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Low temperature gaseous nitriding and

carburising of stainless steel

Article in Surface Engineering · October 2005

DOI: 10.1179/174329405X68597

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Low temperature gaseous nitriding and
carburising of stainless steel
T. Christiansen and M. A. J. Somers*
The response of various austenitic and duplex stainless steel grades to low temperature gaseous
nitriding and carburising was investigated. Gaseous nitriding was performed in ammonia/
hydrogen mixtures at temperatures ,723 K; gaseous carburising was carried out in carbon
monoxide/hydrogen mixtures for temperatures (783 K. The case developed by thermochemical
treatment was examined using reflected light microscopy, X-ray diffraction analysis and
microhardness testing. Both nitriding and carburising led to the development of expanded
austenite in the surface adjacent zone, irrespective of the phase constitution of the substrate. A
two step process, consisting of carburising followed by nitriding, provides great flexibility with
regard to adjusting the hardness–depth profile.
Keywords: Gaseous nitriding, Gaseous carburising, Stainless steel, Reflected light microscopy, X-ray diffraction, Microhardness testing

Introduction nitrides/carbides is obtained when large amounts of

Stainless steel is widely applied in the chemical and food
processing industries owing to its favourable corrosion
performance, which relies on the presence of a very
stable (passive) surface (hydr)oxide layer. Despite the
superb corrosion resistance, the application of stainless
steels in tribocorrosive environments is limited, owing to
its poor tribological properties and inability to with-
stand extensive wear. Gaseous nitriding and carburising
could, in principle, improve the hardness and wear
resistance of stainless steel, but will generally cause
unwanted deterioration of the corrosion performance, as
such processes are carried out at temperatures (well)
above 773 K (for nitriding) and 1000 K (for carburis-
ing), where chromium nitrides/carbides develop upon
thermochemical treatment.
In the last 20 years, plasma and implantation
technologies have opened the possibility for improving
the wear performance of stainless steel through low
temperature (,723–823 K) carburising/nitriding, with-
out impairing the corrosion resistance.1–4 An exhaustive
list of publications is available in the proceedings of the
first conference on low temperature nitriding/carburising
of stainless steel.5 Generally, the passive film on stainless
steel is impenetrable for nitrogen/carbon atoms at low
temperature. Plasma and implantation technologies
circumvent passive layer impenetrability, as sputtering
of the surface is an integral part of the process.
The microstructural feature responsible for the highly
demanded combination of excellent corrosion and wear
performances is so called expanded austenite (hitherto
also called the S-phase).6–8 Expanded austenite without
Department of Manufacturing Engineering and Management, Technical
University of Denmark, Kemitorvet b. 204, DK-2800 Kgs. Lyngby,
Denmark
*Corresponding author, email somers@ipl.dtu.dk
atomic nitrogen and/or carbon are dissolved in stainless
steel at temperatures below, say, 723 K for nitrogen and
,823 K for carbon. The nitrogen/carbon atoms are
presumed to reside in the octahedral interstices of the fcc
lattice.8 Long range order among the nitrogen/carbon
atoms has so far not been confirmed by X-ray
diffraction (XRD) techniques, but one TEM and
electron diffraction investigation indicates the presence
of nanoscale ordered domains (with the same ordering
among nitrogen atoms as in c9-Fe4N12x) separated by
antiphase boundaries.9 Typically, nitrogen contents in
expanded austenite range from 20 to 30 at.-%N; carbon
contents range from 5 to 12 at.-%C.2,4,10 In terms of the
N : Cr ratio the homogeneity range of nitrogen expanded
austenite spans from ,1 : 1 to 3 : 1.11 Expanded austenite
is metastable and tends to develop chromium nitrides/
carbides.12–14 The high interstitial content of C/N is
obtained because of the relatively strong affinity of Cr
atoms for N and (to a lesser extent) C atoms, leading to
anticipated short range ordering of Cr and N/C. Owing
to the low mobility of Cr atoms compared with
interstitial N/C atoms at low treatment temperatures,
chromium nitrides/carbides do not precipitate until after
long exposure times, and N/C is kept in solid solution by
the Cr ‘trap sites’.
Hardness values (1700 HV have been reported;15,16
the strengthening mechanism has so far not been
elucidated. It is suggested here that a combination of
solid solution hardening by the high interstitial atom
content, as well as the presence of stacking faults on the
fcc sublattice of substitutional atoms contribute to
strengthening. Moreover, in the light of the above
mentioned nanosized ordered domains,9 a contribution
of antiphase boundary strengthening could be expected.
Spectacular wear reductions of several decades have
been reported for stainless steels nitrided under condi-
tions where expanded austenite develops.17,18 In the

