, and con-
sequently diffusivity. Manova et al. have reported that slower diffusion
rate was observed in larger grains in AISI 304 stainless steel [14]. Tong et
al. have indicated that a decrease in grain size from 1000 μm to 13 nm
causes a faster diffusion rate by order of 1000 in AISI 304 stainless
steel [15]. Additionally, different data sets are reported in the literature
concerning nitrogen diffusion in austenitic stainless steel without
providing any information about the grain size [16–18]. There is no
model explaining these quite diverging results [14]. Moreover, scanty
studies have been performed on nitrogen diffusion in connection with
microstructure, so the published diffusion values could be misleading.
The present work focused on the effect of nanograins on diffusion
depth of nitrogen in AISI 321 stainless steel through plasma nitriding.
In addition, the effect of nanograins on mechanical properties and
corrosion behavior of nitride layer was investigated.
2. Materials and experimental procedures
The substrate material was made of AISI 321 austenitic stainless steel
with the composition of: C 0.06 wt.%, Si 0.75 wt.%, Mn 1.22 wt.%, P
0.043 wt.%, S 0.003 wt.%, Cr 17.88 wt.%, Ni 9.28 wt.%, Ti 0.36 wt.% and
Fe balance. The mean grain size of the as received material was about

http://dx.doi.org/10.1016/j.surfcoat.2016.03.058
0257-8972/© 2016 Elsevier B.V. All rights reserved.
 M. Golzar Shahri et al. / Surface & Coatings Technology 296 (2016) 40–45
45 μm. The smallest grain was about 4 μm and the largest grain was
about 130 μm. The microstructure evaluations were performed using
clemex software. Hot rolled steel strips with 10 mm initial thickness
were rolled with 90% thickness reduction at best possible temperature
of −20 °C [19]. The cold rolling was followed by annealing treatments
in an electrical furnace at 800 °C for 4,6,8,10,15,20,30 min to achieve
grain size ranges of 0.13–5 μm. The nitriding process was performed
in a pulsed DC plasma nitriding unit. Prior to nitriding the specimens
were polished and cleaned ultrasonically in acetone for 15 min. In
order to carry out plasma nitriding, the vacuum chamber was pumped
down to 0.05 Torr and then the specimens were subjected to
sputtering for surface cleaning using an atmosphere composition of Ar
33 vol%\\H2 67 vol% under the pressure of 0.3 Torr for 1 h. Afterwards,
plasma nitriding was performed for 5 h for various temperature ranges
from 400 to 500 °C by using a gas mixture N2 20 vol%\\H2 80 vol% under
the pressure of 3 Torr. The process was conducted on specimens with
average grain size of 0.13–45 μm. At the end of the treatment, the
samples were slowly cooled down under vacuum.
The microstructures were studied by Optical Microscope (OM,
Olympus GX71), Scanning Electron Microscope (SEM, COXEM CX100)
and Transmission Electron Microscope (TEM, JEOL JEM-ARM300F).
Feritscope device (Fischer FMP30) was employed to measure the
austenite volume percentage after heat treatment. The structure and
thickness of the S phase was evaluated by SEM. The diffusion depth of
nitrogen and surface composition of nitrided steel was measured by
means of Glow Discharge Optical Emission Spectroscopy system
(GDOES, HORIBA JOBIN YVON). Mechanical properties of S phase was
determined using micro-hardness testing (Shimadzu, HMV-2) with a
load of 0.1 N. Average results were reported after five trials for micro-
hardness testing.
3. Results and discussion
Optical micrograph of as-received material (micro-grain steel)
consisting austenite grains has shown in Fig. 1. This indicates that the
average grain size prior to cold rolling was approximately 45 μm. The
microstructure evaluations were performed using clemex software
according to ASTM E112-12 [20]. Fig. 1b shows the higher magnification
Fig. 1. (a) Optical micrograph of as received AISI 321 stainless steel, (b) SEM micrograph of the specimen annealed at 800 °C for 15 min and (c) TEM micrograph of the specimen annealed
at 800 °C for 4 min.
41
SEM micrograph after thermo-mechanical process, i.e. cold rolling
process and 15 min annealing at 800 °C. Fig. 1c displays the TEM micro-
graph after cold working and 4 min annealing at 800 °C.
As be seen, average grain sizes achieved to 130 nm and 3 μm
(nanostructured and fine grain steels) after 4 and 15 min annealing
respectively. Feritoscopic results show that the annealed samples have
fully austenitic structure. It revealed that the reversed austenite
grains have fully recrystallized and no martensite lathes remain in the
matrix.
The SEM micrograph and GDOES profile of the micro-grain steel
after plasma nitriding at 500 °C are presented in Fig. 2. As shown in
Fig. 2a, the nitride layer thickness for as-received steel is about 24 μm.
Besides, grain boundary precipitation of chromium nitride, which
causes chromium depletion in the matrix, is observed in the grain
boundaries. The chromium nitride precipitations have been seen in
other investigations at temperatures above 450 °C [21–24]. In such
temperatures, chromium atoms can diffuse rapidly and facilitate the
chromium nitride formation. The Chromium depletion could be respon-
sible for the lower corrosion resistance of the layer and unfold the CrN
precipitation [21–26]. The GDOES analysis also demonstrates that
nitrogen atoms have diffused into the substrate with a depth of about
24 μm (Fig. 2b).
The plateau like appearance of the nitrogen GDOES profile indicates
that the nitrogen atoms diffusion don't obey the fickian models. In the
literature, plateau shape refers as trapping-detrapping model sign [18,
21,27,28]. In addition, the hardness of the nitride layer was determined
to be about 1200 HV. It is due to the supersaturated structure of the
nitride layer. Nitrogen atoms in the interstitial sites, reduce the mobility
of dislocations and improve the mechanical properties of the layer.
Fig. 3a shows that the nitride layer thickness of fine grain steel is
about 13 μm. it is much thinner than that of the micro-grain steel
(Fig. 2a). However, the presence of CrN precipitates is also observed in
some areas of the grain boundaries. Besides that, the GDOES profile
reveals that diffusion depth of nitrogen is also about 14 μm (Fig. 3b).
The plateau shape of the nitrogen GDOES profile indicates the
trapping-detrapping mechanism of nitrogen atoms. Moreover, the
hardness of the nitride layer was about 1250 HV. Further hardness of
the fine grain steel nitride layer rather than micro-grain steel is due to
42 M. Golzar Shahri et al. / Surface & Coatings Technology 296 (2016) 40–45

