ORIGINAL RESEARCH ARTICLE

Comparative Plasma Nitrocarburizing of AISI 316L

and AISI 304 Steels Using a Solid Carbon Active
Screen: Differences in the Developing
Microstructures
S.M. JAFARPOUR, S. MARTIN, C. SCHIMPF, A. DALKE, H. BIERMANN,
and A. LEINEWEBER

This paper features a direct comparison of the response of AISI 316L and AISI 304 austenitic
stainless steels to active screen plasma nitrocarburizing applied for a wide range of treatment
temperatures from 380 C to 480 C (653 K to 753 K). Thereby, an active screen made of solid
carbon was used without applying bias plasma to the treated steel samples. Since it is believed
that the result of treatment strongly depends on the concentration of in-situ generated hydrogen
cyanide, the conditions of the treatments were adapted to keep this concentration constant.
Under such treatment conditions, it was shown that AISI 316L has a lower tendency to form
CrN than AISI 304 at comparable treatment temperatures, where the threshold temperature
was found below 480 C (753 K) for the former and below 440 C (713 K) for the latter. In
addition, the decomposition of expanded austenite generated on the treated AISI 316L at high
temperatures leads to CrN and (mainly) Cr-depleted austenite phase, which is possibly
accompanied by minor amounts of a-ferrite. Instead, for the treated AISI 304, decomposition
leads to CrN and transformed a-ferrite phase. The modified layer thicknesses achieved after a
given treatment duration and the kinetics of the layer growth showed a characteristic
temperature dependence for each steel, which is discussed in accordance with the results of
microstructure analysis.

https://doi.org/10.1007/s11661-024-07351-6
 The Author(s) 2024

I. INTRODUCTION temperature and atmosphere.[1–3] However, in addition to

AUSTENITIC stainless steels are an important class
of metallic materials with a wide range of applications due
to the combination of excellent mechanical properties
along with high uniform corrosion resistance. The high
uniform corrosion resistance is achieved due to sponta-
neous formation of few nanometre-thick metal (mainly
chromium, Cr) oxide/hydroxide passive film at ambient
S. M. JAFARPOUR, A. DALKE, and H. BIERMANN are with
the Institute of Materials Engineering, Technische Universität
Bergakademie Freiberg, Gustav-Zeuner-Str. 5, 09599 Freiberg,
Germany and with the Center for Efficient High Temperature
Processes and Materials Conversion, Technische Universität
Bergakademie Freiberg, Winklerstrabe 5, 09599 Freiberg, Germany.
Contact e-mail: saeed.jafarpour@iwt.tu-freiberg.de S. MARTIN and
C. SCHIMPF are with the Institute of Materials Science, Technische
Universität Bergakademie Freiberg, Gustav-Zeuner-Str. 5, 09599
Freiberg, Germany. A. LEINEWEBER is with the Center for
Efficient High Temperature Processes and Materials Conversion,
Technische Universität Bergakademie Freiberg and with the Institute
of Materials Science, Technische Universität Bergakademie Freiberg.
Manuscript submitted November 20, 2023; accepted February 8, 2024.
their excellent intrinsic properties, many advanced engi-
neering applications require austenitic stainless steels
with high surface hardness, wear resistance, and high-cy-
cle fatigue life.[4] These improved surface properties can
be achieved by enriching the near-surface region of the
steel by interstitial nitrogen (N) and/or carbon (C) atoms
using a so-called thermochemical diffusion treatment.[5–7]
One can incorporate up to several 10 at. pct N and
somewhat lower contents of C into the austenitic stainless
steels to develop an apparently homogeneous interstitial
solid solution, the so-called expanded austenite or
S-phase. This is allowed by the high affinity of the
substitutional Cr towards N and C.[8–10] This solid
solution is, however, metastable with respect to forma-
tion of chromium nitride (CrN) or chromium carbide.
Their development binds the Cr which is then unavailable
for building up the passive film ensuring the corrosion
resistance.[8–10] In order to avoid this, the thermochemical
diffusion treatment conditions should be adapted. While
treatment at high temperatures accelerates the interstitial
diffusion of N and/or C atoms, which is necessary to
developed the expanded austenite at an acceptable treat-
ment time, high temperatures also accelerate the