ß 2005 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 8 February 2005; accepted 24 May 2005
DOI 10.1179/174329405X68597 Surface Engineering 2005 VOL 21 NO 5–6 445
Christiansen and Somers Nitriding and carburising of stainless steel

Table 1 Nominal compositions of investigated stainless
steels in wt-% (balance Fe)
AISI C Mn Si P S Cr Ni
316 0.08 2.00 1.00 0.045 0.030 16–18 10–14 2–3
316L 0.030 2.00 1.00 0.045 0.030 16–18 10–14 2–3
303 0.15 2.00 1.00 0.20 .0.15 17–19 8–10 0.60
329 0.20 1.00 0.75 0.040 0.030 23–28 2.5–5 1–2
worst case, the electrochemical properties remain
unaltered, but they can be improved, in particular the
pitting potential.19,20
Very recently an ex situ pretreatment of stainless steel
was developed, which enables subsequent low tempera-
ture gaseous nitriding and/or carburising and allows
controlled formation of an expanded austenite layer.21
The pretreatment can also be applied locally and
tolerates intermediate storage without losing the excel-
lent nitriding/carburising ability. Examples of low
temperature nitriding/carburising are presented in the
present article. Hereafter, expanded austenite stabilised
by dissolved nitrogen and carbon atoms are referred to
as cN and cC, respectively.
Experimental
Various types of stainless steel were investigated, and
the nominal compositions are given in Table 1. Types
AISI 316 and AISI 316L are austenitic stainless
steels; type AISI 303 is a free machining austenitic
stainless steel grade, intended to provide a good
combination of cold formability and machinability;
AISI 329 is a duplex (ferritic and austenitic) stainless
steel grade.
Discs of diameter 20 mm and thickness 3–4 mm were
applied in addition to 2 mm thick plate material. The
specimens were polished with successively finer emery
paper/diamond polish until a mirror like finish was
obtained. For AISI 303, the final grinding step was
1000 mesh emery paper. In order to allow for gaseous
nitriding/carburising, the specimens were pretreated
according to the method described in Ref. 21.
Nitriding and carburising experiments were con-
ducted in a custom built vertical tube furnace equipped
with six individual heating zones and an alumina tube.
Additionally, a Netzsch STA 449C thermal analyser was
used for gaseous nitriding. The thermal analyser
required a small flow of N2 through the measurement
compartment in order to protect the balance chamber
from ammonia during nitriding. Both types of nitriding
furnaces were equipped with Brooks TYPE 5850S
electronic mass flow controllers for accurate gas flow
Mo control. Heating to the process temperature was
achieved within 45 min and was performed in the
process gas for nitriding and in hydrogen for carburis-
ing. Process times were taken as the time at the
treatment temperature. After nitriding or carburising,
the samples were cooled in the furnace to ambient
temperatures in inert gas. Cooling to a temperature
,373 K was achieved within 15 min.
Nitriding was performed in mixtures of NH3 and H2
(and a small flow of N2 in the thermobalance, see
above), the partial pressures of H2 and NH3 determine
3=2
the so called nitriding potential, KN ~pNH3 =pH2 ; the
dimension of the nitriding potential is in bar21/2.
Carburising was performed in mixtures of CO and H2,
the partial pressures of CO and H2 are contained in the
so called carburising potential, KC ~pCO pH2 =pH2 O ; the
dimension of the carburising potential is in bar. Since
the partial pressure of H2O was not adjusted and was
therefore unknown, the carburising potential was not
known. For the special case of carburising in 100%CO
the carburising potential corresponds to infinity, assum-
ing that no soot is formed during carburising, which
would reduce the carbon activity at the surface to 1 (with
reference to graphite). The occurrence of limited
amounts of soot could not be prevented for the present
experiments; recent developments in the authors’
laboratories do allow carburising without soot forma-
tion. The various treatments performed are listed in
Table 2.
XRD analysis for phase identification was carried out
in the conventional symmetric Bragg–Brentano geome-
try, using a Bruker D8 AXS X-ray diffractometer
equipped with a Cr anode and a Göbel mirror in the
incident beam or, occasionally, a Philips PW3710
diffractometer equipped with a Cu anode.
Microhardness indentations were performed on a
Neophot 32 (Carl Zeiss) equipped with a Hanemann
microhardness tester from Carl Zeiss. A load of 6.25 g
was used. Micrographs of the indentations were taken
on a Neophot 30 (Carl Zeiss) operated with polarised
monochromatic light and a 1006 oil immersion
objective for optimal resolution. The lengths of the
diagonals of the indentations were measured from the
digitally recorded micrographs.
Samples investigated by reflected light microscopy
were prepared by standard metallographic techniques
and etched in 50HCl–25HNO3–25H2O (vol.-%).