Fig. 2. (a) SEM micrograph of nitride layer, (b) GDOES analysis of micro-grain size steel after plasma nitriding at 500 °C.

Fig. 3. (a) SEM micrograph of nitride layer, (b) GDOES analysis of the fine grain steel after plasma nitriding at 500 °C.
 M. Golzar Shahri et al. / Surface & Coatings Technology 296 (2016) 40–45 43

Fig. 4. (a) SEM micrograph of nitride layer, (b) GDOES analysis of the nanostructured steel after plasma nitriding at 500 °C.

the increased grain boundary volume fraction that causes to decrease
dislocation mobility.
This is obvious from Fig. 4a that, the nitride layer thickness of
nanostructured steel is also near 12 μm. So, the thickness layer is
much thinner than that of the micro-grain steel and slightly thinner
than that of fine grain steel. As can be seen from this micrograph, the
S phase microstructure is free of CrN precipitations and has a uniform
Appearance. The uniform Appearance of the S phase indicates that the
corrosion resistance of the layer is more than that of the micro-grain
and fine grain steel. The GDOES profile also illustrates that nitrogen
atoms have diffused in to the depth of around 12 μm (Fig. 4b). The hard-
ness of the layer was measured to be almost 1400 HV. Because of CrN
formation in saturated austenite, the hardness of the nanograin steel ni-
tride layer is the highest measured hardness.
In addition, studies demonstrate that chromium atomic concentra-
tion curve has positive slope from bulk to the surface in nanostructured