METALLURGICAL AND MATERIALS TRANSACTIONS A

substitutional diffusion of Cr necessary to form the
nitrides/carbides. To avoid their unfavourable formation,
one has to remain below a steel-dependent threshold
temperature in the order of 400 C to 500 C (673 K to
773 K),[11–13] which, however, also depends on the
treatment duration and the actual treatment conditions
(resulting in a treatment environment adjacent to the
treated steel).
Combination of the active screen (AS) technology with
plasma-assisted thermochemical diffusion treatment in a
cold wall reactor is an advanced technological develop-
ment for the surface engineering of steel components
providing several advantages over conventional
plasma-assisted treatments.[14,15] It offers the generation
of a treatment environment with higher concentrations of
treatment-relevant species with enhanced activities.[16,17]
Recently an AS made of a solid carbon material such as
carbon fibre-reinforced carbon (CFC) was applied for
active screen plasma nitrocarburizing (ASPNC) by intro-
ducing N2–H2 feed gas into the reactor.[18] Here, the
required carbon-containing species for the carburizing
effect are generated in-situ by chemical sputtering of the
plasma-activated CFC-AS[19,20] which can be adjusted by
the level of plasma power applied to the AS.[17,21] In
addition, it was shown that in case of ASPNC treatments
of austenitic stainless steels with a CFC-AS, the applica-
tion of bias plasma at the treated steel is not mandatory
for the formation of a thick expanded austenite layer due
to the generation of a highly reactive treatment environ-
ment consisting of hydrogen cyanide (HCN) and ammo-
nia (NH3) with high concentrations.[17] Although the
PNC treatment of steels with AS technology has been
realized in industrial-scale reactors, the governing mech-
anisms as well as their relationships are not fully
understood. Therefore, it is of great interest to check
the fundamental behaviour of the generated modified
layer by applying ASPNC with a CFC-AS to austenitic
stainless steels with different chemical compositions as a
function of treatment temperature to make a connection
and comparison with already available results using
conventional plasma nitrocarburizing (CPNC).
In this paper, the effects of low-temperature ASPNC with
CFC-AS on two different austenitic stainless steels treated in
a wide temperature range of 380 C to 480 C (653 K to
753 K) are compared. AISI 316L and AISI 304 were chosen
as the most common representatives of the AISI 300 series
stainless steels. To this end, the present work concerns the
following aspects of low temperature ASPNC of austenitic
stainless steels: (i) investigation of the experimental condi-
tions for expanded austenite formation by ASPNC treat-
ments using two different austenitic stainless steels, (ii) the
phase stability of the formed expanded austenite as a
function of the treatment temperature, and (iii) the resulting
microstructural characteristics of the treated steels in case of
expanded austenite formation with and/or without CrN
precipitates.
II. MATERIALS AND METHODS
Commercial steel grades of AISI 316L and AISI 304
(chemical compositions are available in Table I) were
used in this work. Disc-shaped samples of 20 mm
diameter and 5 mm thickness were machined from a
cylindrical bar. All samples were ground down to 800
SiC emery paper, cleaned with ethanol in an ultrasonic
bath and dried in hot air prior to the ASPNC treat-
ments. The treatments were carried out in an indus-
trial-scale cold wall ASPNC reactor with a CFC-AS
schematically shown in Figure 1(a). For both austenitic
stainless steels, ASPNC treatments at six different
treatment temperatures under a constant treatment
duration of 5 hours have been carried out.
After inserting the samples inside the reactor, the
ASPNC treatment started by evacuating the reactor to a
base pressure of 0.8 mbar. Subsequently, the feed gas of
N2–H2 with a volumetric ratio of 1:1 (used throughout
the subsequent steps) and a total flow rate of 60
standard-litre per hour (slh) was introduced into the
reactor to maintain a total pressure of 1.6 mbar
(0.16 kPa), and the CFC-AS plasma was turned on
(Figure 1(b)) to heat up the samples to the desired
treatment temperature. After reaching a desired treat-
ment temperature, the total flow of the feed gas was
adjusted to 80 slh to increase the pressure to 3 mbar
(0.3 kPa). These treatment conditions were maintained
for 5 hours under a non-biased condition and a constant
AS plasma power for all investigated temperatures.
After the treatment was finished, the reactor was cooled
down to the opening temperature under 20 slh H2 flow
at 1.6 mbar (0.16 kPa) pressure.
During the ASPNC treatments under the described
conditions, the AS plasma power increases by increasing
the set treatment temperature.[21] Consequently, an
increase in the AS plasma power leads to the increase
in the concentrations of crucial carbon-containing
species such as HCN due to the higher chemical
sputtering rate of CFC-AS. As a result, the treatment
response of the samples was affected not only by the
treatment temperature, but also by the resulting variable
concentrations of the generated reactive species. There-
fore, in order to keep the concentrations of the
generated species at different treatment temperatures
constant, an internal heating element (Figure 1(a)) was
utilized inside the reactor below the workload to run all
the treatments at a constant AS plasma power (and
consequently constant concentrations of the generated
species).[22,23] Here, the output power (Table II) of the
heating element was selected in a way to achieve the AS
plasma power corresponding to the minimum investi-
gated temperature (380 C) which is about
4.3 ± 0.1 kW. In such a condition, the concentrations
of HCN and NH3 measured by in-situ laser absorption
spectroscopy (LAS) were estimated around
1.8 9 1015 cm3 and 1.2 9 1015 cm3 respectively.[23]
The further treatment temperatures were set by the
internal heating element.
For metallographic analysis, cross-sections of the
treated samples were mechanically polished and chem-
ically etched using a solution of Beraha II to study the
microstructure and to assess the thickness of the
modified layer using an optical light microscope (Carl
Zeiss Jena GmbH, Oberkochen, Germany) equipped
with a JVC TK C1381CCD camera. Therefore, each
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table I. Mass Fractions of Alloying Elements for AISI 316L and AISI 304 Austenitic Stainless Steels in Wt Pct (Balance-Fe)
Measured by Analytical Methods of Combustion for S and C Elements as Well as Spark Spectrometry for Other Elements