Table 2 Overview of carburising/nitriding treatment parameters temperature T, time t, partial pressure p, KN nitriding
potential and KC carburising potential performed on various AISI type stainless steels

AISI T, K t, h pNH3, bar pH2, bar pCO, bar pN2, bar KN/KC, bar21/2/bar

316L 723 18 0.91 … … 0.09 infinite

703 20 0.55 0.36 … 0.09 2.49
783 4 … 0.60 0.40 … unknown
316 718 22 0.55 0.36 … 0.09 2.49
718 22 0.18 0.73 … 0.09 0.293
780 6 … … 1 0 infinite
773 4 … … 1 … infinite
713 1 … … …
303 673 2318.5 1 … … … infinite
329 673 23 1 … … … infinite
723 23 1 … … … infinite

446 Surface Engineering 2005 VOL 21 NO 5–6


a, b T5723 K, t518 h, KN5‘; c, d T5703 K, t520 h, KN52.49 bar21/2
1 Micrographs of nitrided AISI 316L
Results and interpretation
Gaseous nitriding
AISI 316 and AISI 316L
Micrographs of cross-sections of nitrided austenitic
stainless steel 316L are shown in Fig. 1. Nitriding brings
about a uniform layer of nitrogen expanded austenite
(cN). Applying a temperature of 723 K and infinite
nitriding potential yields a layer thicker than 20 mm
(Fig. 1a and b). The use of an infinite nitriding potential
results in a nitrided layer with a high content of nitrogen
(cf. Ref. 11). The occurrence of small cracks (arrowed in
Fig.1b) is believed to originate from large compressive
stresses associated with the lattice expansion in cN.
Lowering the nitriding potential and the nitriding
temperature gives a layer of thickness 15–16 mm, where
the occurrence of small cracks is reduced considerably
(Fig. 1d). This is directly related to the nitriding
potential, the associated nitrogen content in the layer
and, consequently, the (hardness and) compressive stress
level in the layer. No indications of the development of
CrN precipitates were observed with reflected light
microscopy in the nitrided layers on AISI 316L under
the given conditions.
Nitriding of relatively large grained AISI 316 samples
at two different nitriding potentials for 22 h at 718 K
resulted in the cN layers depicted in Fig. 2. No
indications of brittle cracks were observed in either of
the layers. After nitriding, the samples had the same
mirror like finish as the untreated surfaces. Evidently,
Christiansen and Somers Nitriding and carburising of stainless steel
KN is an important parameter in controlling the growth
kinetics of the cN layer: the layer thickness is 7.8
(¡0.7) mm and 13.5 (¡0.8) mm for KN50.293 bar21/2
and KN52.49 bar21/2, respectively. Presuming local equi-
librium between nitrogen in the gas mixture and nitrogen
in the solid state (at the surface), applying a higher nitrid-
ing potential corresponds to a higher nitrogen content in
the solid state.11 Consequently, a higher driving force for
inward diffusion of nitrogen is obtained. Moreover, it
was demonstrated from denitriding experiments on
homogeneous thin foils of expanded austenite that the
diffusivity of N in cN strongly increases with the
nitrogen content for contents (33 at.-%N (Ref. 28).
Thus, if growth of the cN layer is (largely) diffusion
controlled, the nitriding potential governs the layer
thickness and its evolution as a function of time.
Generally, it was observed that the grain boundaries
of the austenite grains continue in the cN layer,
consistent with the dissolution of nitrogen in the
austenite rather than by nucleation and growth of the
new cN grains (Fig. 2). Since the cN layer is not as
heavily attacked by the etching agent as the underlying
austenite substrate is, favourable electrochemical prop-
erties are expected for cN compared with c.
X-ray diffractograms of nitrided AISI 316 are given in
Fig. 3. The characteristic feature of cN is readily
