Surface and Coatings Technology 184 (2004) 176181

Plasma nitriding of sintered AISI 316L at several temperatures

S.D. de Souzaa,*, M. Olzon-Dionysioa, E.J. Miolaa, C.O. Paiva-Santosb
b

Carlos SP, Brazil

Departamento de Fsica
UFSCar, 13565-950 Sao

Laboratorio
Computacional de Analises
Cristalograficas
e Cristalinas Instituto de Qumica
UNESP, 14800-900 Araraquara SP, Brazil

Received 15 May 2003; accepted in revised form 7 November 2003

Available Online 27 February 2004

Abstract
Samples of sintered AISI 316L stainless steel were plasma nitrided in a mixture of H2 20% N2 , for 3 or 4 h. The treatment
temperature was selected in 400550 8C interval, in steps of 50 8C. X-ray diffraction (glancing angle geometry-GAXRD),

conversion electron Mossbauer

spectroscopy (CEMS), optical microscopy and Vickers microhardness were used as analytical
techniques. For TG500 8C and ts4 h, a 40-mm layer is formed. The GAXRD results showed a transformation of the austenite
g phase to the martensite in the sinterization process and showed as well, that the g9 (Fe4 N) phase is the predominant nitride
besides small amounts of -Fe2 N, gN CrN, Cr2 O3 and the fcc nitrogen supersatured solid phase gN . The CrN phase seems to
decrease with temperature while the gN phase fraction is almost F10%, independently on the temperature. The CEMS results
indicated that while the gN fraction decreases with temperature of plasma nitriding, the g9 fraction increases proportionally.
2003 Elsevier B.V. All rights reserved.
PACS: 81.65.Lp; 87.64.Pj; 61.10.-i

Keywords: Plasma nitriding; Mossbauer

spectroscopy; X-Ray diffraction; Sintering; AISI 316L stainless steel

1. Introduction
Several nitriding techniques have been used for a
long time in industry to improve the engineering components tribomechanical properties. In the past years,
nitriding treatments have been extensively used for the
surface treatment of powder metallurgy (PyM) steel,
mainly in the automotive industry w13x.
Plasma diffusion treatment of sintered materials has
some advantages over conventional processes, such as
gas or salt bath nitriding w4x. In fact, conventional
process as nitriding by salt bath does not fit for sintered
materials, owing to the presence of porosity in these
materials. After salt bath treatment, a thorough cleaning
of the sintered part is necessary to avoid corrosion
caused by the salt remaining into the pores of the
material. During gas nitriding, the gas penetrates into
the bulk material causing an excessive hardening penetration, so that the sintered component becomes brittle.
The presence of dissolved nitrogen in large amount may
also lead to undesirable dimensional changes. These
*Corresponding author. Fax: q55-16-261-4835.
E-mail address: dsys@df.ufscar.br (S.D. de Souza).

problems can be solved only by closing the pores with

sealing pre-treatments w5x. On the other side, the ion
nitriding reduces the influence of pores on the characteristic of the modified layer, producing samples, which
present a better control of hardness and case depth. So,
pores-closing treatment are not usually needed for samples prepared by this method w6x.
In addition to its environmental acceptability, ion
nitriding also enables the production of layers with
specific structure and properties; a consequence of the
large number of freely adjustable treatment parameters,
like treatment time and temperature, gas mixture and
different pulse frequencies. Surface layers with defined
phase constitution can be produced depending on the
material composition. The best response to nitriding
usually occurs when steels contain alloying elements
that have high affinity for nitrogen, such as Cr, Al, Mo,
Mn, V and Ti. From this point of view, AISI 316L
stainless steel has been chosen as test material. Although
austenitic stainless steel tribological properties are
improved by a nitriding treatment, a reduction of the
corrosion resistance is attributed to the precipitation of
CrN and ferrite w7x.