AISI C Cr Ni Si Mn P S Mo Co Cu
316L 0.029 16.9 10.3 0.28 1.72 0.028 0.029 2.19 0.20 0.29
304 0.019 18.5 8.2 0.25 1.830 0.034 0.026 0.13 0.15 0.41
The results are the average of 3 single measurements

Fig. 1—Schematic drawing of a cold wall ASPNC reactor equipped with an internal heating element (a), a photograph illustrating the formation
of plasma at the CFC-AS under non-biased condition (b).

Table II. Different Power Settings for the Internal Heating Element (PHE) at Non-biased Condition to Adjust a Constant Plasma
Power of 4.3 kW at the CFC-AS for Different Treatment Temperatures

Power Settings PHE as a Function of ASPNC Treatment Temperature

T [C] ([K]) 380 (653) 400 (673) 420 (693) 440 (713) 460 (733) 480 (753)
PHE [W] 0 80 150 230 310 405

mechanically polished cross-section was immersed into
the prepared Beraha II solution while it was slightly
moved inside the solution. As soon as a clear colour
change was observed at the cross-section, it was
removed from the solution, cleaned with ethanol and
dried in hot air. The required duration for the observa-
tion of colour change was slightly varied from sample to
sample (it was recorded between 10 and 15 seconds)
depending on its passive film and the aging. Therefore,
when the cross-sections were examined by optical light
microscope, the unaffected bulk materials appeared
slightly different in colour as a function of immersion
duration, i.e. blueish or brownish, as it is more sensitive
to Beraha II etchant than the modified layer at the
surface. Then, the total thickness of the generated
modified layer was extracted from the optical micro-
graphs, where each value of the layer thickness repre-
sents the mean of at least eight measurements taken in
different regions. An analysis of the present phases in
untreated and treated samples was performed by X-ray
diffraction (XRD) with a URD6 diffractometer (Seifert
FPM, Ahrensburg, Germany) operated at a voltage
40 kV and a current of 30 mA. For this, a conventional
h to 2h Bragg-Brentano symmetric diffraction geometry
with Co-Ka (wavelengths ka1 = 1.78897 Å, ka2 =
1.79285 Å) radiation was used. Each diffractogram
was recorded in an angular range from 20 to 150 deg
with a step-width D2h of 0.01 deg realised by a Dectris
Meteor 1D detector (DECTRIS AG, Baden, Switzer-
land). The XRD data were evaluated based on the