identified: ‘satellite’ fcc peaks at lower Bragg angles
than the parent fcc austenite. The shift of fcc peaks to
lower Bragg angles is caused, primarily, by lattice
expansion as a consequence of the dissolution of
Surface Engineering 2005 VOL 21 NO 5–6 447
Christiansen and Somers Nitriding and carburising of stainless steel
a KN50.293 bar21/2; b KN52.49 bar21/2
2 Micrographs of nitrided AISI 316 (T5718 K, t522 h)
nitrogen atoms in the octahedral interstices of the fcc
lattice. Compressive residual stresses (macro stresses),
invoked by the expansion of the fcc lattice in the near
surface region, also shift the position of the cN peaks
to lower Bragg angles (for the present measurement
geometry), albeit an (hkl) dependent shift. Furthermore,
stacking faults, being an intrinsic feature of cN, cause an
(hkl) dependent peak shift to either lower or higher
Bragg angles (depending on (hkl)). The massive broad-
ening of the cN peaks is associated with the nitrogen
concentration depth gradient in the volume probed.
Additionally, the presence of so called microstrains due
to stress gradients and stacking faults causes broadening
of the cN peaks. Comparing the patterns for the two
applied nitriding potentials shows different peak shifts
for the cN peaks, reflecting the difference in nitrogen
concentration depth profile. The shifts are consistent
with the highest nitrogen content for the highest
nitriding potential. For the highest nitriding potential,
the austenite substrate peaks are no longer visible owing
to the attenuating effect of the (thick) cN layer on the
X-radiation reaching the substrate and, consecutively,
reaching the surface upon diffraction in the substrate.
Hardness–depth profiles were obtained for AISI 316
nitrided at different nitriding potentials and are given in
Fig. 4 for the same samples as in Fig. 2a and b.
Clearly, the hardness–depth profiles show a strong
difference between the samples nitrided at different
3 X-ray diffractograms measured with CrKa radiation on
nitrided AISI 316 (t522 h, T5718 K) with the nitriding
potentials KN50.293 bar21/2 and KN52.49 bar21/2
448 Surface Engineering 2005 VOL 21 NO 5–6
nitriding potentials. The appearance of the profiles is
somewhat similar: A smooth decrease near the surface
followed by a sharp drop in hardness at a position close
to the ‘layer/substrate’ interface in Fig. 2. For a nitriding
potential of KN52.49 bar21/2, the hardness falls from
,1000 HV to 500 HV. The hardness values measured
directly at the surface with the same load give 1585 HV
and 1417 HV for KN52.49 bar21/2 and KN50.293 bar21/2,
respectively. Evidently, a layer of expanded austenite is
very hard, and the transition from the hardened zone to
the (soft) substrate occurs within a few microns.
AISI 303
The micrographs of AISI 316 and AISI 316L presented
in Figs. 1 and 2 are representative of typical austenitic
stainless steel (including AISI 304). Other, less widely
applied, stainless steel types may also be surface
hardened by low temperature nitriding. The free
machining sulphur bearing AISI 303 stainless steel was
successfully nitrided (Fig. 5). The obtained layer differs
from the layers obtained for AISI 316(L), as distinct
features (dark lines) within the cN layer are observed
preferentially at the near surface. The lines inclined
with respect to the surface may be sliplines (plastic
4 Hardness–depth profiles of nitrided AISI 316 (T5718 K,
t522 h) with the nitriding potentials KN50.293 bar21/2
and KN52.49 bar21/2. Surface hardness as measured
by indentation into the surface was 1417 HV and
1585 HV for KN50.293 bar21/2 and KN52.49 bar21/2,
respectively; lines are drawn to guide eye

