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Low-temperature gaseous surface hardening of stainless steel: The current

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Article in International Journal of Materials Research (formerly Zeitschrift fuer Metallkunde) · October 2009
DOI: 10.3139/146.110202

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T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Thomas L. Christiansen, Marcel A. J. Somers
Technical University of Denmark, Department of Mechanical Engineering, Kgs. Lyngby, Denmark
Low-temperature gaseous surface hardening of
stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.
The present review addresses the state of the art of low-tem-
perature gaseous surface engineering of (austenitic) stainless
steel and is largely based on the authors’ own work in the last
10 years. The main purpose of low temperature gaseous sur-
face engineering of stainless steel is to develop a hardened
case at the surface, while maintaining the superior corrosion
performance. This can be achieved by dissolving colossal
amounts of nitrogen and/or carbon without forming nitrides
and/or carbides, thus developing so-called expanded auste-
nite. The present work gives an overview over results ob-
tained on homogeneous expanded austenite and covers the
crystallography for nitrogen- and carbon-stabilised expanded
austenite, the solubility for nitrogen and carbon, the diffusion
of these interstitials as well as the stability of expanded aus-
tenite with respect to nitride and carbide formation. Subse-
quently, the fundamental understanding acquired on homo-
geneous samples is applied to understand the morphology,
composition, and residual stress distribution in functionally
graded material, as obtained by nitriding, carburising or ni-
trocarburising of austenitic stainless steel. Thereafter, as-
pects of modelling the compositional changes occurring dur-
ing nitriding are addressed. The overview summarises with
www.ijmr.de
an outlook towards future scientific challenges.
Keywords: Expanded austenite; Residual stress; Surface
engineering; Modelling
W 2009 Carl Hanser Verlag, Munich, Germany
1. Introduction
In the last 20+ years, plasma and implantation technologies
have opened the possibility for improving the wear perfor-
mance of stainless steel through low-temperature (< 723 –
823 K, i. e. < 450 – 550 8C) carburising and/or nitriding,
without impairing the corrosion resistance [1 – 4]. An excel-
lent state-of-the-art review on thermochemical surface en-
gineering of stainless steel in the year 2000 was given in
Ref. [5]. The incorporation of C and/or N relies on the sput-
tering away of the passive chromium(oxy)hydroxide film
from the surface, which is an integral part of the plasma
and implantation processes, and the subsequent implanta-
tion of C and N atoms as interstitials in the, usually fcc, lat-
tice. In the last 10 years ex-situ [6 – 8] and in-situ [9 – 12]
pretreatments of stainless steel were developed, which en-
able low temperature gaseous carburising and/or nitriding
and allow accurate control of the composition (profile) and
hardness (profile).
The industrial application of surface-engineered stainless
steels is obvious, because the potential of this widely used
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
F Feature
material is expanded to applications where a combination
of corrosion and wear resistance is required. Unfortunately,
due to the high cost and the restricted capacity of the pre-
sently few commercially available long-term treatments,
application has so far been limited to selected products.
The microstructural feature responsible for the highly de-
manded combination of excellent corrosion and wear per-
formances is so-called expanded austenite, cI (where
I = N, C), which in many publications in the field also is re-
ferred to as S-phase [13 – 15]. A first indication of nitrogen-
expanded austenite or S-phase as a very thin transition zone
between a zone containing Cr-nitrides and the unaffected
austenite was first observed in the early 1970s [16]. The
first scientific publication reporting the occurrence of a ni-
tride-free zone of expanded austenite of about 20 microns,
obtained through plasma nitriding is due to Zhang and Bell
[1]. Expanded austenite without nitrides/carbides is ob-
tained by dissolving colossal amounts of atomic C and/or
N in stainless steel at temperatures below, say, 823 K
(550 8C) for carbon and about 723 K (450 8C) [5, 8] for ni-
trogen.
The present review is largely based on the research of the
present authors (and co-workers) throughout the last
10 years. Our research has dealt exclusively with gaseous
nitriding, carburising, and nitrocarburising. Gaseous pro-
cesses have the advantage over plasma-assisted and implan-
tation processes that expanded austenite is obtained by dis-
solving colossal amounts of atomic C and/or N in stainless
steel through an adjustable chemical potential of carbon
and/or nitrogen in the gas mixture. Moreover, no additional
defects, such as self interstitials, vacancies, and redeposi-
tion of sputtered atoms, associated with the implantation
of charged species are introduced, which may affect the
case developed. Furthermore, it was demonstrated [15] that
homogeneous expanded austenite as thin foils or powder
can be achieved, which allows the investigation of homoge-
neous expanded austenite of uniform composition. This is
of major importance in order to be able to determine funda-
mental data on crystal structure, thermodynamics and ki-
netics of dissolution of interstitials. Such fundamental data
is essential to design new process variants, tailor the pro-
cess parameters to obtain optimal combinations of materi-
als properties and simulate the development of the hardened
case during processing as an element of process control.
Also, such data is imperative for the design of new materi-
als with optimized performance towards this class of sur-
face engineering treatments.
In this review, firstly, the preparation of expanded aus-
tenite in a gas mixture is described. A prerequisite for the
incorporation of N and/or C into stainless steel is to by-pass
1361
F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
the passive nature of the surface, which is necessary for the
corrosion resistant behaviour, but also hinders the direct in-
corporation of N and C from gas mixtures generally used in
thermochemical surface engineering of steels, i. e. NH3/H2
in the case of nitriding and CO/CO2/ H2/H2O for carburis-
ing. Two patented techniques used in our work are de-
scribed in Section 2. An overview of the investigations of
homogeneous foils of expanded austenite to determine the
Not for use in internet or intranet sites. Not for electronic distribution.
crystallography, solubility, and diffusivity of interstitials
as well as the thermal stability is provided in Section 3. Sur-
face engineering of stainless steels where (graded) ex-
panded austenite zones develop in the surface region, are
described in Section 4 and interpreted in terms of the funda-
mental understanding reached in Section 3. The state of the
art of modelling the growth kinetics of expanded austenite
zones is described in Section 5, followed by a summary
and outlook in Section 6.
For experimental details of the experiments that have pro-
vided the results shown in the present work, the reader is re-
ferred to the original publications mentioned in the figure
captions and the associated text. Generally, the stainless steel
quality used for the investigation has been of AISI 304 (L) or
AISI 316 (L) type. The nominal compositions of these com-
mercially available materials are given in Table 1.
Table 1. Nominal compositions (in wt.%) of austenitic stainless
steel alloys used in the present work.
Alloy Cr Ni Mo Mn Si Fe
AISI 304 19.60 8.68 0 1.66 1.26 balance
AISI 304L 19.45 9.49 0 1.17 0.98 balance
AISI 316 19.11 12.70 1.40 1.74 1.45 balance
AISI 316L 18.93 13.55 1.69 1.76 0.62 balance
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2. Thermochemical treatment of stainless steel;
surface activation
The passive nature of stainless steel surfaces hinders the di-
rect surface engineering of this material in currently applied
gaseous atmospheres for nitriding, carburising and nitrocar-
W 2009 Carl Hanser Verlag, Munich, Germany
burising. In our work we have developed two independent
techniques to circumvent the passivity of stainless steel sur-
face, which are shortly described below.
2.1. Activation of stainless steel with
a catalytic metal layer
This pre-treatment involves chemical stripping of the pas-
sive film, followed by electrochemical deposition of Ni in
a Wood’s nickel bath (NiCl2 + HCl). The maximum thick-
ness of the deposited layer is 20 nm, as calculated from
Faraday’s law and assuming an efficiency of 3 % during
electrodeposition.1 The purpose of the thin electrodeposited
nickel layer is twofold: preventing the repassivation of the
stainless steel surface during handling and catalyzing the
dissociation of N or C bearing gases at the surface. Alterna-
tively, the passive chromium oxide layer can be removed in
a NiCl2-based electrolyte for pH < 4.2 and an anodic poten-
1
This value is an upper estimate of empirically realised efficiencies;
the remaining 97 % of the current is used for H2 development.
1362
tial, such that the combination of pH and applied potential
allows the development of the CrCl2+ complex at the sur-
face, which dissolves in water. Subsequently, reversing the
polarity of the applied potential will lead to Ni being depos-
ited on the stainless steel surface.
After the development of a nano-scale Ni layer at the sur-
face, nitriding, carburising or nitrcarburising can be carried
out in the usual gas mixtures.
Gaseous nitriding is generally performed in mixtures of
NH3 and H2. The partial pressures, pj, of H2 and NH3 deter-
mine the so-called nitriding potential, KN ¼ pNH3 =p3=2 H2 . The
nitriding potential is straightforwardly related to the nitrogen
activity, aN , aN ¼ KT
KN , where KT is the temperature de-
pendent equilibrium constant of the overall dissolution of N
into the solid state from a NH3/H2 gas mixture. Analogously,
gaseous carburising can be performed in a CO/H2(/H2O) gas
mixture. The associated carbon potential, KC, follows from
KC ¼ pCO
pH2 =pH2 O , which shows that the carburising po-
tential can only be adjusted precisely when the partial pres-
sures of CO, H2, and H2O are controlled.
2.2. Carburising with unsaturated hydrocarbon gas
A method for simultaneous activation and low temperature
carburising of stainless steel involves the use of unsaturated
hydrocarbon gas. Exposing stainless steel to a mixture of
unsaturated hydrocarbon gas and hydrogen at an elevated
temperature leads to removal or breakdown of the passive
layer and results in ingress of carbon, i. e. development of
carbon-expanded austenite. This method has recently been
patented by the present authors [12]. The unsaturated hy-
drocarbon gas acetylene has proven especially effective,
which most likely has its origin in the highly reactive unsa-
turated triple bond. Consequently, this method enables sim-
ultaneous activation and carburising of stainless steel speci-
mens without the use of pre-treatments for surface
activation. The mechanism of simultaneous surface activa-
tion and carburising in acetylene containing gas has so far
not been elucidated. However, it is hypothesised that the
combination of a high carbon activity in combination with
the occurrence of highly reactive radicals makes it possible
to activate the surface by removal or breakdown of the
oxide layer and to run the carburising process. It appears
that the presence of hydrogen is a prerequisite for the acti-
vation/carburising process to take place; this hints at a
free-radical process mechanism, where hydrogen promotes
the development of free radicals. In this respect, it should
be noted that the thermal decomposition of C2H2 results in
development of H2.
The carburisingppotential
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffifor
ffi a C2H2/H2 gas mixture fol-
lows from KC ¼ pC2 H2 =pH2 and is therefore easier to ad-
just under practical circumstances than for CO/H2/H2O gas
mixtures, because control of the water vapour pressure,
which often is neglected in heat treatment practise, is no
longer of importance. It should be emphasized that even
minute amounts of acetylene in the carburising atmo-
spheres lead to high carbon activities. A major advantage
of C2H2/H2 gas mixtures is that they are oxygen free, which
minimizes the risk for repassivatation during carburising.
By adding NH3 to the C2H2/H2 gas mixture nitrocarburising
with controlled activities of both nitrogen and carbon is
possible. However, when applying reactive – and hence un-
stable – unsaturated hydrocarbon compounds, there is an
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
 F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status