METALLURGICAL AND MATERIALS TRANSACTIONS A

Rietveld refinement technique using software Material
Analysis Using Diffraction[24] and TOPAS[25] to confirm
assignment of diffracted intensities to specific phases.
Due to the very complex diffraction effects because of
the anisotropic stresses and the layered structure, the
refinements could only lead to semi-quantitative results.
It has to be noted that the calculated reciprocal linear
absorption coefficient amounts to about l1 = 10 lm
for both steels (base material). Taking into account the
symmetric geometry of the (symmetric) diffraction
experiment, this leads to a diffraction-angle dependent
information depth of several lm.
The microstructure was further investigated by scan-
ning electron microscopy (SEM) on cross sections after
vibrational polishing for 24 h (Vibromet, Bühler, Lein-
felden-Echterdingen, Germany) employing a field emis-
sion gun JEOL JSM 7800F operated at 20 kV with
electron backscatter diffraction (EBSD) and energy
dispersive X-ray spectroscopy analysis (EDS) systems
(both AMETEK EDAX). Microstructure images indi-
cating the grain size and the phase distribution were
obtained by recording backscattered electron images
(BSE). The EBSD measurements were done using a
250 nm step size. For the indexing of the Kikuchi
diffraction patterns of austenite, expanded austenite,
a-ferrite/a0 -martensite the structural model of face-cen-
tred cubic (fcc) iron and body-centred cubic (bcc) iron
was used, respectively. Also, the B1 type structure of
CrN was considered as candidate structure, but no
patterns were indexed accordingly.
III. RESULTS AND DISCUSSION
A. Optical Microscopy
Optical micrographs of cross-sectioned AISI 316L
and AISI 304 samples treated at 420 C to 480 C
(693 K to 753 K) are shown in Figures 2 and 3,
respectively, revealing the modified layer at the surface
of the specimen. Micrographs pertaining to the lower
treatment temperatures are not shown due to the very
small layer thicknesses. In accordance with the previ-
ously reported action of the applied colour etchant
Beraha II,[23,26] the unstained bright layer formed near
the surface is expanded austenite. As expected, the
thickness of the expanded austenite regions increases
with increasing treatment temperature for both steels.
For some of the treated samples, the known dou-
ble-layer structure[8,10,27] with near-surface N-rich
expanded austenite, cN, and C-rich expanded austenite,
cC, underneath can be discerned from slight colour
differences in the etching (see Figures 2(a) through (c)
and 3(a)). It is believed that such a double-layer
structure exists at the surfaces of all treated samples
from both steels shown in Figures 2 and 3, even if not
discernible. See e.g.[27–29] for glow-discharge optical
emission spectroscopy (GDOES) revealing such cN/cC
double layers.
Above some steel-dependent threshold temperature,
typical dark-etched regions appeared for both steels near
to the surface, which, in accordance with similar
observations,[13] are ascribed to CrN-rich regions being
the result of decomposed expanded austenite. While in
the case of AISI 316L, such regions occurred only for
the highest applied treatment temperature of 753 K
(Figure 2(d)), in the case of AISI 304, dark-etched
regions occurred already from 713 K and above, with a
non-uniform extension which apparently increases
somewhat irregularly with temperature (Figures 3(b)
through (d)). It was noted for these treated AISI 304
samples that if the CrN-rich regions occurred in an
irregular fashion, the generated expanded austenite
layers were thicker at places where CrN-rich regions
occurred at the surface (Figures 3(b) and (d)). In
addition, the austenite substrates in both steels showed
different amounts of dark-etched features typical for
a0 -martensite. The highest amounts are visible in
Figures 3(a) and (c). The a0 -martensite is known to
develop in slip bands of metastable austenitic steels,[30,31]
particularly more pronounced for AISI 304 as compared
to AISI 316L. A certain degree of pre-deformation was
present in both steel grades. It can be speculated that the
high degree of pre-deformation evidently contained in
the AISI 304 treated at 733 K (Figure 3(c)) might have
led to the particularly pronounced and uniform forma-
tion of CrN-rich regions near to the surface. This
consequently also leads to a higher degree of thickness
uniformity as compared to Figures 3(b) and (d).
B. Scanning Electron Microscopy
The microstructure of the cross-sectioned samples
treated at 693 K and 753 K was further investigated by
SEM for both steels (Figure 4). Slight colour changes in
the IPF maps (Figures 4(a), (c), (e) and (g)) next to the
treated surface (best visible in Figure 4(a)) are an
indication for plastic deformation, which compensates
for the volume increase due to the N + C uptake,[32,33]
but also due to the 800 SiC ground surface finishing
applied prior to the treatment. Occasionally, deforma-
tion twins were observed (black arrow in Figure 4(a)),
obvious from the trace analysis and the resulting
characteristic misorientation of R3 boundaries. The
lattice curvature is additionally visible by changing
contrasts in the BSE images close to the surface (e.g.
Figures 4(b), (d) and (f)). Dislocations and dislocation
arrangements are the reason for the observed lattice
curvature. The deformation process at the surface
becomes apparent from another feature, as the typical
dislocation pattern changes after a certain depth below
the surface (~ 6 lm in Figure 4(b) and ~ 10 lm in
Figure 4(d)), which coincides with the effective diffusion
depth of N and C (c.f. Figures 2(a) and (d)), describing
the transition between the expanded austenite and the
base material (and likely corresponding to the contrast
change in the optical micrographs). As the base material
was pre-deformed in the untreated state (see section A),
a certain dislocation density i.e. deformation pattern
was pre-existing. Due to the diffusion of the interstitials
into the austenite, a chemically driven deformation
occurred.[32,33] Therefore, dislocation interactions took
place, which changed the existing dislocation arrange-
ment into the observed one. For a precise interpretation
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 2—Optical micrographs of etched (etchant Beraha II) cross sections of AISI 316L samples treated by active screen plasma nitrocarburizing
using the described conditions (see text) and the indicated temperatures, revealing the modified layers having formed at the surface of the
samples. In (a) through (c), cN and cC indicate the N-/C-expanded austenite sublayers, respectively, distinguishable from the achieved contrast.
This was not achieved in (d) where the expanded austenite is indicated by cN,C. In (d), the dark-colour regions indicate local decomposition of
the expanded austenite under the formation of CrN.

