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Surface & Coatings Technology 202 (2008) 3607 – 3614

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Application of Mössbauer spectroscopy to the study of corrosion resistance

in NaCl solution of plasma nitrided AISI 316L stainless steel
M. Olzon-Dionysio a , S.D. de Souza a,⁎, R.L.O. Basso b , S. de Souza c
a
Departamento de Física, Universidade Federal de São Carlos, 13565-950, São Carlos, SP, Brazil
b
Instituto de Física “Gleb Wataghin”, Universidade Estadual de Campinas, 13083-970, Campinas, SP, Brazil
c
Instituto de Química de São Carlos, Universidade de São Paulo, 13560-970, São Carlos, SP, Brazil
Received 27 April 2007; accepted in revised form 29 December 2007
Available online 11 January 2008

Abstract

Corrosion research in steels is one of the areas in which Mössbauer spectroscopy has become a required analytical technique, since it is a
powerful tool for both identifying and quantifying distinctive phases (which contain Fe) with accuracy. In this manuscript, this technique was used
to the study of corrosion resistance of plasma nitrided AISI 316L samples in the presence of chloride anions. Plasma nitriding has been carried out
using dc glow-discharge nitriding treatments, in medium of 80 vol.% H2 and 20 vol.% N2, at 673 K, and at different time intervals: 2, 4, and 7 h.
Treated samples were characterized by means of phase composition and morphological analysis, and electrochemical tests in NaCl aerated
solution in order to investigate the influence of treatment time on the microstructure and the corrosion resistance, proved by conversion electron
Mössbauer spectroscopy (CEMS), glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM) and potentiodynamic
polarization. A modified layer of about 8 μm was observed for all the nitrided samples, independently of the nitriding time. A metastable phase, S
phase or γN, was produced. It seems to be correlated with γ′-Fe4 N phase. If the γN fraction decreases, the γ′ fraction increases. The γN magnetic
nature was analyzed. When the nitriding time increases, the results indicate that there is a significant reduction in the relative fraction of the
magnetic γN (m) phase. In contrast, the paramagnetic γN (p) phase increases. The GAXRD analysis confirms the Mössbauer results, and it also
indicates CrN traces for the sample nitrided for 7 h. Corrosion results demonstrate that time in the plasma nitriding treatment plays an important
role for the corrosion resistance. The sample treated for 4 h showed the best result of corrosion resistance. It seems that the ε/γ′ fraction ratio plays
an important role in the corrosion resistance since this sample shows the maximum value for this ratio.
© 2008 Published by Elsevier B.V.

Keywords: AISI 316L stainless steel; Plasma nitriding; Mössbauer spectroscopy; Glancing angle X-ray diffraction; Corrosion

