Surface and Coatings Technology 150 (2002) 263268

A study of martensitic stainless steel AISI 420 modified using plasma

nitriding
I. Alphonsa*, A. Chainani, P.M. Raole, B. Ganguli, P.I. John
Institute for Plasma Research, Bhat, Gandhinagar, 382 428 Gujarat, India
Received 15 May 2001; accepted in revised form 27 September 2001

Abstract
We studied martensitic stainless steel AISI 420, modified using glow discharge plasma nitriding. Microhardness measurements,
X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Auger electron
spectroscopy (AES) were used to investigate the surface microhardness, crystal structure, microstructure and chemical bonding in
the modified surfaces. High surface microhardness (;1300 HV) over a case depth of about 60 microns is obtained. Glancing
incidence X-ray diffraction (GIXRD) indicates the presence of a predominantly Fe3 N phase with dispersed CrN within 2 5
microns on the surface. In addition, using Bragg Brentano geometry, we measured the presence of a minor phase of Fe4 N in the
case depth. SEM confirms that the microstructure within 2 5 microns of the surface is different from that of the bulk. XPS
shows nitride phase formation on the surface. AES measured over the cross-section of the case depth shows a direct relation of
the increased surface microhardness to the high nitrogen content. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nitriding; Vickers hardness test; Auger electron spectroscopy; Photoelectron spectroscopy; Martensitic

1. Introduction
The protection of material surfaces from hostile environments and severe operating conditions is of great
technical interest and economic necessity in the mechanical engineering industry. This is because the surface
subsurface properties of materials determine their performance. The requirements of high hardness, with
improved wear, corrosion and fatigue properties can be
attained by surface modifications using nitriding w1x.
The improvement in properties is due to the diffusion
of nitrogen into the surface andyor formation of nitrides
of the metal elements, constituting the steel. However,
stainless steel in general is considered difficult to nitride
conventionally because of the high temperatureyactivation energy for nitrogen diffusion, and the existence of
a surface oxide film, which hinders diffusion w2x. In
contrast to conventional nitriding, plasma nitriding is
known to be a better choice because the target material
is continuously subjected to a flux of ions and neutrals
present within a glow discharge. The bombardment of
these ions and neutrals in the presence of a chemically
* Corresponding author. Tel.: q91-79-323-5018; fax: q91-79-3235024.
E-mail address: alphonsai@yahoo.com (I. Alphonsa).

reactive medium removes the oxide film by sputtering

and simultaneously promotes nitrogen diffusion. Many
attempts have been made in the past few decades to
modify the surfaces of mostly austenitic stainless steels
to increase their surface hardness and in general improve
their tribological properties w35x. Martensitic steels can
also be nitrided like austenitic steels to obtain improved
wear and friction properties. However, the improvement
in hardness in austenitic and martensitic steel is accompanied by a reduction in corrosion strength, particularly
at high temperatures ()400 8C) w612x. While austenitic steel has attracted significant attention, few studies
have attempted a detailed analysis of martensitic stainless steel and in particular, AISI 420. Though, nitrided
austenitic steels are more widely used in industry,
nitrided martensitic steel remains a good choice, for
mildly corrosive environments and low temperature
applications w1315x. Moreover, plasma nitriding of a
martensitic stainless steel, particularly AISI 420 and its
detailed investigation using XRD, SEM and electron
spectroscopy on the same samples have not been
reported.
In this work, we investigate surface modifications by
plasma nitriding a martensitic stainless steel AISI 420.
After characterizing the modified surface using micro-

0257-8972/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 0 1 . 0 1 5 3 6 - 5

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hardness measurements, XRD and SEM, we have carried

out a detailed electron spectroscopy study using XPS
and AES. The atomic concentrations have been determined as a function of depth, and we find a direct
correlation of the high nitrogen content to the high
surface hardness measured for the same samples.
2. Experiment
AISI 420 martensitic stainless steel was selected as
the substrate material with the following composition:
Element C
Mn
P
S
Si
Cr
Fe
Wt.%
)0.15 -1.0 -0.04 -0.03 -1.0 12 14 Balance