of this effect, measurements with undeformed samples
as reference material need to be conducted in future
work.
At a treatment temperature of 753 K, the CrN-rich
regions were included in the SEM analyses in the case of
the AISI 304 steel. Larger magnification SE images
(Figure 5) revealed a lamellae microstructure similar as
depicted earlier and known to typically a-ferrite and
CrN, being a result of a eutectoid decomposition
cN fi CrN + a.[34–36] The Kikuchi diffraction patterns
recorded for EBSD analysis were ascribed to the bcc
structure of a-Fe. No distinct orientation relationship
was encountered of the indexed a-Fe to the underlying
cN. The microstructure was evidently too fine to be
indexed to the CrN separately.
C. X-Ray Diffraction
X-ray diffraction patterns recorded using Co-Ka
radiation of untreated samples as well as samples
treated at different temperatures are shown in
Figure 6. The patterns of the untreated AISI 316L and
AISI 304 are typical for the original c-austenite with its
fcc-structure, including the prominent Bragg peaks at
51.2 deg (c111) and 59.8 deg (c200). In the case of the
AISI 304, there is also an additional peak at 52.2 deg

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 3—Optical micrographs of etched (etchant Beraha II) cross sections of AISI 304 samples treated by active screen plasma nitrocarburizing
using the described conditions (see text) and the indicated temperatures, revealing the modified layers having formed at the surface of the
samples. In (a), cN and cC indicate the N-/C-expanded austenite sublayers, respectively, distinguishable from the achieved contrast. This was not
achieved in (b-d) where the expanded austenite is indicated by cN,C. In (b) through (d), the dark-colour regions indicate local decomposition of
the expanded austenite under formation of CrN.