1. Introduction ings are a viable alternative to attenuate excessive corrosion in

Austenitic stainless steels are widely used in many industrial
fields [1] as well as in the reparation or replacement of human
body parts [2]. Two of the most important parameters in de-
termining the suitability of a material for biomedical appli-
cations are its biocompatibility and corrosion resistance. The
corrosion of the metallic piece implanted in the human body
may result in the releasing of corrosion products with harmful
biological consequences [2,3]. Then, protective nitrided coat-
⁎ Corresponding author. Fax: +55 16 3361 4835.
E-mail address: dsys@df.ufscar.br (S.D. de Souza).
0257-8972/$ - see front matter © 2008 Published by Elsevier B.V.
doi:10.1016/j.surfcoat.2007.12.040
aggressive environments [1,3–9]; also, it is important to com-
bine good mechanical and tribological properties [1,10–16].
Numerous studies have been published in which various
nitrided coatings obtained in different conditions of plasma
nitriding treatment (i.e. time [1,14,17–21], temperature [4–
6,10–14,22–24], pressure [1,14,15], and dose ions implantation
[7,8]) and some others that emphasized the influence of the
plasma nitriding on corrosion resistance of different metals and
alloys [1,3–16].
Plasma nitriding is a common surface processing in which
nitrogen is introduced into a metal for improving its wear,
hardness, and corrosion resistance. At relatively high tempera-
ture (773 K or above), the traditional nitriding can improve the
3608 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614
wear and hardness resistance; while the corrosion resistance is
generally diminished due to the formation of a very stable and
hard precipitate, the chromium nitride (CrN) [25]. The depletion
of chromium in the austenitic matrix zone cannot therefore form
a uniform and protective passive film and the metal surface is
subjected to active corrosion [26]. Borgioli et al. [13] carried out
a study about the influence of temperature in the glow-discharge
nitriding of AISI 316L stainless steel. They show that for the
samples nitrided at temperatures up to 723 K, besides the S
phase, small chromium nitride precipitates are present in the
surface, while using higher treatment temperatures both
chromium (CrN) and iron (γ′-Fe4 N) nitrides precipitate along
the grain boundaries and in the middle of the grains, and their
amount increases as treatment temperature increases. Therefore,
it is important to prevent the large amounts of chromium nitrides
by carrying out treatments at temperatures lower than about
723 K. In fact, at these temperatures, the chromium diffusion is
reduced and, consequently, the formation of these nitrides is
inhibited. Using low treatment temperatures the modified sur-
face layer consists essentially of a metastable phase, known as
supersaturated nitrogen solid-solution FCC phase, or expanded
austenite γN phase, or S phase, or m phase, which has proved to
have good mechanical and tribological properties and corrosion
resistance [1,10–16].
The purpose of this study is to investigate the influence of the
treatment time in the dc glow-discharge nitriding of AISI 316L
austenitic stainless steel, by using treatment temperature of
673 K. Three different time intervals were employed (2, 4, and
7 h). The microstructural composition, corrosion resistance in
environment with chloride ions, and metallographic appearance
of nitrided samples were studied as a function of the treatment
time and were compared with those of the untreated stainless
steel. In this research area, Mössbauer spectroscopy plays an
important role, since it can identify and quantify the iron phases
that are formed on and that are nearly transparent to most other
spectroscopy techniques.
2. Experimental procedure
The material used in this study was AISI 316L austenitic
stainless steel with chemical compositions (in wt. %) of Cr
(17.03), Ni (10.16), Mo (2.16), C (0.032), and Fe balance. In the
industry, the stainless steel was solubilized at 1323 K (1050 °C)
for 60 min and cooled in water. Samples were obtained from a
rod of 2.0 cm diameter to discs of 0.3 cm thick and, later, were
grinded and polished. After that, these samples were submitted
to plasma nitriding, following the process already described in
the literature [27]. A conventional dc glow-discharge (DCGD)
was applied, in a gas mixture of 80 vol.% H2 and 20 vol.% N2,
between the work piece (cathode) and the furnace walls (anode).
This gaseous mixture was applied under a pressure of about
6 mbar. Voltage (≈ 450 V) and current density (≈500 mA) were
adjusted to maintain the cathode temperature (or nitriding
temperature, TN = 673 K). After the plasma nitriding process,
during different time intervals (nitriding time, tN = 2 h, tN = 4 h,
and tN = 7 h), the samples were submitted to slow cooling inside
the treatment chamber, under vacuum.
CEMS and GAXRD analyses were performed in order to
identify the phases present in surface layers. The Mössbauer
spectra were obtained in the backscattering geometry, using a
conventional constant acceleration Mössbauer spectrometer. A
self-built detection chamber was used, with a 95 vol.% He and
5 vol.% CH4 gas mixture flux. A 57Co source in Rh matrix with
nominal activity of 25 mCi was employed. The CEMS measure-
ments were performed at room temperature, and the isomer
shifts are given relative to α-Fe. X-ray diffraction analysis
(CuKα radiation) was performed in glancing angle geometry
(GAXRD) by using a D5000 Siemens diffractometer equipped
with a graphite monochromator. The conditions were: 2θ scan
step 0.03°, range from 30°–100°, incidence angle fixed at 3°, 4 s
counting time. For this incidence angle the thickness of the X-
ray probed layer is nearly the same as the one probed by the
CEMS technique (≈ 0.2 μm).
The corrosion performance of untreated and nitrided samples,
in 3% NaCl aerated electrolytic solution, was investigated using
a 273A Potentiostat/Galvanostat. Potentiodynamic polarization
curves were obtained using the EG&G-Pal M352 Software.
The scanning potential was in the range between −1.0 V(SCE)
(cathodic potential) and + 1.2 V(SCE) (anodic potential), and the
scan rate was 1 mV/s. Electrochemical experiments were per-
formed in a conventional Pyrex cell using untreated and nitrided
AISI 316L as working electrodes and a platinum sheet as counter
electrode. The potentials were referred to the saturated calomel
electrode (SCE) in a KCl solution and all electrochemical
experiments were performed at 298 K. After the corrosion tests,
microscopy analysis was carried out in order to evaluate the
corrosion morphology and the extension of damaging, using a
JEOL scanning electron microscope, JSM — 5800 LV model.
3. Results and discussion
3.1. Characterization of plasma nitrided layer
3.1.1. Conversion Electron Mössbauer Spectroscopy (CEMS)
The analysis of the untreated sample spectrum, in Fig. 1,
shows that the surface is formed by 42% of austenitic FCC
phase represented by one single-line (IS = − 0.10 (1) mm/s). The
remaining 58% of the surface was found to be one double-line
component (IS = − 0.09 (1) mm/s and EQ = 0.12 (1) mm/s),
which means that the FCC cubic symmetry is affected by the Fe
Fig. 1. CEMS spectrum for the sample before nitriding, showing the subspectra
used in the fitting procedure.
 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614 3609