Fig. 5. Variation of chromium and nitrogen concentration in nanostructured stainless steel after plasma nitriding.
44 M. Golzar Shahri et al. / Surface & Coatings Technology 296 (2016) 40–45
stainless steel (see Fig. 5). In other word, the positive slope goes from
the bulk to the surface, indicated the chromium atoms diffusion from
the bulk to the surface of the substrate.
Three main mechanisms are proposed to describe the diffusion
behavior of nitrogen atoms in austenitic stainless steel: “Simple
diffusion based on Fick's laws”, “nitrogen diffusion coefficient depen-
dence of nitrogen concentration” and “trapping-detrapping at Cr sites
mechanism” [18,21,27–29]. In ion nitriding “simple diffusion” and
“diffusion coefficient dependence of concentration” mechanisms often
deals with single-phase substrates with negligible mobility of substrate
atoms compared to that of nitrogen. Other mechanism “the trapping-
detrapping of the nitrogen by chromium atoms” is relevant for the
diffusional transport in ion nitriding of austenitic stainless steel at low
temperatures. As experimental results revealed, decreasing the grain
size reduces the nitrogen diffusion depth in austenitic matrix. Reduction
in nitrogen diffusion depth can be explained considering the trapping-
detrapping mechanism. When grains become finer, rapid diffusion
paths such as grain boundaries and crystal defects like dislocations
and vacancies increase. So, thermal mobility of substrate atoms such
as chromium and iron increases. Therefore, trapping-detrapping
mechanism plays an important role and simple diffusion mechanism
has handicapped. In nanostructured matrix (with high defect density)
chromium atoms diffuse faster than microstructured one and trap the
nitrogen atoms closer to the substrate surface. While, nitrogen diffusion
rate does not change obviously with increasing grain size, because
diffusion in any path (grain boundary, among dislocation and lattice)
is easy for small atoms. Moreover, as reported before, crystal defects
also act as trap sites for nitrogen [30]. It is evidence that in nanostruc-
tured steel and fine grain steel with high level of dislocations and crystal
defects, the trap sites density for nitrogen atoms are greater than coarse
grain steel. Therefore, the finer the grains, the thinner the nitrided layer
thickness (S phase). The mobility of the chromium atoms and trapping
of the nitrogen atoms are also clear from Figs. 2b, 3b and 4b. The varia-
tion of chromium concentration in nanostructured steel after plasma ni-
triding is represents in higher resolution in Fig. 5. As can be seen,
chromium concentration has positive slope from bulk to surface. Virtual
decline in chromium atomic percent in nitrided layer is due to the
presence of nitrogen atoms in the layer that virtually decrease the
chromium percent in the GDOES curves. The increment of chromium
atomic percent from bulk to surface demonstrates the replacement of
consumed chromium atoms in nitride layer (S phase) with chromium
atoms in the periphery. The chromium replacement, as a result of high
diffusion rate of substitutional atoms, leads to overall chromium trans-
port from the bulk to the surface. As realized from SEM micrographs
(Fig. 4a), chromium depletion did not occur in nanostructured S phase
as a result of fully uniform distribution of chromium atoms in nano-
structured matrix i.e. grain boundaries and crystal defects [31]. In such
matrix, nano-sized CrN precipitates form and chromium atoms can dif-
fuse rapidly and compensate depletion. It is evident that nanostructured
S phase hardness (1400 HV) is higher than those of the micro- grain and
fine grain (1200 and 1250 HV respectively) as a result of nano-sized CrN
precipitates. In addition, it is reported that, the nitrogen diffusivity in
CrN is four orders of magnitude lower than in Fe4N and two orders of
magnitude lower than that in austenitic matrix [32]. So, chromium ni-
tride and uniform distribution of chromium nitride might act as barrier
with trapping-detrapping occurring on the periphery. It has been
shown that the presence of nano-sized precipitates having coherent in-
terface against matrix, can extremely improve the mechanical proper-
ties of materials by locking dislocations [33].
4. Conclusion
1- Contrary to the impressions, our results indicated that nitrogen
diffusion rate in austenitic stainless steel during plasma nitriding
decreases with decreasing grain size. This is due to the increasing
in diffusion rate of chromium atoms as substitutional atoms in
contrast of the diffusion rate of nitrogen atoms as interstitial
atoms. Furthermore, decreasing led to increasing crystal defects
that act as trap sites for nitrogen. Therefore, chromium atoms and
crystal defects trap the nitrogen atoms preventing the migration for-
ward of nitrogen atoms. Another reason for decreasing nitrogen dif-
fusivity in nanostructured steels is CrN precipitations and uniform
distribution of CrN precipitates that decelerate the nitrogen
mobility.
2- Hardness of the nitride layer was improved by substrate decreasing
grain size. Nanometric CrN precipitation having coherent interface
against matrix is responsible for hardness increment by causing
dislocations pile up. The uniform appearance of the S phase in nano-
structured steel indicates the appropriate corrosion resistance of the
layer. The uniform appearance and higher hardness of the S phase in
nanostructured steel verified this mechanism.
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