indicative for deformation-induced a¢-martensite
(a¢110).[37,38] The Rietveld fitting reveals lattice param-
eters in the order of 3.59 to 3.60 Å, whereby peak shifts
characteristic for stacking faulting obstruct perfect
description of the diffraction profiles.[39] Note that after
the treatments, the a0 -martensite disappeared since the
dissolution of N and C causes martensite to transform
to expanded austenite.[40] Generally, the modified layer
developing upon nitrocarburizing attenuates the reflec-
tions due to the austenite base material. Hence, it is no
surprise in view of the information depth of a few lm
(see section II) that the reflections become undetected in
view of the larger thicknesses of the modified layer for
the highest treatment temperatures (733 K and 753 K).
The treated samples of both steels showed similar
diffraction peaks attributable to expanded austenite,
marked with cN,C111 and cN,C200 in Figures 6(a) and
(b). Due to the expansion of the lattice, these peaks are
shifted to lower diffraction angles as compared to c111
and c200 and appeared broader.[41] By increasing the
treatment temperature, the lattice expansion became
more pronounced as evidently N and C were dissolved,
leading to shifts of the cN,C111 and cN,C200 peaks to
even lower angles (see arrows in Figure 6). Sometimes,

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 4—SEM characterization of the cross-sections of the two steels treated at 693 K and 753 K: EBSD measurements (a, c, e, g) with the same
scale bar of (a), crystallographic orientation of the austenite phase is represented in inverse pole figure colouring with respect to the vertical
ASPNC treatment direction, except the a-ferrite phase fraction, which is coloured in dark blue in (g) as marked by an arrow; Backscattered
electron contrast images (b, d, f, h) all shared the same scale bar of (b) and are depicting the samples’ surface. White areas are related to
oversaturated intensities at the edges.

contributing to the diffraction profiles. In any case, the

Fig. 5—SEM images of the cross-section of AISI 304 sample treated
at 753 K using secondary electron contrast show the lamellae
microstructure of the decomposed areas.
distinct low- and higher angle expanded austenite
reflections appear, which can tentatively be attributed
to the N- and C-rich sublayers (see, however, also[42] on
double-peaked expanded austenite in diffraction
analysis).
The CrN which was supposed to have formed within
the dark-etched regions at 753 K for AISI 316L
(Figure 3(d)) and at and above 713 K C for AISI 304
(Figures 3(b) through (d)) was confirmed to be present
according to the diffraction profiles (see in particular
isolated CrN111 peaks in Figure 6). To some extent
surprisingly, tiny CrN111 peaks were encountered in the
diffraction profiles of the samples treated at somewhat
lower temperatures (see Figure 6; e.g. 733 K for AISI
316L and 693 K for AISI 304). This may suggest that
small amounts of CrN may be present outside of the
dark-etched regions, i.e. continuously precipitated
within the expanded austenite or on the surface. Further
study is required to reveal such forms of CrN
appearance of pronounced CrN peaks attributable to
the dark-etched CrN-rich regions seems to be associ-
ated, at least for AISI 304, with a stop or reversal of the
low-angle shifting of expanded austenite peaks encoun-
tered at low temperature prior to formation of larger
amounts of CrN (see arrows in Figure 6(b)).
In case of AISI 304, the formation of CrN is
accompanied by formation of the a-ferrite phase (see
also Figure 4(g)), which is also confirmed by corre-
sponding peaks in the diffraction profiles. In case of the
AISI 316L treated at 753 K, it seems that the observed
intensity around the position of the CrN200 reflection is
too high. This may be attributed either to a strong
texture of the CrN or to small amount of a-ferrite phase.
Although the decomposition of cN is usually described
to yield Cr-depleted c phase (and which is likely the
main product accompanying the CrN formation), ther-
modynamic calculations indicated that a-ferrite phase
may well form alongside (Cr-depleted) c, but to a lesser
extent than for AISI 304.[36]
D. Layer Growth Kinetics
Utilizing PNC with CFC-AS at non-biased condition
for treatment of the austenitic stainless steels has several
potential benefits over the conventional PNC including
better control over the generation of treatment-relevant
reactive species with high concentrations,[17,28] elimina-
tion of the edge effects upon the removal of active
plasma at the treated samples and consequently forma-
tion of a thick modified surface layer, i.e. a pure