The composition was confirmed by using XPS for

Fe, Cr, Mn and Si atomic concentrations. The trace
elements could not be measured on the surface, since
the sensitivity of XPS is ;1%. There was no evidence
of nitrogen on the surface.
The material was in the form of square blocks having
dimensions 1=1 cm2. It was annealed at 870 and
austenized at 1025 8C for 30 min, followed by oil
quenching. The sample surfaces were fine-ground using
600 grit SiC paper and finally polished with 0.05 mm
Al2O3 powder. The surfaces were thoroughly degreased
with petroleum ether before carrying out the nitriding
process.
Plasma nitriding was carried out in a 50-cm diameter
stainless steel Bell jaryvacuum chamber using a pulsed
dc glow discharge, operating at 10 kHz. The samples
were placed on the sample holder behaving as a cathode
with respect to the chamber wall. Sputter cleaning was
performed above 250 8C, prior to the processing, to
remove the oxide layers present on the surface of the
sample. Sputter cleaning was achieved using a pulsed
dc glow discharge operating at 500 V in a N2:H2 (1:4)
gas mixture at a pressure of 1 mbar. Plasma nitriding
was carried out subsequently at a voltage of 600 V, with
the same gas composition but at a higher pressure of 3
4 mbar. The cathode current density was ;2 mAy
cm2. AISI 420 steel was nitrided for a time period of
20 h at a substrate temperature of 530 8C. The substrate
temperature was controlled to an accuracy of "5 8C,
using a feedback circuit, which varied the duty cycle of
the pulse. After completion of the nitriding, the sample
was cooled in the chamber to room temperature in the
presence of nitrogen flowing gas to minimize surface
oxidation.
X-Ray diffraction of the samples was performed on
XRD3000PTS X-ray diffractometer manufactured by
Rich Seifert & Company, Germany, using a CuKa
source in the BraggBrentano mode. A
(ls1.5418 A)
graphite crystal monochromator was used for the glancing incidence (GI) mode.

SEM measurements were carried out on a Leo electron microscope, UK, model no. 440I on cross-sectioned
plasma nitrided AISI 420 samples. The samples were
sectioned using diamond wafering blades. They were
first polished with different grit size emery papers and
finally mirror polished with 0.05 mm Al2O3 powder.
The samples were cleaned in ultrasonic cleaner after
every polishing step. Nital solution (2%) was used as
an etchant to reveal the case microstructure. XPS and
AES measurements were done using the multitechnique
spectrometer model no. 5700 made by Physical Electronics, USA. XPS studies were done using monochromatic Al Ka photons with a resolution of 0.6 eV FWHM
of the Ag3d5y2 peak, which was also used to calibrate
the binding energy scale. AES measurements were done
at a primary energy of 3 keV electrons with a spot size
of ;5 micron diameter. Surface cleaning was achieved
using in-situ argon ion bombardment and was monitored
by measuring the C1s and O1s signals, which were
found to be negligible. The Argon ion bombardment
was carried out with 4 keV ion beam energy at a beam
current of 0.4 mA for a time period of 5 min. The low
energy (4 keV) ion beam used for surface cleaning
ensures that the surface contamination is removed and
no impact induced mixing occurs due to sputtering.
Microhardness experiments were performed on the
cross-sectioned samples with a Vickers indentor using a
load of 100 g and a dwell time of 20 s with the major
axis of the indentor parallel to the free surface. Hardness
measurements were carried out over a distance of 200
microns from the surface in order to define the microhardness depth profile. Plasma nitriding was carried out
on three sets of samples followed by the characterization
measurements for every set confirming the consistency
in the results.
3. Results and discussion
In Fig. 1, we show the glancing incidence XRD
patterns of the untreated AISI 420 compared with the
modified surface taken at 28 incidence angle. While the
pattern for the untreated sample (Fig. 1a) shows the aFe peak, the treated surface shows peaks in addition to
that of a-Fe, which are assigned to hexagonal -Fe3N
(Fig. 1b). The broad and weak peak at 37.78 could be
due to overlap of a minor phase of CrN with -Fe3N,
which we confirm with higher resolution XRD and with
XPS studies. Note also the asymmetry in the a-Fe peak,
which is due to hexagonal -Fe3N. This is clearly seen
when we plot the difference of the two patterns as
shown in Fig. 1c. We find no evidence for any other
phase within the sensitivity of the technique, which
probes -1 micron of the surface in GIXRD. However,
bulk sensitive XRD (Fig. 1d) done on the same sample
in the powder mode, which also affords higher resolu-