5 Micrograph of nitrided AISI 303: T5673 K, t523 h,
KN5‘
deformation) produced by compressive stresses. XRD
analysis (Fig. 6) shows that hcp e-phase has formed in
addition to cN. Therefore the lines observed in the
micrograph in Fig. 5 are interpreted as contrast
originating from glidelines and former deformation
martensite regions (see below) decorated with hcp
e-phase. It is not ascertained whether the hcp e-phase
is stress induced (martensite) or chemically induced
(nitride). The stress induced hcp e-phase has a dis-
ordered arrangement of nitrogen atoms, whereas the
chemically induced hcp e-phase has an ordered arrange-
ment of nitrogen atoms. The hcp e-nitride is associated
with additional reflections in the XRD pattern due to
the long range order of nitrogen. It is not discernable
from the X-ray diffractogram in Fig. 6 whether long
range order of N atoms occurs in the hcp e-phase. The
development of e-martensite is promoted by the com-
position induced stresses associated with high nitrogen
contents.
The XRD pattern for untreated AISI 303 contains an
a9(110) peak, indicating the presence of stress induced
(deformation) martensite, which originates partly from
polishing of the sample surface before nitriding and
deformation in the as delivered state of the material
(Figs. 5 and 6). The absence of the a9(110) reflection in
6 CuKa XRD pattern of nitrided AISI 303: T5673 K, t523 h, KN5‘
Christiansen and Somers Nitriding and carburising of stainless steel
the diffractogram after nitriding indicates that deforma-
tion martensite is transformed into cN during nitriding,
owing to the strong austenite stabilising ability of
nitrogen, and that the cN layer is too thick to observe
a9 still present in the substrate.
AISI 329
Nitriding of duplex stainless steel alloys is also possible,
as evidenced by the micrograph in Fig. 7. The basic
microstructure consists of austenite grains dispersed in a
ferritic matrix. The austenite and ferrite regions have
different compositions as a consequence of the parti-
tioning of the ferrite and austenite forming alloying
elements during heat treatment (cooling).
Nitriding of AISI 329 at 673 K produced a contin-
uous layer (Fig. 7a). Interestingly, both ferrite and
austenite were transformed into cN. The thickness of
cN is not the same for austenite grains and former ferrite
matrix, which is ascribed to the effect of different
chemical compositions of the former ferrite and
austenite regions on the solubility and diffusivity of
nitrogen in the developing cN. According to the X-ray
diffractogram in Fig. 8, cN extends over a broad 2h
range. This reflects the composition difference between
cN on former c regions and cN on former a regions. Since
a is anticipated to have the highest Cr content, it is
expected that cN on former a regions has the highest N
content. This would be consistent with the highest
intensity observed at the lowest Bragg angle for the (200)
cN reflection, because the ferrite content in the untreated
AISI 329 is higher than the austenite content (cf.
diffractograms for untreated and treated at 673 K in
Fig. 8). At 723 K a thick layer was obtained (Fig. 7b)
and the occurrence of CrN/a- and e-phase in addition to
cN follows from the corresponding X-ray diffractogram
(Fig. 8). It cannot be assessed whether the e-phase is e-
martensite or e-nitride (cf. previous subsection). The
dark region in Fig. 7b is former a-phase; the darkening is
attributed to the presence of precipitates smaller than
the resolution of reflected light microscopy (50.15 mm
for the present conditions). Evidently, these precipitates
have developed prior to the aRc transformation,
because a shade of grey is also observed as a thin layer
ahead of the a/c interface (Fig. 7b), while such shading is
Surface Engineering 2005 VOL 21 NO 5–6 449
Christiansen and Somers Nitriding and carburising of stainless steel

a T5673 K, t523 h, KN5‘; b T5723 K, t523 h, KN5‘

7 Micrographs of nitrided duplex stainless steel AISI 329

absent for cN on former c. The development of, most
likely, CrN precipitates in the a-phase (and not in the c-
phase) is consistent with the higher Cr content in a and
the possibility of coherent nucleation of CrN in a
through a favourable crystallographic orientation rela-
tion between CrN and a (cf. Ref. 26).
Carburising of AISI 316
Cross-sections of carburised AISI 316 and AISI 316L are
presented in Fig. 9. It is evident that relatively thick layers
of ,20 mm of carbon expanded austenite (cC) were
obtained within a relatively short carburising time (e.g.
4 h). The transition from the substrate to the transformed
zone (cC) is not as pronounced as for nitriding, which is
probably due to a lower interstitial atom content in cC
compared with cN, and a smoother transition from the
treated case to the core. The grain boundaries from the
substrate continue into cC, fading out as the surface is
approached (higher C contents) (Fig. 9a). cC is not
attacked by the applied etchant, as is especially evident
in Fig. 9b. This, as for nitriding, hints at a higher
electrochemical potential of cC compared with austenite.
The XRD pattern of carburised AISI 316 is shown in
Fig. 10. cC is identified as the only phase present in the
surface adjacent region, i.e. within the information
depth for the probing X-ray beam. A marked difference
is observed compared with nitrided AISI 316 (Fig. 3): a
smaller shift of the austenite peaks to lower 2h, which
indicates a substantially lower content of the intersti-
tially dissolved atoms, provided that nitrogen and
carbon induce a similar distortion in the fcc lattice.
The asymmetrical (200) austenite peak in Fig. 10
indicates a depth gradient of the carbon content in the
near surface zone.
The hardness–depth profile of carburised AISI 316 is
characterised by a relatively smooth transition from the
surface to the substrate (Fig. 11). The hardness is
considerably lower than for nitriding (see above), but
still significantly higher than the hardness of the
substrate. Measured directly at the surface with the
same load, a value of 926 HV was obtained, which,
compared with a substrate hardness of 200–300 HV, is a
significant increase.
Carburising and nitriding of AISI 316
Micrographs of consecutively carburised and nitrided
AISI 316 are depicted in Fig. 12. The combination