Fig. 2. CEMS spectrum for the sample nitrided during 1 h, showing the
subspectra used in the fitting procedure.
Fig. 3. CEMS spectra for samples nitrided during different times, 2, 4, and 7 h.

atom neighbors. These hyperfine parameters are in good agree- phases, other subspectra were necessary to good fittings, corre-
ment with results of other authors [28,29]. sponding to the γ′-Fe4 N, γN (p), ε and α⁎ phases.
Now we discuss in detail the results for the samples nitrided The γN (p) phase, a paramagnetic FCC N solid-solution
during 1 h The spectrum shown in Fig. 2 was decomposed into phase, contains less N in solution than γN (m) [30]. The α⁎ phase
four components giving the best fitting results. Table 1 presents is a superposition of multiple sextets referring to α (Fe, Cr, Ni),
the adjusted parameters. α′-martensite and α″-Fe16 N2 phases. It probably results from
The high concentration of interstitial nitrogen atoms and induced stress during the N implantation [33].
inhomogenously distributed alloying elements (Ni, Cr, and Mo) Table 2 presents the interval values of the Mössbauer para-
make it impossible to characterize the surrounding of the reso- meters used for the samples nitrided during different times.
nating iron atoms more precisely and an application of distri- These parameters are similar to those previously published
bution of hyperfine induction values was therefore inevitable. [20,23,33–42].
Consequently, Table 1 presents the mean value of the distributions Fig. 4 shows the phase fractions obtained from the
of hyperfine magnetic corresponding to the dominant component. Mössbauer fits as a function of nitriding time, where γN = γN
As it can be seen, the two first components, both identified as γN (p) + γN (m). The γ′ phase seems to be correlated with the γN
(m) phase, present the major fraction, 73% (54% + 19%). Our phase. If the γN fraction decreases, the γ′ fraction increases.
parameters are similar to those previously published [30–33]. This correlation was observed in a previous study, regarding
Williamson et al. [34] have found that a high content of N variation of nitriding temperature [23].
determines the ferromagnetic character of this phase. Besides, our As CEMS results can reveal the behavior of the magnetic
mean values agree with their results and of other authors [33]. The nature of the γN phase, it is interesting to discuss it from the point
third component of surface region was ascribed to ε-Fe2,02 N, a of view of nitriding time. Table 3 shows the relative fraction for
paramagnetic hexagonal Fe2 N-like phase which probably the paramagnetic and magnetic γN phase for different nitriding
contains Cr and Ni as well. The remaining fourth component is times.
the matrix.
Fig. 3 shows the CEMS data for the samples nitrided at 2, 4,
and 7 h. The fitting of these spectra did not need distribution on Table 2
hyperfine magnetic field. Besides the γN (m) and ε-Fe2,02 N Interval of values of the parameters used to fit the different CEMS spectra for
nitriding time of 2, 4, and 7 h
Phase H (T) EQ (mm/s) IS (mm/s)
Table 1
Hyperfine parameters of the samples nitrided for 1 h γN (m) 17.5 ± 0.5 – 0.11 ± 0.07
γN (m) 13.1 ± 0.5 – 0.28 ± 0.01
Phase H (T) EQ (mm/s) IS (mm/s) R.A. (%) Reference
ε-Fe2.02N – 0.36 ± 0.02 0.35 ± 0.04
γN (m) 19.9 – 0.16 54 31 γ′-Fe4N 33.6 ± 0.3 – 0.29 ± 0.18
γN (m) 15.4 – 0.07 19 32 21.5 ± 0.4 0.15 ± 0.01 0.22 ± 0.11
ε-Fe2.02N – 0.36 0.25 11 33 21.1 ± 0.2 −0.19 ± 0.02 0.25 ± 0.08
Γ – – − 0.11 16 34 γN(p) – – − 0.20 ± 0.03
ε-Fe2 + xN 26.4 ± 3.0 – 0.23 ± 0.14
H (T), mean value of the distribution of hyperfine magnetic induction; EQ,
x = 0.47, 0.5, 0.67, 1, 1.2
quadrupole splitting; IS, isomer shift; R.A., relative area.
α⁎ 29.5 ± 4.0 – − 0.01 ± 0.09
Typical errors are ±5%.