imminent risk of soot deposition. In this respect tempera-

ture, gas composition, and pressure play a dominant role in
order to avoid soot depositions and, hence, maintain para-
equilibrium control of the process by adjusting the gas com-
position.

3. Homogeneous expanded austenite

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In this Section the results shown were obtained on homoge-

neous thin foils or powder of uniform composition, unless
stated otherwise.

3.1. Crystallography of expanded austenite

(a)
The crystallographic identity of expanded austenite or
S-phase2 has been under debate since the very first observa-
tion of this phase. This can largely be attributed to the in-
vestigation of inhomogeneous samples, consisting of a rela-
tively thin zone of expanded austenite on a stainless steel
substrate. As a consequence the investigated depth range
with X-rays contains a (steep) composition gradient as well
as a (steep) macro stress gradient. In addition to these influ-
ences, faulting of the fcc lattice causes both an hkl-depen-
dent shift of the Bragg peaks as well as asymmetric broad-
ening, depending on the stacking fault (and twin)
probability [17, 18]. A recent review attempts to reconcile
the crystallographic data available [19]. The outcome of
this reconciliation was that a combination of faulting and
(lattice) strains can explain the diverting observations in
the literature. The notion of combined stress and faulting is
(b)
not new and was originally proposed by Sun et al. [2]. Ob-
viously, the remedy to unambiguously assess the crystallo- Fig. 1. (a) X-ray diffractogram of homogeneous expanded austenite
graphy of expanded austenite is the investigation of homo- measured with Co Ka radiation, reflecting the fcc crystal lattice
geneous samples, i. e. samples with a known and uniform (23.7 % NH3); (b) comparison of experimental and predicted peak
shifts from perfect fcc position [15].
composition, such that asymmetric broadening as a conse-
www.ijmr.de

quence of a composition-depth profile and the role of com-

position-induced stresses can be ruled out. Indeed, such
measurements were performed and published [15, 20], but
not recognized as such in [19]. The results showed for the
first time that expanded austenite is fcc and that systematic
hkl-dependent peak shifts with respect to the perfect fcc
peak positions can be explained from the presence of stack-
W 2009 Carl Hanser Verlag, Munich, Germany
stainless steel alloy. For cC lattice parameters in the range
0 < yC < 0.16 were obtained [22]; for cN lattice parameters
were obtained in the range 0.17 < yN < 0.61. The reason
that the minimum nitrogen content amounts to yN = 0.17 is
only partly a consequence of the experimental method used
to obtain homogeneous foils, which involves full nitriding

ing faults [15, 20], which were recently shown to be most followed by reduction in flowing hydrogen [20]. Evidently,
likely deformation-induced [21]. An example of a Co-Ka
diffractogram of homogeneous strain-free expanded auste-
nite of uniform composition is given in Fig. 1a. The peak
shifts due to faulting are given in Fig. 1b for a range of sam-
ples of different composition; an excellent agreement was
observed between the experimental peak shifts of 111,
200, and 220 and Warren’s theory (for experimental details
see [15, 20]). Note that for the low stacking fault probabil-
ities, a < 0.04, under consideration in [15, 20], the simpli-
fied theory of Warren is applicable and that only a small de-
viation from the superior theory of Velterop et al. [18] is
obtained for the main diffraction peaks taken into consid-
eration in [15, 20] (see Fig. 4 in Ref. [18]).
The composition dependence of the lattice parameters of
cN and cC are given in Fig. 2 as a function of the contents of
interstitial atoms yN and yC, respectively, which express the
number of interstitial atoms N or C per metal atom in the
Fig. 2. Lattice parameter, a, of nitrogen-stabilized and carbon-stabi-
2
In the literature review provided in Ref. [17] m-phase and j phase lized expanded austenite (cN and cC, respectively) as a function of the
were also included. number of interstitial atoms N or C per metal atom (yN or yC) [20, 22].

Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10 1363

F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
nitrogen atoms amounting to an atomic ratio Cr : N = 1 : 1
cannot be removed by NH3 development at the foil surface
(see further discussion below). It is anticipated though that
only a small content of nitrogen can be dissolved before
trapping of N by short range ordering with Cr atoms occurs.
The lattice parameters of both cN and cC depend linearly
on the contents of interstitial atoms yN and yC, respectively.
The expression yI (I = N, C) could be interpreted as the oc-
Not for use in internet or intranet sites. Not for electronic distribution.
cupancy of the lattice formed by the octahedral interstices
in fcc, provided that all interstitial atoms reside at these po-
sitions. The straight lines fitted through the data in Fig. 2
are parallel within experimental accuracy. Extrapolation of
the two linear dependencies shows a systematically larger
lattice parameter for cN. It is believed that the isotropic dila-
tation of the lattice of cN in addition to the dilatation caused
by the dissolved N atoms, has a microstructural origin.
New EXAFS work on unnitrided, homogeneous fully ni-
trided and denitrided AISI 316 foils sheds a light on the lo-
cation of nitrogen in expanded austenite [23]. Qualitative
interpretation of the pseudo-radial distribution functions
(pRDFs), obtained from EXAFS data and shown in Fig. 3,
provides the following picture. Clearly, in the reference
AISI 316 sample the pRDFs for Fe, Cr, and Ni are identical
within experimental accuracy. The main peak in the pRDFs
www.ijmr.de
W 2009 Carl Hanser Verlag, Munich, Germany
Fig. 3. Pseudo Radial Distribution Functions (pRDFs) extracted from
EXAFS investigation of unnitrided stainless steel, fully nitrided ex-
panded austenite and denitrided expanded austenite [23].
1364
is associated with the average distance to the nearest neigh-
bour Me (= Fe, Cr, Ni) of the probed atom. The additional
peak for Ni at r = 1.4 Å is an artifact, associated with the
poorer counting statistics for Ni as compared to Fe and Cr
(see Ref. [23]). Nitriding at maximum nitriding potential af-
fects the EXAFS data for Cr, Fe, and Ni differently. Com-
mon to all is a shift of the pRDFs to higher r values and
the appearance of an additional peak to the left of the main
peak. The shift is a consequence of an increase of the Me–
Me distances caused by the presence of N atoms and is lar-
gest for Cr and least pronounced for Ni. The additional peak
is attributed to the presence of nitrogen as a nearest neigh-
bour and the intensity would reflect the probability of find-
ing N as a nearest neighbour to the probed metal atom, i. e.
the (average) coordination number. This additional peak
appears largest for Cr and smallest for Ni, which indicates
enhanced probability for finding N as a nearest neighbour
to Cr as compared to Fe and Ni, and consistent with larger
interatomic Me–Me distances for Cr than for Fe and Ni. Re-
ducing the nitrogen content by denitriding essentially
brings the pRDFs of Fe and Ni back to that of the unnitrided
reference, while the pRDF for Cr is still shifted as com-
pared to the unnitrided sample, but not as pronounced as
for the fully nitrided sample. This observation proves for
the first time that the nitrogen atoms which cannot be re-
gained from solid solution by denitriding are “trapped” by
the Cr atoms. Quantitative analysis of the EXAFS data
yields that the number of nitrogen neighbours to the Cr
atoms is 2 – 3 in the denitrided sample and that the Cr–N
bond length is compatible with expanded austenite and con-
siderably smaller than in CrN. These results exclude the
possibility that Cr and N are present as monatomic CrN pla-
telets, for which the coordination number would be 4 and
the bond length would reflect the lattice parameter of CrN.
Since the nitrogen coordination numbers for Fe and Ni are
below the detection limit, the EXAFS results also exclude
the possibility that N is present in mixed substitutional in-
terstitial atom clusters (MSIACs) [24]. In order to reconcile
the coordination number of the Cr atoms of 2 – 3 with a ni-
trogen content in the denitrided alloy conforming to
Cr : N & 1 : 1, the occupied octahedral interstices have to
be connected through the Cr atoms that share these octahe-
dra and, accordingly, form a 3D network (cage structure)
in the solid state. It is hypothesized that this network in-
duces a dilatation of the austenite lattice in cN and conse-
quently enhances the nitrogen solubility in the octahedral
interstices that are unoccupied in the denitrided sample,
but become re-occupied on re-nitriding. Evidently, a simi-
lar dilatation of the austenite lattice does not occur in cC,
for the composition range investigated, which is attributed
to a lower (maximum) interstitial atom content as a conse-
quence of the lower affinity of Cr for C as compared to N
[8].
3.2. Nitrogen and carbon solubility in expanded austenite
The interstitial solubility of nitrogen and carbon in ex-
panded austenite that can be achieved through a gaseous
treatment should be considered as a para-equilibrium, i. e.
a metastable equilibrium between N/C in the gas phase
and N/C in the solid state at a temperature where substitu-
tional solutes are effectively immobile, whereas interstitial
solutes are able to diffuse [25 – 27]. A thermodynamic mod-
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10

T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
el that realistically describes the relation between the che-
mical potential of the interstitial atoms, lI, and their inter-
stitial content, yI, in expanded austenite has so far not been
presented. A first attempt to predict the solubility of carbon
in cC under the assumption of para-equilibrium conditions,
indicated that, although a marked increase of the solubility
was obtained as compared to the carbon solubility under
equilibrium where carbides are present, still a major discre-
Not for use in internet or intranet sites. Not for electronic distribution.
pancy occurred with experimental solubilities as deter-
mined with various techniques on an as grown cC zone on
stainless steel substrates [27]. Actually, in order to assess
the solubility of N/C in expanded austenite under para-equi-
librium conditions, homogeneous samples of uniform com-
position saturated in a gas atmosphere of known composi-
tion should be investigated. Using inhomogeneous samples
containing composition gradients, the influence of compo-
sition-induced stresses of several GPa’s on the solubility
cannot be avoided. Such stress-affected deviations from
the para-equilibrium solubility were calculated to be as high
as DyN & 0.15 (see Table 3 in Ref. [28]). The solubility of
nitrogen in homogeneous cN of uniform composition in
para-equilibrium with a NH3/H2 gas mixture of adjusted
composition as determined for AISI 304 and AISI 316 are
presented in Fig. 4. The absorption isotherm in Fig. 4 de-
picts the occupancy yN as a function of the nitrogen activity,
aN, calculated from the NH3 and H2 contents in the furnace
at the temperature under consideration, taking N2 as the re-
ference state [20]. Clearly, a linear relation applies between
yN and ln aN for nitrogen activities ranging from ln aN = 3
to ln aN = 10. For nitrogen activities lower than aN = e3 a
stronger dependence of yN on ln aN applies. The minimum
and maximum nitrogen contents attainable in AISI 304
and AISI 316 are indicated in Fig. 4 by the horizontal lines
denoted by aN = 0 and aN = 1, respectively. The data in
Fig. 4 demonstrates convincingly that colossal quantities
of nitrogen can be dissolved reproducibly by imposing a ni-
www.ijmr.de
trogen activity adjusted through the nitriding potential, KN,
of the gas mixture and the temperature of the sample.
Formal models to describe the relation between nitrogen
solubility and nitrogen activity were applied unsuccess-
fully. In order to obtain a reasonable description of the data
by the Redlich–Kister formalism [29] 5 fit parameters were
W 2009 Carl Hanser Verlag, Munich, Germany
Fig. 4. Nitrogen solubility in expanded austenite, yN, as a function of
nitrogen activity, aN, applied for nitriding AISI 316 at 693 K and
718 K and for nitriding AISI 304 at 693 K. Straight lines through the
data are indicated to guide the eye. The solubility levels for the nitro-
gen activities nil and infinity are indicated by horizontal bars [20].
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
F Feature
required, which makes the description physically meaning-
less. Neither did the Wagner–McLellan cell model [30]
with 4 fit parameters provide an accurate, physically mean-
ingful description. Clearly, taking the EXAFS investiga-
tions from Ref. [23] into consideration (cf. Section 3.1), a
thermodynamic model that describes nitrogen in solid solu-
tion in expanded austenite should account for short-range
ordering of N and Cr and an anticipated enhanced lattice so-
lubility. Quantitative analysis of the pRDFs in Fig. 3 shows
that the coordination numbers of Cr, Fe, and Ni for the fully
nitrided expanded austenite are 4.9, 3.3 and 3.0, respec-
tively [23], which emphasizes the importance of short-
range order of Cr and N in dissolving N in cN. Conse-
quently, the average distance of Cr atoms to neighbouring
Me atoms (Fe, Ni or Cr) is considerably larger than the
Me–Me distances for Fe and Ni [23], which is a major chal-
lenge in a physically realistic thermodynamic model for ex-
panded austenite.
Absorption isotherms as shown for cN in Fig. 4 have so
far not been published for cC. Recent work indicates that
the maximum solubility in carbon expanded austenite in
para-equilibrium cannot exceed approximately yC = 0.16
(cf. Fig. 2); beyond this carbon content carbides develop
[22]. The underlying chemical or physical reasons for these
observations remain to be unravelled.
3.3. Diffusion kinetics of interstitials
in expanded austenite
Solid-state diffusion of N and C through an expanded auste-
nite zone is likely to play a major, if not dominant, role in
controlling the growth rate and thus the thickness of the ex-
panded austenite zone during processing. Several attempts
to determine the diffusion coefficients of N and C have
been published in the literature [31 – 38]. Since an investi-
gation of diffusion of interstitials during low-temperature
surface hardening of stainless steel has almost exclusively
been based on implantation/plasma-based methods, no
straightforward determination of the concentration depen-
dent diffusion coefficient has been possible, as part of the
steel surface is concurrently removed by sputtering [39].
This simultaneous layer removal has to be taken into con-
sideration when the diffusion coefficient is evaluated. An-
other effect of implantation/plasma-based treatment is that
the surface is altered by the introduction of defects in the
solid state, which affect the diffusion mechanism of the in-
terstitial atoms in the damaged region. Furthermore, the
strong interaction of N (and to a lesser extent C atoms) with
Cr atoms, implies that not all nitrogen atoms contribute to
the same extent to layer growth (see Ref. [40] in this re-
spect). Last but not least, extremely high composition-in-
duced compressive lattice strains and lattice strain gradients
occur in growing expanded austenite layers [41], which are
likely to affect the actual diffusive flux of the nitrogen
atoms through the layer. The diffusivity of N in cN was de-
termined from the stepwise denitriding kinetics of initially
fully nitrided expanded austenite coupons [41]. From the
average diffusion coefficient for a series of narrow compo-
sition intervals the composition-dependent diffusivity of N
was reconstructed (Fig. 5). Clearly, the diffusion coeffi-
cient of nitrogen in expanded austenite increases with nitro-
gen content up to a maximum value of approximately
yN = 0.45 and thereafter decreases again. For yN < 0.45 the
1365
F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.
Fig. 5. Average (intrinsic) diffusion coefficient for N in expanded aus-
tenite at the temperatures 693 K (AISI 304 & AISI 316) and 718 K
(AISI 316). The horizontal bars indicate the concentration range
wherein the thermogravimetric denitriding data were fitted. The drawn
lines are given to guide the eye [41].
diffusion coefficients for N in AISI 304 and AISI 316 are
more or less equal at 693 K. Beyond the maximum value
the diffusivity of N in AISI 316 is systematically higher
than in AISI 304. The occurrence of a maximum value can
be discussed qualitatively as follows. The nitrogen atoms
in austenite are presumed to reside (preferentially) at octa-
hedral interstices of the fcc lattice of metal atoms. Dissol-
ving more N atoms in expanded austenite is associated with
an expansion of the fcc lattice [20]. Upon isotropically di-
lating the fcc lattice with increasing nitrogen content the
sizes of octahedral and tetrahedral interstices increase and
a reduction of the activation energy for nitrogen diffusion
will occur. Consequently, the diffusivity of nitrogen will in-
crease with nitrogen content. The data in Fig. 5 suggest that
the activation energy for diffusion of nitrogen decreases
with increasing nitrogen content for nitrogen contents up
www.ijmr.de
to the value corresponding to the maximum diffusivity
yN = 0.45. A similar decrease of the activation energy with
carbon content has previously been observed for carbon dif-
fusion in austenite, albeit for much lower interstitial atom
content than in the present work [42]. As a consequence of
the increase of the nitrogen occupancy, an antagonistic ef-
W 2009 Carl Hanser Verlag, Munich, Germany
fect is expected as more and more nitrogen atoms are dis-
solved in expanded austenite and the probability that a
neighbouring octahedral site is empty decreases. Similarly,
the probability that a tetrahedral interstice is occupied by
nitrogen increases. These consequences will affect the dif-
fusivity of nitrogen adversely, such that the pre-exponential
factor decreases with nitrogen content. Evidently, the an-
tagonistic effects on diffusion of dissolving more N in ex-
panded nitrogen result in a maximum value at the observed
nitrogen content.
Composition-dependent diffusivities for C in cC have so
far not been determined experimentally from the carburising
or decarburising kinetics of homogeneous thin foils. A simu-
lation of three different procedures to determine the compo-
sition-dependent C diffusivity experimentally, yielded that
the best approximation of the composition dependent diffu-
sivity is obtained for an incremental sorption method [43].
In this method the mass increase rate, which is directly re-
lated to the inward flux of C atoms at the surface, is meas-
ured for different initial carbon contents in the homogeneous
foil of uniform composition.
1366
3.4. Stability and decomposition of expanded austenite
Since expanded austenite can only exist under para-equili-
brium conditions, and thus is metastable, there is a tendency
for expanded austenite to decompose. Nitrogen-stabilized
expanded austenite tends to develop CrN, while for car-
bon-stabilized expanded austenite the Cr-based carbides
M23C6 and M7C3 as well as the Fe-based carbide M5C2
(Hägg carbide) have been reported.
The stability of expanded austenite in AISI 304L and
AISI 316L was investigated in Ref. [44], where isochronal
annealing of synthesized nitrogen expanded austenite was
carried out. Both inert (N2) and reducing (H2) atmospheres
were investigated. The thermal stability of synthesized ni-
trogen expanded austenite in AISI 304L (saturated at
KN = inf) in a reducing atmosphere of hydrogen and nitro-
gen is given in Fig. 6 for AISI 304L. On isochronal anneal-
ing in nitrogen gas weight loss of the sample coincides with
an exothermal heat effect and commences at approximately
500 8C (773 K). The identical experiment in hydrogen gas
shows the occurrence of weight loss and heat release already
at approximately 270 8C (443 K), followed by another heat
release above 500 8C (773 K). Obviously, the weight loss at
low temperature in a hydrogen atmosphere has to be attribu-
ted to the development of NH3. Not all dissolved nitrogen
can be retracted from the sample; an amount slightly larger
than corresponding to Cr : N = 1 : 1 remains in the sample
[44] (cf. Sections 3.1 and 3.2). The second heat release for
the H2 annealed sample can then be attributed unequivocally
to the development of CrN. For annealing in a nitrogen at-
mosphere the development of CrN and the release of nitro-
gen from the sample, by N2 development, occur simulta-
neously. This indicates that the nitrogen in excess of
Cr : N = 1 : 1 can no longer be accommodated in the solid
state. Owing to overlap of the heat effects involved in CrN
and N2 development, a kinetic analysis of the stability of ex-
panded austenite is not possible for the samples annealed in
nitrogen gas. A kinetic analysis of the decomposition of ex-
panded austenite in hydrogen yields that the second peak is
observed at a lower temperature for AISI 304L as compared
to AISI 316L, which indicates that nitrogen expanded auste-
nite is more thermally stable in AISI 316L. A third peak is
observed for AISI 304L which is ascribed to a transition
from ferrite to austenite. The decomposition products in the
synthesized materials were characterised with X-ray diffrac-
tion, showing that cN decomposes into c + CrN for AISI
Fig. 6. Simultaneously measured heat evolution (lines with 1 or 2 peaks)
and weight loss (continuously falling lines) due to nitrogen release in N2
(drawn lines) and H2 (dashed lines) on isochronal annealing of fully
nitrided 304L at a heating rate of 0.417 K · s – 1 [44].
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
 F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status