I. Alphonsa et al. / Surface and Coatings Technology 150 (2002) 263268

Fig. 1. Glancing-incidence X-ray diffraction patterns of (a) untreated

and (b) plasma-nitrided AISI 420. (c) The difference pattern (b a)
obtained after normalizing to the a-Fe peak, so as to see the changes
due to plasma nitriding. (d) The XRD pattern obtained in the Bragg
Brentano geometry to investigate the phases present in the casedepth.

tion, clearly shows the presence of CrN and a minor

phase of Fe4N, in addition to the Fe3N. XRD on the
surface of other plasma nitrided martensitic stainless
like AISI 410 steel revealed a mixture of g9-Fe4N and
-Fe3N phases w15x. We speculate that one possible
reason for the predominance of Fe3N in AISI 420 steel
could be due to the presence of higher carbon content
()0.15%) compared to the other martensitic stainless
steels mentioned above having 0.13% carbon content.
Moreover, it is reported by Vogel w16x that percentages
of -Fe3N phase in the case depth is very high in highly
alloyed steel even in the absence of carbon containing
atmosphere due to the input of carbon into the compound
layer from the base material. However, the specific

265

reason for this predominance is not yet clear to us and

requires further study. In the following, we confirm
nitride formation on the surface using XPS, which is a
good probe to study the chemical state or charge transfer
from cation to anion in a material.
Fig. 2 shows the cross-sectional SEM micrograph
obtained at a magnification of ;3000= in order to
observe the case depth. The case depth is measured to
be 61 microns, but note that the microstructure over the
case depth is different from that within the first 25
microns from the surface. This is consistent with the
GIXRD and bulk sensitive XRD data shown in Fig. 1,
which indicates predominantly Fe3N within 1 micron of
the surface. The present results are very similar to
phase formation on the surface on nitriding of pure airon w17x.
Figs. 3 and 4 show the Fe2p and N1s X-ray Photoemission spectra obtained for the modified surfaces using
monochromatic Al Ka photons. The Fe2p spectrum of
the modified surface (Fig. 3) consists of single peak
Fe2p3y2 and Fe2p1y2 featuring at 707 and 720.17 eV
due to spin-orbit splitting. Note that the binding energies
and the asymmetric spectral shape are quite like that of
metallic Fe, indicating that the processing has not
resulted in contaminating the surface into an oxide. It is
well-known that the oxidation of Fe results in a large
chemical shift and satellite structure in Fe2p spectrum,
which is not observed here w18x. The binding energy of
Fe and Fe3N does not show a measurable chemical shift
for the Fe2p3y2 and Fe2p1y2 peaks but only a small
broadening on the higher binding energies. N1s spectrum
(Fig. 4) with a binding energy of 397 eV is a peak
typical of a metal nitride. N1s binding energies for iron
nitride and chromium nitride are very close w19,20x,
which may give unresolved single peak due to the
overlapping. Using a least-square curve-fitting procedure, we have fitted the Fe2p and N1s core level spectra.
The results are shown as a thick line superimposed on
the raw spectrum. We used single asymmetric Voigt
functions for the Fe2p3y2 and 2p1y2 peaks as well as the
N1s spectrum and the good fits obtained confirm that
the nitride is formed on the surface. In contrast, a recent
study on 9Cr18 martensitic steel showed three peaks of
N1s spectrum indicative of multiphasic nitride surfaces
w21x.
In order to investigate the content of CrN in the
surface, we measured the Cr 2p core level spectra using
monochromatic Al Ka photons. The spectra are shown
in Fig. 5 along with a curve fit superimposed as a thick
line. We were unable to fit the spectra using single
peaks for the 2p3y2 and 2p1y2 spectra. Instead an additional set of two peaks, shifted from the main peak by
2.5 eV, was necessary to obtain the fit shown in Fig. 5.
This is suggestive of CrN formation, since we had
negligible O or C on the surface. The total intensity of