3610 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614
Fig. 4. Fractions of the adjusted phases as function of different time intervals, for
samples nitrided at 673 K.
As the nitriding time increases, the results indicate sig-
nificant reduction in the relative fraction of the γN (m) phase. In
contrast, the paramagnetic γN (p) phase increases. This situation
was observed before, when the γN (m) phase (produced in 304
stainless steel) transformed systematically on annealing at
673 K to a thicker γN (p) phase with less N in solution and less
lattice expansion, thereby destabilizing the magnetic state of the
γN (m) [43].
3.1.2. Glancing angle X-ray diffraction (GAXRD)
Fig. 5 shows the XRD diffractograms for the samples before
and after nitriding, during different time intervals. In some way,
they indicate the tendency of nitriding time to influence on the
microstructure of the modified layer. Besides the substrate
peaks, it is also possible to see the broader γN phase peaks that
are shifted to lower angles, signifying a great degree of nitrogen
supersaturation, indicating that the nitrided layers that are
formed are rich in defects and highly stressed. As the nitriding
time increases, the γN phase peaks shift decreases as well as its
full widths at half maximum. Fossati et al. [1] observed an
opposite behavior, for the nitrided 316L samples. Their γN
phase peaks shift towards lower angles as the nitriding time
increases. However, their conditions were distinct: a mixture of
gases of 80% N2–20% H2, besides a higher temperature, 703 K.
On the other hand, Öztürk and Williamson [30], who used
T = 673 K, observed not only does the shift of the γN phase peak
positions depend on the nitrogen concentration, but also that the
full widths at half maximum are bigger when the γN phase
presents magnetic character.
Table 3
Paramagnetic and magnetic γN phases relative fraction for different nitriding
times
Nitriding time (h) γN (p) (%) γN (m) (%) γN = γN (p) + γN (m) (%)
1 0 73 73
2 4 18 22
4 9 20 29
7 25 12 37
Fig. 5. GAXRD data for samples nitrided during different times, 2, 4, and 7 h.
As seen before, the CEMS results indicate the magnetic
nature of the γN phase for samples nitrided at 1 h, which can
justify the bigger enlargement for its diffractogram. It seems
difficult to affirm that the γ′ and ε phases are present for
nitriding time tN ≤ 4 h, because of the proximity of its peaks
positions and the γN phase peaks. However, its presence is
possible for the sample nitrided for 7 h. Besides, CrN traces are
possibly present. It is important to emphasize that the
Mössbauer spectroscopy is a powerful tool to quantify and to
identify distinctive phases (which contain Fe, in this study) with
safety, since the parameters of each phase are well defined and
distinct. In this paper, this technique indicates the occurrence of
both phases, γ′ and ε, in the nitrided samples surface.
Regarding the γ′ phase, in a previous study on AISI 316L
nitrided samples, Borgioli et al. [44] indicated that for smaller
values of the gas pressure used in the nitriding, there is a higher
formation of the γ′ phase. This result confirmed the article
published by Jeong et al. [45], in the same sample, in similar
conditions of gas, temperature and time, but lower pressure.
These latter authors seem to have observed higher amounts of
γ′ phase than Borgioli et al. [44] observed. In comparison with
these preceding results, in the current paper, a pressure of
6 mbar was used, beyond a less proportion of N2 in the gas
mixture, both favoring the γ′ phase formation.
3.1.3. Scanning Electron Microscopy (SEM)
The thickness of the plasma nitrided layer at different times
was estimated using SEM analysis. Fig. 6 shows the cross-
 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614 3611