sence of molybdenum in AISI 316L and the difference in de-

composition mechanism.
The thermal stability of carbon stabilized expanded auste-
nite has not been investigated systematically. Ernst et al. [45]
reported that v-carbide M5C2 and M7C3 developed in an ex-
panded austenite zone with a maximal carbon content of
yC = 0.12 at the surface, upon prolonged carburising for
44 h at 475 8C (748 K). Isochronal annealing of homoge-
Not for use in internet or intranet sites. Not for electronic distribution.

neously carburized expanded austenite powder revealed that

for a relatively low carbon content (yC = 0.056) the main car-
bide that develops is M23C6, whereas for a relatively high
carbon content (yC = 0.15) M7C3 was observed (Fig. 8). In
neither of the samples was it possible to identify the presence
of M5C2. These observations are in accordance with a ther-
modynamic prediction of the equilibrium carbides (Fig. 9).
Fig. 7. Isothermal stability plot for expanded austenite, calculated
from the kinetic parameters obtained from isochronal annealing experi-
ments [44].

316L and into a + CrN for AISI 304L. The formed ferrite in
AISI 304L transforms into c at approximately 680 8C
(953 K) (see Fig. 6). The values obtained for the activation
energy for the decomposition of expanded austenite are
128 (± 9.9) kJ · mol – 1 for AISI 304L and 187 (± 17.7) kJ · mol – 1
for AISI 316L. Clearly, a marked difference is observable
for the two investigated alloys, which could be associated
with the mechanism of the transformation. The development
of ferrite in 304L simultaneously with the precipitation of
CrN is expected to lower the nucleation barrier for the trans-
formation, because of the favourable orientation relationship
{001}a-Fe //{001}CrN and <100>a-Fe //<110>CrN. It is sug-
(a)
gested that expanded austenite in 304L decomposes accord-
ing to a eutectoid transformation and in 316L according to a
discontinuous transformation. Quantitative kinetic analysis
of isochronal annealing experiments allowed the prediction
of the isothermal annealing behaviour in terms of the stabi-
www.ijmr.de

lity diagram in Fig. 7. The stability diagram shows that ex-

panded austenite is more stable in AISI 316L than in AISI
304L. This could straightforwardly be ascribed to the pre-
W 2009 Carl Hanser Verlag, Munich, Germany

(b)

Fig. 9. Thermocalc equilibrium calculations showing the stable phases

in carbon expanded austenite (a) yC = 0.056 and (b) yC = 0.16 as a
function of temperature.

4. Inhomogeneous expanded austenite; surface

hardening of stainless steel.

Growth of an expanded austenite zone into a bulk substrate of

Fig. 8. X-ray diffractograms (Cr-Ka radiation) of decomposed homo-
geneous expanded austenite powder with the carbon contents, yC, men-
tioned. The peak position of uncarburized austenite is indicated as hklc.
For a low carbon content M23C6 develops; for a relatively content
M7C3 develops. The samples were decomposed by annealing to
1000 8C (1273 K) at a heating rate of 0.67 K · s – 1, while recording the
DTA signal [22].
stainless steel is, contrary to homogenous expanded austenite
as discussed in Section 3, associated with the development of
composition induced stresses as a consequence of misfitting
interstitials dissolved in the fcc lattice and the constraining
substrate. Development of inhomogeneous expanded auste-
nite “layers” by incorporation of N and/or C in the surface of
stainless steel is associated with highly beneficial mechani-
cal, tribological, and partly chemical properties.

Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10 1367

F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
The present chapter presents an overview of results ob-
tained for growth of inhomogeneous expanded austenite,
i. e. gaseous surface hardening of stainless steel through
the development of an expanded austenite case at the sur-
face.
For more extensive treatises of gaseous carburising, ni-
triding, nitrocarburising, and combination of carburising
and nitriding of bulk stainless steel with the application of
Not for use in internet or intranet sites. Not for electronic distribution.
a Ni-layer the reader is referred to [8, 46]. The topic of resi-
dual stress in expanded austenite “layers” on a substrate of
stainless steel has been dealt with extensively (for carbon
expanded austenite) in [47]. For an in-depth treatise of si-
mulation of nitrogen diffusion profiles in stainless steel the
reader is referred to [28].
4.1. Carburising
Metallographic cross sections of carburised AISI 316 are
presented in Fig. 10. It is evident that relatively thick zones
of approximately 25 lm of carbon expanded austenite (cC)
can be produced within a short carburising time (e. g. 4 h).
Lowering the temperature to 300 8C (573 K) and increasing
www.ijmr.de
(a)
W 2009 Carl Hanser Verlag, Munich, Germany
(b)
Fig. 10. Light optical micrographs of carburised stainless steel AISI 316
using Ni surface activation. (a) 510 8C (783 K)/4 h/40 % CO–60 % H2.
(b) 470 8C (743 K) / 20 h / 40 % CO – 60 % H2.
1368
the carburising time to 20 h results in a comparable case
thickness. It should be noted that carburising in atmo-
spheres of CO-H2 cannot directly be related to a carburising
potential or carbon activity unless the partial pressure of
H2O (g) is known (see Section 2.1).
The transition from the substrate to the expanded auste-
nite zone, cC, is smooth and not as pronounced as is ob-
served for nitriding (cf. below), which can be attributed to
a continuous carbon solubility in expanded austenite ran-
ging from yC = 0 to yC = 0.16 whereas a “discontinuity” in
the nitrogen content occurs from yN = 0 to yN = 0.18 (cf.
Fig. 2). The grain boundaries from the austenite substrate
continue into cC – fading out as the surface is approached
(higher C contents). The chemical resistance of cC to the
etching reagent is clearly observed in Fig. 10; the cC ap-
pears featureless contrary to the substrate. This phenomen-
on, as for nitriding, hints at a higher electrochemical poten-
tial of cC as compared to austenite in the etchant applied.
A typical X-ray diffraction pattern of cC obtained by car-
burising in CO–H2 is depicted in Fig. 11. Obviously, the fcc
reflections are shifted to lower diffraction angles, although
not as dominant as is the case for cN (see below). This is a
clear illustration of the implications of the lower interstitial
content in cC as compared to cN (cf. Section 3.2 and Fig. 2).
An alternative method for carburising of stainless steel
without the necessity of a pre-treatment is the use of acety-
lene. This method enables direct carburising, i. e. simulta-
neous surface activation and incorporation of carbon (see
Section 2.2). Acetylene carburising is carried out in mix-
tures of acetylene and hydrogen, which implies that the car-
burising potential and hence the carbon activity can be ac-
curately adjusted. In the temperature range associated with
low temperature carburising the imposed carbon activities
in acetylene-hydrogen can be very high, analogous to am-
monia-hydrogen gas mixtures, which provide high nitrogen
activities.
Micrographs of (cold-worked) stainless steel AISI 316
carburised in C2H2–H2–N2 atmospheres are depicted in
Fig. 12. The major difference between the two samples de-
picted in Fig. 12a and 12b is the gas composition. The sam-
ple in Fig. 12a was carburised with only 1 % C2H2 in the gas
mixtures and shows clearly that acetylene is a potent car-
burising agent. The extent of the expanded austenite zone
in Fig. 12a is approximately 15 lm. The expanded austenite
zone depicted in Fig. 12b was obtained with a C2H2 content
Fig. 11. X-ray diffraction patterns of nitrided and carburised stainless
steel AISI 316. Nitriding was carried out at 445 8C (718 K) for 22 h in
NH3–H2–N2 gas mixtures. The nitriding potentials are indicated in the
figure. Carburising was carried out in 20 % CO–80 % H2 gas atmosphere
at 515 8C (788 K) for 5 h.
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10

T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.
(a)
www.ijmr.de
(b)
Fig. 12. Light optical micrographs of acetylene activated/carburised
(initially cold worked) stainless steel AISI 316. (a) 420 8C (693 K)/
48 h/1 % C2H2–90 % H2–9 % N2. (b) 420 8C (693 K)/67 h/48 % C2H2–
48 % H2–4 % N2.
W 2009 Carl Hanser Verlag, Munich, Germany
of almost 50 vol.% and yields a thickness of 25 lm. The
higher content of acetylene in the gas atmosphere is asso-
ciated with a higher carburising potential and hence a high-
er carbon activity. Closer examination of the expanded aus-
tenite “layer” in Fig. 12b suggests that the carbon content is
higher compared to the sample carburised with 1 % acety-
lene. The enhanced thickness is a direct consequence of this
and only partly a result of the prolonged carburising time. It
should be emphasized that it is not straightforwardly valid
to “translate” the gas compositions and their carburising po-
tentials into the para-equilibrium experienced by the solid
state, because the present carburising conditions resulted
in a slight greyish soot deposition and nanotube develop-
ment on the steel surface. The samples were carburised in
a thermobalance, which basically is a small vertical tube
furnace. However, process conditions can be established,
which allow carburising without soot deposition, and hence
thermodynamic control of the gaseous process.
The hardness–depth profile of the carbon expanded aus-
tenite “layer” depicted in the micrographs in Fig. 11b is
given in Fig. 13. The hardness exceeds 900 HV in the near
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
F Feature
Fig. 13. Hardness–depth profile of acetylene activated/carburised
stainless steel AISI 316. Process conditions 420 8C (693 K)/67 h/
48 % C2H2–48 % H2–4 % N2 (the corresponding micrograph is depicted
in Fig. 12 b).
surface region, as measured in cross section, and decays
gradually towards the austenite substrate. This is character-
istic for low-temperature carburising of stainless steel and
is not a feature that is unique for acetylene carburising.
The smooth and gradual decrease in hardness towards the
substrate is consistent with a gradual change in the carbon
content (cf. Fig. 2, the discussion above and Ref. [47]) as
well as a smooth in-depth decay of composition-induced re-
sidual stress (see below).
A comprehensive discussion of the mechanisms of acety-
lene carburising is contemplated in a future article. For
more examples the reader is referred to Ref. [12].
4.2. Nitriding
Nitriding of austenitic stainless steel AISI 316 at 718 K
leads to the development of a nitrogen expanded austenite
zone as shown in Fig. 14. The expanded austenite zone,
which has a layer-like appearance, because of the steep ni-
trogen composition profile and associated change in the re-
sponse of the etchant, is generally featureless as compared
to the underlying austenite. Still, grain boundaries from the
substrate are observed to continue into the expanded auste-
nite region close to the substrate, which is consistent with
the development of expanded austenite merely by the disso-
lution of interstitials in existing austenite grains, rather than
by a nucleation and growth process. The rapid fading of any
features on approaching from the substrate into the ex-
panded austenite zone is attributed to the locally steep dif-
fusion profile of nitrogen (thin region with low N content).
The appearances of the layers are greatly influenced by
the applied nitriding potentials: nitriding potentials 0.294
and 2.49 yield very homogeneous featureless expanded
austenite zones. Increasing the nitriding potential leads to
a brittle appearance: cracks have developed in the near-sur-
face region (Fig. 14d). This phenomenon is especially evi-
dent for the highest nitriding potential, where whole grains
appear to have been pushed out of the surface. Notice, that
the cracks are associated with angles of approximately 558
with respect to the surface. The brittle behaviour, e. g. grain
push-out, is associated with high contents of nitrogen yield-
ing very high composition-induced stresses, a very high
yield stress and limited ductility. The visual appearance of
the samples after nitriding depends on the nitriding poten-
tial: The mirror-like finish is maintained after nitriding for
1369
F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.