8 CuKa XRD patterns of nitrided duplex AISI 329 stainless steel (nitriding at 693 K and 723 K as indicated; in both
cases nitriding for 23 h at KN5‘)

450 Surface Engineering 2005 VOL 21 NO 5–6

 Christiansen and Somers Nitriding and carburising of stainless steel

a AISI 316, T5780 K, t56 h, KC5‘; b AISI 316L, T5783 K, t54 h, 40 vol.-%COz60 vol.-%H2
9 Micrographs of carburised stainless steel

10 CrKa XRD pattern of carburised AISI 316: T5780 K,
t56 h, KC5‘
treatment produces a relatively thick layer of expanded
austenite: ,25–30 mm at the polished surface and
,40 mm at the unpolished (deformed) surface, as
indicated in Fig. 12a. The layer consists actually of
two separate zones with a somewhat diffuse interface
(which was clearly observed in the microscope, but is
difficult to see in the present micrographs); the outer
zone is cN and the inner zone is cC.
The X-ray diffractogram of carburised and nitrided
AISI 316 shows that two different types of expanded
11 Hardness–depth profile of carburised AISI 316, T5
780 K, t56 h, KC5‘; surface hardness as measured
by indentation at surface, 926 HV; line to guide eye
austenite are present (Fig. 13). The peaks of cN are
shifted more than cC and are most dominant, because cN
has the highest interstitial atom content and is located
near the surface. The expanded austenite peaks (without
distinction between carbon and nitrogen expanded
austenite) are broad, which is indicative of a very
broad composition range. The XRD pattern does not
indicate the development of carbides or nitrides during
treatment.

a both polished and deformed surfaces; b polished surface at higher magnification

12 Micrographs of AISI 316 carburised (T5773 K, t54 h, KC5‘) and subsequently nitrided (T5713 K, t518.5 h, KN5‘)

Surface Engineering 2005 VOL 21 NO 5–6 451

Christiansen and Somers Nitriding and carburising of stainless steel

13 CrKa XRD pattern of AISI 316 carburised (T5773 K, t54 h, KC5‘) and subsequently nitrided (T5713 K, t518.5 h, KN5‘)

The hardness–depth profile depicted in Fig. 14 shows
the combined effect of nitrogen and carbon expanded
austenite. In the near surface region, the hardness is
,1200 HV, the same as for nitriding only under similar
conditions. The hardness decreases smoothly to a depth
of ,18 mm, followed by a steeper transition to the low
substrate hardness. The profiles for nitriding and
carburising are effectively added to give this character-
istic profile. Hence, cC has the role of a transition zone
between the very hard cN zone and the soft substrate.
The drop in hardness of 1200 to 400 HV occurs over a
much broader region for the combination treatment
than for nitriding only (cf. Fig. 14).
Discussion
Thermodynamic stability of Cr carbides and Cr
nitrides
The difference in treatment temperature between nitrid-
ing and carburising treatments is related to the
difference in affinity of Cr for C and N. A higher
affinity of Cr for N promotes the precipitation of CrN,
whereas the lower affinity of Cr for C does not to the
same extent promote the formation of chromium
carbides. An Ellingham diagram for the formation of
chromium nitrides and carbides is given in Fig. 15.22
The development of chromium nitrides is associated
with more negative Gibbs energies of formation (driving
force) than the formation of chromium carbides (per
chromium atom). Thus, the driving force (per Cr atom)
for the actual development of nitrides is higher than the
driving force for the development of carbides.
Moreover, in the present investigations, the interstitial
contents of carbon are significantly lower than for
nitrogen, which reduces the driving force for the
precipitation of carbides compared with that for nitrides
in terms of oversaturation with respect to maximum
solubility. The activation energy for the nucleation of
the nitrides/carbides determines the probability for their

14 Hardness–depth profile of AISI 316 carburised (T5773 K, t54 h, KC5‘) and subsequently nitrided (T5713 K,
t518.5 h, KN5‘); surface hardness as measured by indentation into surface was 1635 HV; hardness–depth profiles
for carburised and nitrided samples given for comparison (for same gas compositions and approximately similar
temperatures and durations); lines to guide eye