the other hand, Dimitrov et al. [46] proposed a model describing

both compound layer and diffusion zone growth. In their re-
search, the total thickness of the compound layer as a function
of square root of time and, starting about 2 h, the thickness of
the compound layer is approximately constant.

3.2. Corrosion behavior

Fig. 7 shows the potentiodynamic curves recorded towards

positive potentials, in a freshly prepared 3% NaCl aerated
electrolytic solution of the following electrodes: 316 L/nitrided
(tN = 2 h), 316 L/nitrided (tN = 4 h), and 316 L/nitrided (tN = 7 h).
The typical linear voltammetry of the untreated AISI 316L
stainless steel sample, obtained in the same experimental con-
ditions, is also reported as a reference.
In particular, in Fig. 7, the potentiodynamic curve obtained for
the untreated electrode shows, between −0.25 and −0.13 V(SCE),
a discreet increase of the anodic current density values. Whereas,
between −0.13 and +0.15 V(SCE), an oscillating behavior is
observed, which is typical of metals in chloride solutions [47].
Also, it can be observed that, starting approximately at
+0.15 V(SCE), the anodic behavior of the matrix in NaCl solution
is represented by a curve with an active dissolution, which rep-
resents a drop in the passivity.
The very large dissolution current observed for uncoated
polished 316L electrode was substantially diminished when this
electrode was coated with a nitrided layer, even in the presence of
chloride anions. For uncoated polished 316L, to E = 1.0 V(SCE),
the anodic current density value of about 2.8 × 10− 4 A/cm2 (see
Table 4). In contrast, to E = 1.0 V(SCE), the anodic current density
values obtained for 316L samples covered with nitride layer were
about 9.4 × 10− 6, 5.7 × 10− 6, and 2.2 × 10− 5 A/cm2 in agreement
with the increase of the nitriding time (2, 4, and 7 h, respectively).
These results show a displacement of the current towards lower
values for the 316L substrate covered with nitrided layer.

Fig. 6. SEM micrographs of the nitrided samples at (a) 2 h, (b) 4 h, and (c) 7 h.

sectional micrographs of the nitrided austenitic stainless steel

samples at (a) 2 h, (b) 4 h, and (c) 7 h. All the nitrided samples
possess compound layer with very similar thickness. The
compound layer is only a few microns in thickness, about 8 μm.
These results are in agreement with the observations provided Fig. 7. j/E potentiodynamic profiles of 316L/untreated, 316L/nitrided (tN = 2 h),
by Wang et al. [26]. In addition, they also related that the 316L/nitrided (tN = 4 h), and 316L/nitrided (tN = 7 h) electrodes in 3% NaCl
thickness of nitrided layer is a function of the temperature. On aerated electrolytic solution.
3612 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614