(a) (b)
www.ijmr.de

(c) (d)

Fig. 14. Light optical micrographs

1
of nitrided AISI1316. Nitriding was carried
1
out in a thermobalance at 445 8C (718 K) for 22 h in NH3–H2–N2 gas
mixtures. (a) KN = 0.293 bar – 2, (b) KN = 2.49 bar – 2, (c) KN = 9.38 bar – 2 and (d) KN = 1.

low nitriding potentials (i. e. 0.294 and 2.49), but for higher Table 2. Measured zone thickness and maximum nitrogen uptake
W 2009 Carl Hanser Verlag, Munich, Germany

nitriding potentials a dark-greyish finish is produced. The for nitriding of AISI 316. The zone thickness is measured from
colour change is related to the surface roughness, associated the surface to the “interface” with the austenite. The maximum ni-
with protruding grains reducing the reflectivity. Scrutinis- trogen uptake was measured with continuous thermogravimetry.
ing the micrographs reveals a thin zone in front of the ex- Nitriding potential, Layer thickness Maximum uptake
panded austenite. This is especially evident for the nitriding 1
KN (bar – 2) (lm) (1018 · N atoms · cm – 2)
potentials 2.49, 9.38, and infinity. This thin zone corre-
sponds most likely to a low-nitrogen containing austenite 0.293 7.8 (± 0.7) 6.39
or alternatively an accumulation of carbon, which is origin- 2.490 13.5 (± 0.8) 20.30
ally present in the alloy and pushed to larger depth by the 9.380 16.3 (± 1.4) 29.80
advancing nitrogen front. The distinct junction between 1 21.7 (± 2.3) 57.20
the expanded austenite and this zone is anticipated to be
caused by a steep change in the nitrogen content. The composition–depth profiles as determined with glow
The expanded austenite zone thickness increases mark- discharge optical emission spectroscopy (GDOES) of the
edly with increasing nitriding potential for the same treat- nitrided samples depicted in Fig. 14 are presented in
ment time (Table 2). Fig. 15. Clearly, these profiles corroborate the microstruc-
Increasing the nitriding potential implies a higher nitro- tural features observed with LOM. Approaching from the
gen activity (at the surface) and therefore a higher nitrogen austenite “substrate” for all nitriding potentials a relatively
content. This consequently establishes a larger driving steep increase in nitrogen content is established after which
force for inward diffusion of nitrogen, yielding thicker the nitrogen content increases smoothly towards the sur-
layers. Evidently, a linear relationship between layer thick- face. Particularly for the higher nitriding potentials the gra-
ness and maximum uptake is not realised (Table 2). dient in the nitrogen content increases again on approaching

1370 Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10


T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.
Fig. 15. Composition–depth profiles of nitrided stainless steel AISI
316 as determined with glow discharge optical emission spectrometry
(GDOES). The corresponding micrographs are depicted in Fig. 14.
the surface. This phenomenon is explained as follows. As
was demonstrated in Section 3.3 the diffusion coefficient
of nitrogen in expanded austenite increases with nitrogen
content for yN < 0.45. Beyond this nitrogen content the ni-
trogen diffusivity decreases with nitrogen content. An im-
mediate consequence of this is an increase of the concentra-
tion gradient for yN > 0.45, which is indeed observed for the
simulated nitrogen-depth profile in Fig. 19a for KN = inf
and further discussed in Section 5. An additional effect is
expected from the occurrence of stress relaxation towards
the surface. Since the composition-induced stresses in the
expanded austenite zone can be as high as 7 – 8 GPa (see
Fig. 18a), it has been demonstrated that it is likely that such
high stress values reduce the nitrogen solubility in ex-
panded austenite [28]. The occurrence of stress relaxation
towards the surface, for example by grain push out (cf.
www.ijmr.de
Fig. 14d), would then imply that the nitrogen content is en-
hanced in the region where stress relaxation applies.
The effect of the nitriding potential is also reflected in the
hardness–depth profiles depicted in Fig. 16. Clearly, the
hardness–depth profiles show a strong difference between
the samples nitrided at different nitriding potentials. The ap-
W 2009 Carl Hanser Verlag, Munich, Germany
pearance of the profiles is somewhat similar: A smooth de-
crease near the surface followed by a sharp drop in hardness
at a position close to the transition from cN to 1
c in Fig. 16.
For a nitriding potential of KN = 2.49 bar – 2 the hardness
Fig. 16. Hardness–depth profiles of nitrided AISI 316. The corre-
sponding micrographs and composition profiles are shown in Fig. 14
(LOM) and Fig. 15 (GDOES), respectively.
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
F Feature
falls from approximately 1000 HV to 500 HV. The hard-
ness values measured directly at the surface with the same 1
load gives 1585 HV and 1417 HV for KN = 2.49 bar – 2 and
– 12
KN = 0.293 bar , respectively. Evidently, a layer of ex-
panded austenite is very hard and the transition from the
hardened case to the (soft) core occurs within a few mi-
crons.
X-ray diffraction analysis showed that the nitrogen con-
tent is significantly higher in the sample nitrided at the
highest nitriding potential (Fig. 11). Comparing the diffrac-
tograms for the nitrided samples with the untreated auste-
nite clearly shows that Bragg reflections (peaks) are shifted
to lower 2h angles. This is caused – primarily – by dissolu-
tion of nitrogen which causes a dilation of the fcc lattice
(hence the name expanded austenite), although residual
stress and stacking faults also play a role in this respect
(cf. Section 3.1). Consequently, the highest nitrogen con-
tent occurs in the sample nitrided at the highest nitriding
potential. Peaks originating from the austenitic substrate 1
are visible in the sample nitrided at KN = 0.293 bar – 2, in-
dicating that the cN zone 1is not as thick as for the sample ni-
trided at KN = 2.49 bar – 2. The broadening of the peaks for
the nitrided samples is a consequence of gradients in the ni-
trogen content, composition-induced lattice strains, and mi-
crostructural defects, i. e. stacking faults, dislocations [48].
Comparing the X-ray diffraction patterns for the nitrided
samples with the carburised sample, a higher content of in-
terstitials is realized in nitrogen expanded austenite and, ap-
parently, no gradual transition from expanded austenite to
austenite for cN as for cC; again, these observations are con-
sistent with the data in Fig. 2 and the morphological and
hardness observations discussed above.
4.3. Combining nitriding and carburising; nitrocarburising
Micrographs of nitrocarburised (cold worked) AISI 304 and
consecutively carburised and nitrided AISI 316 are depicted
in Fig. 17. The combination treatment (Fig. 17b) produces a
relatively thick layer of expanded austenite of approxi-
mately 35 – 40 lm. The layer consists actually of two sepa-
rate zones with a somewhat diffuse transition; the outer
zone is cN and the inner zone is cC. The same is clearly ob-
served for the nitrocarburised sample although the thick-
ness of the cN zone is significantly larger than the cC zone.
This can directly be attributed to the applied gas composi-
tion, i. e. the imposed nitrogen and carbon activities. The
application of unsaturated carbon gas, i. e. propene, and
NH3 allows direct control of the thermodynamics. Conse-
quently, tailoring of a combination of cN and cC may indeed
be possible, which also implies larger flexibility in tailoring
the materials properties.
4.4. Residual stress in expanded austenite
Taking into account the large unconstrained lattice expan-
sion of austenite by dissolving N or C into the fcc lattice
(cf. Fig. 2), huge compressive stresses, of the order of
GPa, can be expected if expanded austenite is constrained
by an austenite matrix underneath. An accurate determina-
tion of the residual stress profile in expanded austenite
layers by the widely applied sin2 w method [49], is a major
challenge, because the presence of both a composition gra-
dient and a residual stress gradient, combined with a varia-
1371
F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.
(a)
www.ijmr.de
(b)
Fig. 17. Reflected light optical micrographs of nitrocarburised and
carburised and subsequently nitrided stainless steel showing two dis-
tinct zones of carbon and nitrogen expanded austenite. (a) AISI 304 ni-
trocarburised in a gas atmosphere of 14 % C3H6–54 % NH3 – 22 % H2–
10 % Ar at 420 8C (693 K) for 19 h. (b) AISI 316. Carburising (2 h at
520 8C (793 K) in an atmosphere consisting of 30 % CO–70 % H2) fol-
W 2009 Carl Hanser Verlag, Munich, Germany
1
lowed by nitriding (23 h at 440 8C (713 K) at KN = 1.14 bar – 2).
tion in information depth with the tilt angle w, can lead to
seriously erroneous results [50, 51]. Special analysis and
evaluation routines should be pursued to unravel the contri-
butions of stress and composition distributions on the X-ray
diffraction line profiles and to prevent the occurrence of so-
called ghost stresses in the quantitative stress values. Such
analysis and evaluation procedures were taken into consid-
eration in the investigation of a series of nitrided and car-
burised AISI 316 samples (Fig. 18). Experimental details
of the X-ray diffraction investigations are given elsewhere
(see Ref. [52] for the nitrided samples and Ref. [47] for the
carburised samples).
Carburising was performed in gas mixtures of CO and
H2 at about 793 K (520 8C) for up to 5 h, such that the car-
bon content obtained at the surface was varied, while the
depth of the expanded austenite zone was effectively the
same for the 3 samples. Figure 18a and b present stress
and strain-free lattice parameter depth profiles. The strain-
free lattice parameter was converted to carbon content by
1372
applying the linear relation between composition and lat-
tice parameter from Fig. 2. The occurrence of slightly ne-
gative values for the carbon contents in Fig. 18b at larger
depth is caused by the imprecise values available for the
elastic constants as used on interpolation in sin2 w graphs
to determine the strain-free lattice parameter [47]. The
stress and strain-free lattice parameter profiles in Fig. 18a
and b, respectively, show clearly that a correlation exists
between the composition–depth profile and the stress–
depth profile: the larger the carbon content the higher is
the compressive stress. This observation confirms that
residual stress in the expanded austenite zone is to a large
extent composition-induced. It cannot be totally ruled out
that thermal stresses contribute, because the thermal ex-
pansion coefficient is likely to depend on composition,
too. Then, on cooling from the treatment temperature to
room temperature a thermal stress profile is superimposed
onto the composition-induced stress profile, which had de-
veloped at the treatment temperature. It is anticipated that
such a thermal stress profile has a less pronounced contri-
bution to the stress profile than the composition profile, be-
cause the change in thermal expansion coefficient of auste-
nite by dissolving carbon is expected to be relatively low.
Nitriding was performed in gas mixtures of NH3 and H2 at
718 K (445 8C) for 22 h, such that different nitrogen con-
centration profiles and expanded austenite zone were real-
ized. Figure 18c and d present the determined stress and
strain-free lattice parameter depth profiles. Also, for this
case the strain-free lattice parameters were converted to in-
terstitial atom content from the linear relation for cN in
Fig. 2. Nitrogen contents smaller than zero are a conse-
quence of inaccurate elastic constants and, in particular, to
the offset resulting from an extrapolation of the a vs. yN de-
pendence to yN = 0 (cf. Fig. 2). Comparison with the pro-
files in Fig. 18a and b shows that the nitrogen contents in-
corporated during nitriding are spectacularly higher than
the carbon contents incorporated during carburising and
that dramatic compressive residual stress values up to
– 7.5 GPa are obtained. Also, the maximum stress level
for the higher nitrogen contents does not occur at the sur-
face, but at some depth below the surface. This phenomen-
on is attributed to stress relaxation in expanded austenite.
Such stress relaxation can occur as a consequence of brittle
fracture under the influence of huge compressive stresses
and as a consequence of grain elevation (push out) from
the sample surface (cf. Fig. 14d and Section 4.2).
Clearly the absolute values of the elastic compressive
stresses reported in Fig. 18a – d are dramatically higher than
the ultimate tensile strength of stainless steel, which lies in
the range 205 – 310 MPa. The reason that biaxial stresses
of the reported magnitudes can be accommodated elasti-
cally in expanded austenite relies on a spectacular augmen-
tation of the yield strength that is associated with solid solu-
tion strengthening due to the large amount of dissolved
interstitial atoms. The reason that expanded austenite does
not spall off the austenite substrate is the absence of a sharp
interface, because the austenite lattice from the substrate
continues into expanded austenite.
Depth profiles of the strain-free lattice spacing and resi-
dual stress for a carburised and consecutively nitrided
AISI 316 sample are given in Fig. 18e and f, respectively.
The carburising + nitriding process produces a combination
of the profiles obtained by nitriding and carburising. Exam-
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
 F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.