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.11.007

S.D. de Souza et al. / Surface and Coatings Technology 184 (2004) 176181
Table 1
Chemical composition of powder
Powder

AISI 316L

Chemical composition wt. (%)

Cr

Ni

Mo

Si

Mn

Fe

18.12

12.22

2.16

0.80

0.20

0.03

66.47

The present works objective was to study the effects

of nitriding temperature and time on the surface layer
properties of sintered stainless steel.
2. Experimental procedure
The samples were produced by water atomized AISI
316L austenitic stainless steel powder, that was supplied

by Hoganas,
with average grain size of 2.5 mm. The
chemical composition of the commercial powders is
shown in Table 1.
The powder with 0.6 wt.% of zinc stearate as a
lubricant were mixed for 1 h and compacted at 600
MPa as f 20=3 mm cylinders. They were pre heated
at 450 8C for 30 min to take off the zinc stearate.
Sintering was performed at 1250 8C in a tubular furnace,
in vacuum, for 60 min. After the sintering process, the
samples were slowly cooled until room temperature,
under vacuum.
Afterwards they were nitrided in an equipment similar
to one described by Hudis w8x. A conventional d.c. glow
discharge (DGW) was applied, under a gas mixture of
80% H2q20% N2 between the workpiece (cathode) and
the furnace walls (anode). This gaseous mixture was
applied under a pressure in the range of 610 mbar for
3 or 4 h. The voltage and current density were adjusted
to maintain the cathode temperature TN at 400, 450, 500
or 550 8C. After the nitriding process, the samples were
submitted to slow cooling down under vacuum inside
the treatment chamber.
The samples were cross-sectioned, mechanically polished and then they were slightly etched with Behara
(whose composition is 20 ml of hydrochloric acid and
80 ml of distilled water). Cross-section micro-hardness
profiles were performed by using a Leica VMHT Mot
micro-hardness tester equipped with a Vickers indenter,
by using 0.01 kg load, for 15 s. The layer depth was
measured by the standard JIS G0562 method w9x. The
micrographs were taken by using Leica Leitz MMRX
optical microscope.
X-ray diffraction analysis was performed on the sample surface in glancing angle geometry (GAXRD) by
means of a Rigaku diffractometer using CuKa radiation.
The conditions were: 2u scan step 0.028, range from 30
to 1008, incidence angle fixed at 38, 5 s counting time.
For this incidence angle the thickness of the X-ray
probed layer is nearly the same as that probed by the

conversion electron Mossbauer

spectroscopy (CEMS)
technique ((0.2 mm).

177

Mossbauer
spectra were obtained in the backscattering
geometry, using a conventional constant acceleration

Mossbauer
spectrometer. A self-built detection chamber
was used, with a 95% He5% CH4 gas mixture flux. A
57
Co source in Rh matrix with nominal activity of 50
mCi was employed. The measurements were performed
at room temperature (RT). The isomer shifts are given
relative to a-Fe at RT.
3. Results and discussions
3.1. Characterization of the as sintered steel
The as sintered sample microstructure is shown in
Fig. 1. Porosity has been evaluated as 10"1%. This
figure shows also the interconnected porosity. These
results are similar to those published for the same
material used in the present work w6x. The hardness of
the sample as sintered was found to be approximately
169"20 HV(0,010).
Fig. 2 shows the GAXRD diffractograms for the AISI
316L before and after compacting and sinterizing. The
powder diffractogram showed a fcc austenitic structure
For the sintered
(g) (lattice parameter as3.591 A).
sample, our Rietveld analyses indicate the presence of
approximately 20% austenite, 65% martensite and 15%
of Cr2O3.

Fig. 3 displays the correspondent Mossbauer

spectra.
The sintered sample presents approximately 15% of
austenite and 85% of martesite. As this technique does
not measure the oxide, the results are consistent. The
transformation of austenite to martensite was observed
because the compactness and slow cooling, as also
observed by other authors w10,11x.
3.2. Characterization of the sintered and nitrided
samples
The process is more efficient for TG500 8C, which
forms a layer of approximately 40 mm, and the same

Fig. 1. Micrograph of the as sintered steel.

178

S.D. de Souza et al. / Surface and Coatings Technology 184 (2004) 176181

Fig. 4. Micrograph of sintered AISI 316 L, nitrided at 500 8C for 4

h.

Fig. 2. Glancing-angle X-ray diffractograms for samples (a) before

and (b) after compactation and sinterization.