Table 4 Table 5
Results of the corrosion resistance test in AISI 316L electrodes in 3% NaCl Phases fractions obtained from the Mössbauer fits as a function of nitriding time
solution
Time (h) γN (%) α⁎ (%) ε-Fe2 + xN (%) γ′ (%) ε/γ′ fraction ratio
Samples Anodic current density ≅ J (A/cm2), Corrosion
2 22 9 27 42 0.64
to E = 1.0 V potential ≅ Ecorr (V)
4 29 10 28 33 0.84
Untreated 2.8 × 10− 4 − 0.30 7 41 4 17 38 0.45
Nitrided at 2 h 9.4 × 10− 6 − 0.14
Nitrided at 4 h 5.7 × 10− 6 − 0.13
Nitrided at 7 h 2.2 × 10− 5 − 0.18
corrosion potential (− 0.18 V(SCE)) compared with the other
three samples. In addition, untreated and nitrided (tN = 7 h)
Thus, the protective character of the nitrided layer is clearly samples show a rapid increase in current density above cor-
demonstrated, which is confirmed by the current variation that is rosion potential. Rapid increase in current usually means the
almost two orders of magnitude lower [for 316L/nitrided breakdown of the passive film on stainless steel surface, in-
electrode (tN = 4 h)] than that of untreated electrode in NaCl dicating localized corrosion, commonly known as pitting
solution. corrosion. Indeed, visual and microscopic examinations of the
All the nitrided samples show a higher corrosion potential corroded surfaces revealed that both samples were severely
(Ecorr) in comparison with untreated sample, as reported in attacked by pitting corrosion during the polarization test in
Table 4. The corrosion potential for the nitrided sample at 4 h chloride anions environment, as is presented later.
was shifted in the noble direction by approximately 0.17 V(SCE), The amount and sizes of pits can be clearly seen in the
in comparison with the untreated sample. The sample nitrided at SEM micrographs exhibited in Fig. 8 (a) to (d). The corroded
higher time interval (that is, tN = 7 h) exhibits poorer corrosion surfaces of untreated and nitrided samples were examined after
resistance in chloride solution, having the second lowest polarization tests. Morphological analysis carried out on the