(a) (b)

(c) (d)
www.ijmr.de
W 2009 Carl Hanser Verlag, Munich, Germany

(e) (f)

Fig. 18. (a, c) Residual stress and (b, d) strain–free lattice spacing profiles in expanded austenite obtained by carburizing (a, b) and nitriding (c, d)
of AISI 316. Interstitial contents are given as the occupancy yN or yC. Treatment conditions as given in the legends. (e) Stress–depth profiles and (f)
Strain–free lattice spacing obtained from destructive X-ray diffraction analysis. Carburising + nitriding: 30 % CO–70 % H2 for 2 h at 520 8C (793 K)
1
followed by nitriding at 440 8C (713 K) at KN = 1.14 bar – 2 for 23 h (see also micrograph in Fig. 17b). Curves denoted as carburising and nitriding in
(e, f) are identical to the data shown in (a – d) for the highest interstitial contents [47].

ining the shape of the de=0 profiles (Fig. 18e), it appears that
the overall profile is build up of two separate profiles: close
to the surface a large lattice dilation occurs comparable to
that observed after nitriding, whilst close to the substrate a
shallow lattice dilation profile is observed, reminiscent of
that obtained after carburising. The interpretation is that
carbon incorporated in the first stage of the treatment is
pushed ahead by nitrogen diffusing into the sample in the
second stage. As a result, a smooth transition from cN over
cC to c is obtained, where cC effectively bridges the mis-
match in dilation between cN and the c substrate. This is
consistent with Fig. 2 which shows that the solubility of C
ranges from yC = 0 to about yC = 0.16 and the solubility of
N in expanded austenite commences at yN = 0.17. Thus, a
continuous composition range of expanded austenite is ob-
tained with only carbon for low interstitial solubility and
only nitrogen for high interstitial solubility.
Qualitatively the residual stress–depth profile for carbur-
ized + nitrided stainless steel is a summation of the stress
profiles obtained after carburising and after nitriding.
On comparing the profiles for carburising, nitriding and
carburising + nitriding in Fig. 18f, it is evident that the

Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10 1373

F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
stress profile for the combination treatment can be patched
qualitatively from the individual profiles for nitriding and
carburising. In the surface adjacent part where cN is located,
large compressive stresses have developed, whereas in the
bottom part of the expanded austenite zone, where cC is lo-
cated, a smooth decay of the compressive stresses occurs.
At the transition from cC to cN a steep stress gradient oc-
curs, albeit over a narrower depth range than for the nitrided
Not for use in internet or intranet sites. Not for electronic distribution.
sample. This steep stress gradient is attributed to the rela-
tively steep change in composition (Fig. 18 e) and the dis-
crepancy in lattice parameter between cN and cC at
yI = 0.16 – 017 (see Fig. 2). The technological aspects of a
combination of cN and cC layers comprise an increased
load-bearing capacity due to the underlying cC layer, be-
cause the overall layer thickness is greatly improved, and a
smoother case/core transition, which is anticipated to pro-
vide more favourable fatigue properties and to prevent spal-
ling of the hard cN zone.
It is normally concurred upon that compressive stresses
impose favourable fatigue properties in surface engineering
of surfaces. In the present case unprecedented compressive
stresses in the order of several GPa’s are obtained, which
may imply an improvement of the fatigue properties of
thermochemically treated austenitic stainless steel.
Additionally, it should be evident that a combination of
nitrogen and carbon-expanded austenite, either by a combi-
nation of carburising and nitriding treatments or by a nitro-
carburising treatment, allows tailoring of the composition–
depth profile and associated residual stress–depth and hard-
ness–depth profiles. An important process parameter for
such tailoring is the carburising/nitriding potential (im-
posed gas mixture).
Finally, it should be stressed that, in particular for nitro-
gen-expanded austenite, the present results may be flawed
by invalid property data (as they have not been assessed)
of the expanded austenite. Namely, the X-ray elastic con-
www.ijmr.de
stants (XEC’s) are presently unknown for austenite with
huge quantities of interstitials [47].
5. Modelling of nitrogen diffusion profiles
Modelling of nitrogen diffusion profiles is based on a nu-
W 2009 Carl Hanser Verlag, Munich, Germany
merical finite difference method where a concentration-de-
pendent diffusion coefficient is included. Trapping, i. e. the
strong affinity between, in particular, chromium and nitro-
gen, was incorporated into the model by including the solu-
bility product (i. e. the thermodynamic equilibrium con-
stant) of a pertinent trapping reaction:
1 1
Ke ¼ n ¼ ) KT ¼ ½trap
½Nn ð1Þ
½trap
½N KT
where square brackets denote concentrations of the dis-
solved elements, trap the trapping element on the substitu-
tional lattice (typically Cr), N is interstitial nitrogen (or
other interstitially dissolved elements) and KT is the solubi-
lity product of trap and N at temperature T. For an exhaus-
tive description of the model the reader is referred to the
original literature [28].
It is assumed that the diffusion coefficient of nitrogen in
expanded austenite (AISI 316) is described by a fit through
the data in Fig. 5. For the regime yN < 0.17 an extrapolation
of data for higher N contents is assumed.
1374
The resulting nitrogen diffusion profiles for nitriding at
718 K for 22 h and surface concentrations are given in
Fig. 19a.
The surface concentrations, Cs, can be interpreted in
terms of an applied nitriding potential, provided that para-
equilibrium as prescribed by Fig. 3 exists locally between
the surface and the gas phase. Figure 19a depicts calculated
profiles for 4 different nitriding potentials and 3 values of
the equilibrium constant. The situations corresponding to
no solubility (KCr · N = 0), full solubility (KCr · N = 1) and
an intermediate solubility (KCr · N = 0.0061) with respect to
trapping are illustrated. The surface concentrations for the
calculations of the profiles in Fig. 19a were kept constant,
thus reflecting the occurrence of local (para)equilibrium at
the gas/solid interface.
The effect of varying the equilibrium constant is conspic-
uous; an infinitely high value for KCr · N, i. e. full nitrogen
solubility, yields a smooth transition of the plateau-like ni-
trogen profile into the substrate. Here, the concentration
profile is only determined by the concentration dependence
of nitrogen diffusivity. Conversely, KCr · N equal to nil has a
significant impact on the advancing front of the nitrogen
depth profiles, which is characterised by an abrupt change
in nitrogen concentration. For an intermediate value of
KCr · N an abrupt drop in concentration followed by a slowly
fading tail is observed. The abrupt drop in concentration
can be ascribed to the tendency of Cr atoms to have (at
least) one N atom as their nearest neighbour as soon as the
solubility product is exceeded (short range ordering). The
tail in front of the protruding nitrogen plateau can (pragma-
tically) be interpreted as “randomly” distributed nitrogen,
i. e. nitrogen not trapped by chromium, as long as the solu-
bility product is not exceeded. The particular shape of the
profiles for KCr · N = 0.0061 is in keeping with reflected
light optical micrographs and composition profiles of ga-
seously nitrided bulk stainless steel (see Fig. 14 and
Fig. 15). The light-optical micrographs in Fig. 14 clearly
depict a thin region between the expanded austenite zone
and the substrate; this region could correspond to the tail
on the diffusion profile (or to a carbon accumulation pushed
ahead during nitriding). The “interface” between the ex-
panded austenite zone and this thin region arises as a conse-
quence of the steep change in nitrogen concentration (and
associated change in electrochemical response to etching)
and is not an interface in the thermodynamic or crystallo-
graphic sense.
Comparing the thickness of the nitrided zone, taken as
the distance from the surface to the “interface”, in the simu-
lated profiles (Fig. 19a) and values given in Table 2 clearly
shows that the simulations provide an overestimate of the
thickness of the expanded austenite “layer”.
The kinetics of the total amount of nitrogen incorporated
in the stainless steel and associated weight increase were
calculated by integration of the nitrogen concentration pro-
files (for various times). The calculated nitrogen uptake
profiles are compared with nitrogen uptake profiles as de-
termined by thermogravimetric analysis (TGA) during ni-
triding in Fig. 19b. It is obvious that the calculated inte-
grated nitrogen uptake curves deviate strongly from the
measured nitrogen uptake curves, especially in the initial
stages of nitriding, where the uptake is grossly overesti-
mated in the calculated profiles. This discrepancy strongly
suggests that local para-equilibrium at the gas/metal inter-
Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10
 F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
Not for use in internet or intranet sites. Not for electronic distribution.