Fig. 3. (a) CXMS spectra for samples before compactation and sinterization. (b) CEMS spectra for samples after compactation and
sinterization.

value was found by Bacci w6x. For T-500 8C, the layer
is compact and thin. Fig. 4 shows the micrographs of
the AISI 316L nitrided at 500 8C for 4 h.
Fig. 5 shows the Vickers microhardness profile related
to depth for the samples nitrided at TNs500 8C. It is
practically the same for both nitriding times and is
consistent with some previous results w6,12x. Fig. 5
shows that the hard cases thickness w13x can be estimated
as at least 20 mm, assuming 750 HV as the minimum
hardness of the nitrided layer.
Fig. 6 shows the GAXRD diffractograms for the
samples nitrided at temperatures TNs400, 450, 500 and
550 8C, for 4 h and Fig. 7 shows the correspondent
phases fractions obtained from the Rietveld program fits
as a function of nitriding temperature. The Fe phases
are separated from the Cr phases in the Fig. 7a, b,
respectively. As can be seen, the g9-Fe4 N phase is the
predominant nitride, beside small amounts of -Fe2 N,
gN, CrN and Cr2O3. Moreover, the present results

Fig. 5. Microhardness profiles of sintered AISI 316 L, nitrided at

500 8C for 3 and 4 h.

S.D. de Souza et al. / Surface and Coatings Technology 184 (2004) 176181

179

Fig. 6. Glancing-angle X-ray diffractograms for samples nitrided for 4 h.

indicate that the CrN phase seems to decrease with

temperature.
Bacci et al., who sintered the samples in a hydrogen
atmosphere and measured at deeper thickness, observed
traces of Fe3O4 as well. They discussed also the presence
of a face centered tetragonal (fct) phase, so called S
phase. Our Rietveld analyses indicate that the supersaturated fcc, called gN, fits better to the diffractograms.
However, the structure of their sintered sample was
austenitic, while our sample was martensitic.
In our samples, the gN phase amount is relatively
low, F10%, independently on the temperature. Bacci et
al. observed higher proportion for the S phase, probably

because they used a gas composition of 80 vol.% N2,

while we used 20 vol.%. Moreover, they sintered for
only 30 min, beside they measured at deeper thickness.
Fig. 8 displays CEMS spectra of the samples. These
spectra were fitted as a superposition of sub-spectra
corresponding to the g9 (Fe4 N), gN and phases.
Typical hyperfine parameters used to fit these spectra
are displayed in Table 2, which are quite similar to those
previously published w1418x. Fig. 9 shows the phase

fractions obtained from the Mossbauer

fits, as a function
of nitriding temperature for the sample nitrided for 4 h.
From the comparison between Fig. 7a and Fig. 9, it
can be concluded that the phase fractions seem to follow

Fig. 7. Phase fractions as a function of the nitriding temperature. (a) Fe phases; (b) Cr phases.

180

S.D. de Souza et al. / Surface and Coatings Technology 184 (2004) 176181
Table 2
Typical values of the parameters used to fit the different
spectra shown in this work

the same behavior. Moreover, Fig. 9 indicates that the

g9 phase seems to be correlated with the gN phase. The
gN fraction decreases with temperature, while the g9
fraction increases proportionally.

Fe CEMS

Components

H(kOe)

DEQ(mmys)

d(mmys)

gN
g9-Fe4N

178
340
215
212

y0.20
0.10
0.57

0.25
0.25
0.30
0.30
0.33

-Fe2N

Fig. 8. CEMS spectra for samples nitrided for 4 h at different

temperatures.

57

The microstructure of the nitrided samples treated for

3 h showed a smaller layer depth (5070%) than those
treated for 4 h. For TG500 8C, a layer of approximately
40 mm is formed.
GAXRD and CEMS were used as analytical techniques. The obtained results can be summarized as
follows:
The GAXRD results showed that the g9 (Fe4N) phase
is the predominant nitride besides small amounts of Fe2 N, CrN, Cr2O3 and the fcc phase gN. The CrN
phase seems to decrease with temperature while the gN
phase is F10%, independently on the temperature.
The CEMS spectra results are consistent with that
from GAXRD, indicating that the g9-phase seems to be
correlated with the gN phase. This fraction decreases
with temperature, while the g9 fraction increases
proportionally.
Acknowledgments
This work has been supported by Brazilian agency
FAPESP.

4. Conclusion
The glow discharge nitriding treatment is a useful
tool for hardening the surface layer of stainless steel
sintered components. A systematic investigation of the
chemical state of the compound layer was undertaken
on sintered AISI316 austenitic nitrided for 34 h, under
different temperatures.

Fig. 9. Fractions of the adjusted phases as a function of gN temperature, for samples nitrided for 4 h at different temperatures.

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