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Fig. 2. SEM picture of plasma-nitrided AISI 420 showing a case depth of 61 microns. Note the different microstructure in the first 2 3 microns.

the peaks at higher binding energy amounts to a maximum of 34% of the total Cr content present in the
surface. This indicates that less than one third of the
12% Cr present in the surface has transformed into a
nitride. Since Fe3N and CrN is confirmed to exist in the
surface by XRD and XPS, the N 1s of Fe3N and CrN
appear at the same binding energy and hence are
observed as a single peak.
Having looked at the chemical states of Fe and N on
the surface, we next investigated the relative atomic

Fig. 3. Fe2p core-level X-ray photoemission spectrum of plasma

nitrided AISI 420 (thin line) along with the asymmetric Voigt function
curve-fit (thick line), indicating the absence of oxidation or contamination of the surface.

concentrations on the same sample cut in cross-section

using small spot electron induced AES. This measurement was carried out to study the constituent elements
over the case depth, so as to relate to the microhardness
measured for the same.
In Fig. 6, we show the atomic concentrations of Fe,
Cr and N obtained up to 200 microns, using an analysis
area of about 5 micron diameter (as determined by the
electron beam spot size). The relative concentrations of

Fig. 4. N1s core-level X-ray photoemission spectrum of plasma nitrided AISI 420 (thin line) superimposed with a single peak Voigt profile
(thick line) indicating nitride formation.

I. Alphonsa et al. / Surface and Coatings Technology 150 (2002) 263268

267

on the top surface and up to approximatley 60 microns

is measured to be ;6:1. This concentration ratio is not
consistent with the stoichiometric compound Fe3N and
yor Fe4N and is due to the presence of unreacted Fe
within the case depth. Note that the N concentration
drops significantly at around 65 microns and is consistent with the case depth measured using SEM.
In order to correlate the spectroscopy results with the
surface hardnesses we plot in Fig. 7 the surface microhardness and the N concentration profiles, respectively.
The microhardness measurements were performed on a
cross-sectioned sample. Microhardness measurements
were carried out up to a distance well beyond the case
depth and a comparison with the N concentration depth
profile indicates a direct relation with the nitride phase
formation. As can be seen in Fig. 7, the microhardness
is maximum up to a depth of ;60 microns, at which
depth the nitrogen concentration reduces very sharply.
The reduced N content results in a marked reduction in
surface hardness, and the hardness value reaches that of
the base material by about 8090 microns.
Fig. 5. Cr2p core-level X-ray photoemission spectrum of plasma
nitrided AISI 420 (thin line) decomposed into a main peak and a peak
shifted to 2.5 eV higher binding energy for the 2p3y2 and the 2p1y2
peaks, showing only partial transformation of the Cr into CrN.

Fe, Cr and N are plotted as a line scan, taking in to

account the sensitivity factors for the said elements. As
is seen from the concentration profiles, the Fe:N ratio

4. Conclusion
In conclusion we have obtained plasma nitrided martensitic SS 420 with predominantly epsilon-Fe3N phase
on the surface. The Fe2p, Cr2p and N1s XPS results
confirm nitride phase formation. The AES depth profiles
indicate a direct relation of the increased surface microhardness in plasma nitrided AISI 420 to the nitride
phase formation in the measured case depth.

Fig. 6. Atomic concentration profiles obtained using Auger electron spectroscopy of a cross-sectioned plasma-nitrided AISI 420 sample.

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I. Alphonsa et al. / Surface and Coatings Technology 150 (2002) 263268

Fig. 7. Microhardness and nitrogen concentration profiles across the cross-section of plasma-nitrided AISI 420 showing the direct relation of high
hardness to the high nitrogen concentration in the case depth. Error bars are within the symbol size.

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