Fig. 8. SEM micrographs of the (a) 316L/untreated, (b) 316L/nitrided (tN = 2 h), (c) 316L/nitrided (tN = 4 h), and (d) 316L/nitrided (tN = 7 h) samples after corrosion tests.
 M. Olzon-Dionysio et al. / Surface & Coatings Technology 202 (2008) 3607–3614
surface of all samples is in agreement with electrochemical
results. The 316L/nitrided sample (tN = 4 h) [Fig. 8 (c)], which
had a lower dissolution current, shows considerably lower
amount and size of pits regarding the other samples [Figs. 8 (a),
(b) and (d)]. On the other hand, the sample treated for 4 h
exhibits pits much less deep and wide in comparison with the
pits shown in Fig. 8 (a). The results and observations above
conclusively suggested that the plasma nitriding treatment time
of 4 h improved the corrosion resistance of the austenitic
stainless steel in NaCl solution. This may be mainly due to the
formation of a metastable phase, known as expanded austenite
γN phase or S phase, as deduced by CEMS analysis. This phase
is able to reduce the access of the aggressive environment
towards the substrate, improving the corrosion resistance. Ad-
ditionally, the sample nitrided at higher time (to tN = 7 h) ex-
hibits lower corrosion resistance, showing an increase of the
current density in the anodic region of the polarization curve
(Fig. 7), with consequent increase of the amount and size of pits
[Fig. 8 (d)]. This may be mainly due to the presence of traces of
cubic chromium nitride (CrN), as deduced by GAXRD analysis.
Chromium depletion in the matrix due to the formation of CrN
nitrides, particularly around the nitrides precipitates, could be
responsible for the lower corrosion resistance of the metal. This
prevents the formation of a continuous, dense and passivating
oxide layer on the surface and thus increasing the metal dis-
solution by attack of chloride anions. Although the presence of
CrN in the nitriding layer makes the surface harder [8,10–13], it
becomes more reactive under anodic conditions. Depletion
chromium may play an important role in the poorer corrosion
properties after elevated time plasma nitriding. Therefore,
corrosion analyses allow to conclude that the processing time
during the plasma nitriding treatment plays an important role for
the corrosion resistance of 316L after nitriding.
To better understand this behavior, it is interesting to observe
Fig. 4 and Table 5 that show the phases fractions obtained from
the Mössbauer fits as a function of nitriding time. In Table 5, we
analyze the hexagonal (ε) and cubic (γ′) phases formation with
nitriding time, by comparing the CEMS ε/γ′ fraction ratio
values. For the 316L/nitrided sample (tN = 4 h), the ε/γ′ fraction
ratio is increased to approximately 0.84. While, ε/γ′ fraction
ratio values obtained, for samples nitrided at 2 and 7 h, are about
0.64 and 0.45, respectively. The increase on the ε/γ′ fraction
can be a clear indication of the higher corrosion resistance of the
metal in NaCl solution. Jirásková et al. [48] related that the
close-packed hexagonal structure of ε-nitride prevents corro-
sion. Studies of the effect of the nitrided layers at different
treatment time on the corrosion resistance of ASTM F138 stain-
less steel in NaCl solution showed the same tendency; that is,
corrosion resistance is better for larger ε/γ′ fraction values. This
work will be submitted soon for publication.
According to CEMS, GAXRD, SEM, and corrosion ana-
lysis, in the case of the nitrided AISI 316L samples, the sen-
sibility to the localized corrosion depends on the plasma
nitriding treatment time and phases present. The values of
pitting corrosion resistance of nitrided 316L samples increase in
agreement with the following sequence of treatment times: 7, 2
and 4 h, at 673 K.
3613
4. Conclusions
Glow-discharge nitriding treatments of 316L stainless steel
were carried out at 673 K for different times.
The CEMS analysis for the samples nitrided during 1 h was
done with the application of distribution of hyperfine magnetic
field for the metastable γN phase (of the magnetic nature, γN
(m)) corresponding to the dominant component.
For the samples nitrided for 2, 4, and 7 h, besides γN and
other less important phases, the γ′-Fe4N phase was present and
it seems to be correlated with the γN phase. If the γN fraction
decreases, the γ′ fraction increases.
Concerning the γN phase's magnetic character, the results
indicate that as the nitriding time increases, a significant reduc-
tion in the relative fraction of the γN (m) phase is observed and
the paramagnetic γN (p) phase increases.
The GAXRD analysis shows that, besides the substrate peaks,
the broader γN phase peaks appear at lower angles, signifying a
great degree of nitrogen supersaturation. As the nitriding time
increases, the γN phase peaks shift decreases as well as its full
widths at half maximum. It seems difficult to affirm that the γ′
phase is present for nitriding time t ≤ 4 h, but it seems to be
present, besides CrN traces for the sample nitrided for 7 h.
All the nitrided samples possess compound layer with very
similar thickness of approximately 8 μm, showing that the time
does not influence the thickness for tN ≥ 2 h.
Corrosion measurements demonstrate that the processing
time during the plasma nitriding treatment plays an important
role for the corrosion resistance of 316L after nitriding.
The results suggest that the plasma nitriding treatment time
of 4 h improved the corrosion resistance. While, the sample
nitrided at higher time (to tN = 7 h) exhibits lower corrosion
resistance.
It seems that the ε/γ′ fraction ratio plays an important role in
the resistance corrosion. The 316L/nitrided sample (tN = 4 h),
which presented the best result for corrosion, also presented the
maximum value for this ratio. As it can be seen, the Mössbauer
spectroscopy was decisive in this stydy, since it could identify
and quantify the iron phases that seem to play an important
role on the corrosion resistance of plasma nitrided AISI 316L
samples.
Acknowledgements
This work has been partly supported by the Brazilian agencies
FAPESP and CAPES.
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