452 Surface Engineering 2005 VOL 21 NO 5–6


15 Ellingham diagram: Gibbs energy of formation for chromium carbides and nitrides per Cr atom (N251 bar)
nucleation. This activation energy depends on the
character of the interface (interfacial energy) between
precipitate and matrix and the volume misfit between
precipitate and surrounding matrix (elastic strain
energy). Also in this respect, more favourable conditions
are anticipated for the precipitation of nitrides than for
the precipitation of carbides, because, judging from the
crystallography of carbides and nitrides, favourable
crystallographic orientation relationships with cN/C are
more likely to occur for the Cr nitrides than for the Cr
carbides.
Influence of process parameters
Expanded austenite is readily obtained by gaseous
treatment in various grades of stainless steels and is
not restricted to austenitic stainless steel. The process
parameters have a strong influence on the outcome of
the surface hardening process, which provides the
possibility for adjusting the case developing during
gaseous treatment.
The combination of treatment time and temperature
should be chosen such that precipitation of chromium
nitrides/carbides is effectively avoided. If precipitation
does occur, Cr is removed from solid solution and the
ability for passivation of the steel surface is lost (locally).
As the present results show, temperatures up to 723 K
and 783 K are readily applicable for obtaining nitrogen
and carbon expanded austenite, respectively, without the
formation of undesired precipitates within the chosen
treatment times.
The degree of deformation is another parameter that
has to be taken into consideration when choosing the
combination of time and temperature for the carburis-
ing/nitriding treatment. Generally, lower temperatures
should be applied when the material is deformed,
because the precipitation of chromium carbides/nitrides
is facilitated by the presence of inherent crystallographic
defects associated with deformation; either by creating
nucleation sites or by enhancing diffusion of substitu-
tionally dissolved atoms.
In particular, the nitriding potential is an important
process parameter, as it enables control of the nitrogen
content in cN. Applying a high nitriding potential poses
the risk of brittle cracking, especially for thick layers.
Christiansen and Somers Nitriding and carburising of stainless steel
Moreover, a dark grey surface finish can be obtained,
which is a consequence of surface roughening, caused by
pushing out of individual grains under the influence of
enormously high compositionally induced stresses (cf.
Ref. 23). Lowering the nitriding potential reduces the
nitrogen content and, consequently, the layer growth
kinetics, but produces superior layers and unaffected
surface finish. Adjustment of the nitriding potential
enables control of the surface hardness by controlling
the amount of nitrogen in the cN layers formed,
tentatively in the range (1700 HV. Additionally, the
occurrence of stress induced hcp e-phase is presumably
related to the nitriding potential. The transformation of
cN into this nitrogen rich phase is associated with high
nitriding potentials (high nitrogen contents). Increasing
the nitriding potential entails a higher nitrogen content
and consequently production of large residual compres-
sive stresses. High compositionally induced stresses
promote the stress induced transformation of fcc cN
into hcp e. Furthermore, hcp e-martensite has been
shown to nucleate on stacking faults.24 Tentatively,
higher nitrogen contents in cN are likely to increase the
stacking fault density/probability. The degree of defor-
mation of the material is also related to the development
of hcp e: transformation is more likely to occur in a
heavily deformed material, where there is a higher
density of nucleation sites, e.g. stacking faults. However,
it must be emphasised that the occurrence of hcp e is not
necessarily as detrimental for the corrosion performance
of the material as precipitation of CrN (and ferrite),
because Cr may still be available for passivation of the
stainless steel surface.
Nitriding versus carburising
The process time for carburising can be considerably
shorter than for nitriding. Thick layers of cC (.20 mm)
were obtained within a few hours. Prolonging the
process time for carburising should yield even thicker
layers. Carburising is a more straightforward process
with respect to, say, brittleness. The interstitial content
of carbon compared with nitrogen is significantly lower
(in the present experiments), which can partly be
ascribed to a lower affinity of Cr for C compared with
Cr for N (see discussion below). In addition, the
Surface Engineering 2005 VOL 21 NO 5–6 453
Christiansen and Somers Nitriding and carburising of stainless steel
nitrogen activity of NH3/H2 gas mixtures (with N2 at
1 bar as the reference state) can be very much higher
than the carbon activity of CO/H2 mixtures (with
graphite at 1 bar as the reference state).
The lower interstitial atom content after carburising
is readily reflected in the attainable hardness com-
pared with the hardness obtainable with nitriding.
Additionally, the occurrence of graphite/soot (the stable
form of C) dramatically reduces the carbon activity at
the surface, which eventually will reduce the imposed
carbon activity to the surface and, hence, the carbon