(a) (b)

(c) (d)

Fig. 19. (a) Calculated nitrogen depth profiles for nitriding at 445 8C (718 K) for 22 h and for various values of the nitriding potential and solubility
product (as indicated in the graphs). (b) Nitrogen uptake during nitriding at 445 8C (718 K) as a function of time showing calculated, experimental
(see also figures above) and fitted profiles. (c) Variable surface concentrations for the fitted profiles in Fig. 19b. (d) Nitrogen diffusion depth pro-
files calculated with a variable surface concentration from Fig. 19c for the experimental conditions as given in the1
caption of Fig. 14. Experimental
nitrogen profile (dots) was determined with EPMA for a sample nitrided at 440 8C (713 K) and KN = 1.41 bar – 2 for 23 h [28].
www.ijmr.de

face as assumed in the simulations does not apply, at least
not in an early stage of nitriding.
This prompted the approach that the surface concentra-
tion is not constant throughout the duration of the nitriding
process. By fitting the experimental thermogravimetric
W 2009 Carl Hanser Verlag, Munich, Germany
simulated profiles. In this respect it is noted that the total
amounts of nitrogen uptake for the simulated profiles are
equal to the total amounts dissolved for the experimentally
measured thermogravimetric nitrogen-uptake curves. Con-
sequently, a total nitrogen content in stainless steel ahead

curves in Fig. 19b, assuming a variable surface concentra-
tion, the variable surface concentration shown in Fig. 19c
can be obtained by reverse modelling and assuming an ex-
ponential approach towards a stationary nitrogen content
at the surface. The nitrogen depth profiles depicted in
Fig. 19d are calculated with the variable surface concentra-
tions obtained in Fig. 19c. Obviously, a more satisfactory,
albeit not perfect, agreement between experimental and cal-
culated profiles is now obtained. The extent and shape of
the Electron Probe Micro-Analysis (EPMA) profile de-
picted in Fig. 19d illustrates the validity of the calculated
profiles. Nevertheless a discrepancy persists between the
calculated and the experimental GDOES depth profiles in
Fig. 15. This can partly be attributed to the experimental
uncertainties in GDOES depth profiling as well as the val-
idity of the simplified assumptions in the model used for in-
cluding the role of surface kinetics and composition-in-
duced stress. Apparently, the width of the region of the
nitrogen profile ahead of the “interface”, i. e. where trap-
ping has not occurred, is too thick and the threshold nitro-
gen content above which trapping occurs is too high in the
of the “interface” that is too high, is compensated by a thin-
ner expanded austenite “layer”.
6. Summary and outlook
The present review on the current state of knowledge on
low temperature gaseous carburizing, nitriding, and nitro-
carburising of stainless steel illustrates that an investigation
of homogeneous expanded austenite of uniform composi-
tion (which cannot be achieved by plasma or implantation
processing) allows a consistent interpretation of function-
ally graded materials as obtained by surface engineering of
stainless steel. The dependence of the expansion of the fcc
lattice parameter on carbon and nitrogen contents and the
solubility of these elements in different composition re-
gimes, i. e. 0 < yC < 0.16 and 0.17 < yN < 0.61, provides a
consistent interpretation of the morphology of the expanded
austenite zone on carburised, nitrided, and nitrocarburised
stainless steel. Also, the occurrence of huge compressive
stresses and the occurrence of steep or smooth stress–depth
profiles in carburised, nitrided, and nitrocarburised stain-

Int. J. Mat. Res. (formerly Z. Metallkd.) 100 (2009) 10 1375

F Feature
T. L. Christiansen, M. A. J. Somers: Low-temperature gaseous surface hardening of stainless steel: the current status
less steel can directly be related to the lattice expansion of
cC and cN in different composition ranges. Concerning the
simulation of the development of the hardened case during
low-temperature gaseous surface hardening of stainless
steel, the fundamental data on the nitrogen solubility in
para-equilibrium with the gas phase and the composition
diffusion coefficient allow a straightforward calculation of
the composition–depth profile of nitrogen and its evolution.
Not for use in internet or intranet sites. Not for electronic distribution.
However, major discrepancies still occur. These are most
likely to be associated with the occurrence of the aforemen-
tioned colossal compressive residual stresses in as-grown
expanded austenite zones. The consequence of these stres-
ses is an influence on the (local) para-equilibrium between
gas and solid state and stress-assisted diffusion. Compres-
sive stresses are likely to reduce the interstitial solubility
as compared to para-equilibrium and to enhance the inter-
stitial diffusion due to the contribution of stress assisted dif-
fusion under the influence of a stress gradient. The magni-
tude and impact of these stress-related phenomena is the
topic of present and future research in our group. In this re-
spect it is expected that the interstitial system of nitrogen/
carbon expanded austenite is an ideal (i. e. extreme) model
system for unravelling the influences of composition-in-
duced stress on growth and decomposition kinetics.
Apart from this, the following aspects are currently lack-
ing and therefore should be investigated in future work.
Fundamental data on homogeneous carbon-stabilised ex-
panded austenite is scarce. This implies particularly the so-
lubility of carbon in para-equilibrium with a gas of known
composition and the determination of the composition-de-
pendent diffusion coefficient of carbon in expanded auste-
nite. On a more general level, a physically realistic thermo-
dynamic model of expanded austenite that accounts for the
difference in short-range order behaviour of nitrogen and
carbon atoms has high priority.
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The authors are grateful for financial support from the Danish Research
Council under grants 26 – 04-0240, 274 – 05-0230, 274 – 05-0367 and
274 – 07-0344. Jette Oddershede, Thomas Strabo Hummelshøj, Kris-
tian Vinter Dahl and Steffen Sonne Munch are gratefully acknowl-
edged for their contributions and fruitful collaboration.
W 2009 Carl Hanser Verlag, Munich, Germany
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(2004). Tel.: +45 45 252 250
E-mail: somers@mek.dtu.dk
Not for use in internet or intranet sites. Not for electronic distribution.

(Received June 1, 2009; accepted July 25, 2009)

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