content in the surface near region. Typically, it will be
advantageous to apply a high carburising potential,
presuming that its control is possible. Effectively, for the
process parameters investigated in the present work,
controlling the carbon content in stainless steel entails
control of the hardness in the intermediate range,
tentatively in the range (1000 HV.
Hardness–depth profiles
The shapes of the hardness–depth profiles of carburised
and nitrided stainless steel differ markedly. First and
foremost, this difference has to be ascribed to the affinity
of Cr for C and N. The hardness–depth profiles for
nitriding exhibit a sharp case/core transition. This
characteristic profile can be explained in terms of a
relatively high affinity of Cr for N. The development of
the nitrided case is similar to that for internal oxida-
tion25 or strong interaction26, but with a gradient in the
transformed region. In contrast, the hardness profile
obtained for carburising resembles a diffusion profile.
This can be explained by the lower affinity of Cr for C
compared with the affinity of Cr for N. The develop-
ment of the carburised case follows closely that for
diffusion into a semi-infinite medium with constant
surface concentration and a composition independent
diffusion coefficient: an error function profile (cf.
standard text books on diffusion, e.g. Ref. 27).
The hardness–depth profile obtained by consecutive
carburising and nitriding effectively combines the
profiles obtained by nitriding and carburising. A content
of carbon in the intermediate range effectively bridges
the mismatch between the high nitrogen containing cN
and the austenite substrate. The transition from a very
hard surface (high interstitial contents/lattice dilation) to
the soft substrate occurs smoothly over an extended
distance (cf. Fig. 14). Technologically, this offers the
possibility of tailoring a specific hardness–depth profile
by controlling the process parameters of the carburising
and nitriding stages in the treatment. The combination
of carbon and nitrogen expanded austenite offer
significantly thicker layers, which have both the high
surface hardness from the cN and the load bearing
capacity of the underlying cC layer.
Influence of alloying elements
It was shown that expanded austenite was obtainable in
duplex stainless steel, where, most interestingly, the
ferritic structure transformed into expanded austenite.
This transformation has to occur according to the
sequence aRcRcN. The austenite stabilising effect of
nitrogen enables this transformation. The same trans-
formation applies for nitriding of AISI 303 containing
deformation martensite a9. The difference in layer
thickness of cN on former c and cN on former a regions
454 Surface Engineering 2005 VOL 21 NO 5–6
is associated with different compositions in ferrite and
austenite. Ferrite formers are preferentially located in
the ferrite matrix, whereas the austenite stabilisers are
preferentially located in the austenite grains. Evidently,
significantly faster growth of cN can occur into ferrite. It
is suggested that a higher Cr content yields a higher
nitrogen content, which produces a larger possible
gradient. Additionally, the diffusion coefficient of
nitrogen increases with N content ((33 at.-%N). The
combination of a larger possible gradient and a higher
diffusion coefficient gives a larger possible nitrogen flux
and, hence, faster layer growth. Mo is anticipated to
offer a higher thermal stability for expanded austenite
with regard to the development of CrN due to its
sluggish diffusion (see Ref. 12). Generally, the alloying
elements play a major role on the nitriding (and
carburising) behaviour of stainless steel, and the effect
of the individual elements is largely unexplored.
Conclusions
Low temperature gaseous carburising and nitriding of
various grades of stainless steel were successfully
performed on austenitic and duplex stainless steel. The
surface adjacent region of the treated stainless steels was
transformed into carbon and/or nitrogen expanded
austenite without the occurrence of carbides or nitrides.
Transformation of ferrite into expanded austenite was
observed for the duplex stainless steels investigated.
Brittle cracking occurred for high values of the nitriding
potential, whereas low to intermediate nitriding poten-
tials produced crack free cN layers with an unaltered
visual surface finish. Carburising was not associated
with the occurrence of brittle cracks, and the visual
surface finish remained unaffected.
Hardness–depth profiles were obtained for carburised,
nitrided and consecutively carburised and nitrided
AISI 316. Higher hardness values were obtained for
nitriding compared with carburising. The depth profiles
differ markedly; a smooth profile is obtained for
carburising, whereas nitriding produces a sheer drop in
hardness at the substrate interface. The combination
treatment of carburising followed by nitriding yielded a
layer consisting of a combination of cN and cC.
Technologically, this produces a favourable hardness–
depth profile: very high surface hardness on account of
the cN, with a smooth transition to the substrate
facilitated by the cC.
Acknowledgement
Financial support by the Danish Research Agency under
grant 26-01-0079 is gratefully acknowledged.
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