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 6—X-ray diffraction patterns (Co-Ka) of AISI 316L (a) and AISI 304 (b) in the untreated states as well as after the described active screen
plasma nitrocarburizing treatments. The peaks positions of the substrate material are indicated by vertical lines. The peaks from other phases are
indicated alongside their Miller indices. If this indication is made via a curly brace, it also refers to all higher temperatures below. Note, that the
reflections due to the expanded austenite cN,C may be split, interpreted as originating from the cN (lower angle) and cC (higher angle) sublayers.
In case of CrN, italics have been used to label peaks for the case that the optical micrographs do not show the characteristic CrN-rich regions
(see Figs. 2 and 3). The back arrows illustrate the position of the expanded austenite cN/cN,C111 as a function of treatment temperature.

expanded austenite, with high degree of uniformity is
enabled at low temperatures under a relativity short
duration (see Figures 2(a) through (c) and Figure 3(a)).
In addition, the expanded austenite layer generated by
this technique has a double-layered structure with
special arrangement where the thicknesses of cN and
cC layers are roughly comparable (see Figures 2(a)
through (c)). The increasing thickness of the generated
modified surface layer, d, with increasing treatment
temperature for both steels was already evident from
Figures 2 and 3 and noted in section A. Thereby, it has
to be noted that the typically continuous concentration
depth profiles of N/C in the solid solution we refer to as
expanded austenite, and the absence of classical phase
boundaries[8,43] make definition of the interface towards
the substrate and thus a determination of the layer
thickness somewhat arbitrary. In this work (like in many
others), the etching contrast is regarded as sufficiently
clear and reproducible to define a thickness of the total/
overall modified surface layer (expanded austen-
ite + CrN-rich regions). If diffusion is rate determining
for layer growth and if there are temperature-indepen-
dent boundary conditions with, in particular, a constant
surface concentration and semi-infinite extension of the
steel,[44] the layer thickness of a single (e.g. pure
expanded austenite) layer should evolve according to
d2 ¼ kDt,* with D being some average of the (in general)
composition-dependent diffusion coefficient, t is the
treatment time and k is a parameter, which, in partic-
ular, depends on the surface concentration of N/C. That
*This equation properly works out for a composition-independent
diffusion coefficient. In case of composition dependent diffusion coef-
ficient, the average D also changes upon changing the surface com-
position and thus k. For the present semi-quantitative considerations,
it is, however, sufficient to neglect this complication.
relation can be transformed to:
1 1 1
ln d ¼ ln k þ ln D þ ln t ½1
2 2 2
Upon varying time at constant temperature, the effect
of D should be a constant as long as the surface
concentration is time-independent (constant k). Under
such conditions Eq. [1] predicts parabolic layer growth,
i.e. @lnd=@lnt ¼ 12, which has been reported in a series of
works for growth of expanded austenite.[45–49] In the
present work, t was taken as a constant. Then, according
to Eq. [1] the layer thickness d, measurable at different

METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 7—The logarithm of the total modified layer thickness, ln(d), plotted against the reciprocal of the absolute treatment temperatures, (1000/
T), known as Arrhenius plot, resulting from nitrocarburized AISI 316L (a) and AISI 304 (b) samples at different temperatures.
temperatures, depends not only on the temperature
dependence of D, but also on the temperature depen-
dence of k. An Arrhenius-type plot of ln(d) vs 1/T as in
Figure 7 is then suitable to reveal an apparent activation
energy Q¢ according to
@ ln d 1 @ ln k 1 @ ln D 1 @ ln k Q Q connection of such kinks with CrN evolution.
¼ þ ¼  ¼ ½2
@1=T 2 @1=T 2 @1=T 2 @1=T 2R 2R
Thereby, R = 8.314 J/(mol K) and Q is the (average)
activation energy due to the (composition averaged)
diffusion coefficient. The apparent activation energy Q¢
only corresponds to Q due to diffusion if k is indepen-
dent from T.
The data for both steels as shown in Figure 7 deviate
from a single Arrhenius-type overall linear 1/T depen-
dence. In both cases, a kink in the 1/T dependent
evolution occurs, implying a lower effective activation
energy Q¢ at higher than at lower temperatures. The
threshold temperature appears to correlate with the
onset of pronounced CrN formation evident from
Figures 2 and 3 but also with the phase evolution trend
of the CrN from X-ray diffraction (see arrows in
Figure 6). The latter data show that, in particular, for
AISI 304, the diffraction angles of the expanded
austenite peaks decrease with increasing temperature,
implying an increasing surface content N(+C) with
increasing temperature. Above the threshold tempera-
ture for CrN formation there is not any more such an
increase or even there is a decrease of the surface N(+C)
content with increasing temperature. As ln(k) is
expected to increase (decrease) with increasing (decreas-
ing) temperature, this will lead to @1=T @lnk
>0 and thus
@lnk
Q¢ > Q below the threshold temperature and to @1=T <0
and thus Q¢ < Q above the threshold temperature.
Similar data on AISI 316L and AISI 304 exist already
in the literature, however, in most cases for (plasma)
nitriding or carburizing. One of the earliest works seems
to be by Sun et al.[13], who, however, evaluated slopes
corresponding ½Q¢ because they did not include the
‘‘2’’s contained in denominators in Eq. [2]. While these
METALLURGICAL AND MATERIALS TRANSACTIONS A
authors also observed kinks with smaller Q¢ values at
higher than at lower temperatures, they noticed the kink
at the same temperature for AISI 316L and for AISI
304. However, the CrN evolution starts at lower
temperatures for AISI 304 than for AISI 316L as it is
the case in the present work, speaking against a clear
Evaluation of similar data from even more
works[46,47,49–52] produces an incoherent picture and a
large variation of (apparent) activation energies from
work to work. In any case, if there is non-linearity in the
ln(d) vs 1/T type plots, higher values of Q¢ are encoun-
tered at lower temperatures than at higher temperature,
or the plots are generally concave (e.g. References 46 and
50), whereas the opposite behaviour has been encoun-
tered upon nitriding of a martensitic steel.[53]
The large variation of the temperature dependence of
the layer thickness at constant treatment time may hint
at a crucial rule of the temperature dependence of ln k in
Eq. [2], which is well understandable in view of the large
variability of the (temperature dependent) plasma com-
position and properties in different furnaces, which is
responsible for the temperature-dependent surface com-
position of the expanded austenite. It should be pointed
out that in our set of experiments, the plasma power at
the AS, which generates the active species was kept
constant and the desired treatment temperatures were
set by an additional heating element.
It should be noted that the decreased activation
energy at elevated temperature has been ascribed[13] to a
lower (effective) activation energy of diffusion of N/C in
the multi-phase microstructure developing upon CrN
formation than in the original expanded austenite.
Without explicit modelling such a view is difficult to
verify, because the CrN-rich regions form under kinetic
control. Moreover, their growth is unlikely rate-deter-
mining for the growth of the overall layer. In any case,
the effect due to the temperature dependence of ln k
should exist and hence the overall temperature depen-
dence of the achieved layer thickness upon using a
constant treatment time cannot be interpreted solely in
terms of a true activation energy for diffusion.
 Nevertheless, enhanced diffusivity through the
CrN-rich regions as proposed in Reference [13], seems
to play a role on a local scale for AISI 304; see
Figures 3(b) and (d): At places, where Cr-rich regions
have developed locally, the overall thickness of the
modified layer is larger than at other places, leading to a
generally corrugated ‘‘interface’’ of the expanded
austenite to the base material. This effect is, however,
absent for AISI 316L; see Figure 2(d). This difference
can be easily related to the pronounced development of
a in the case of decomposition of expanded austenite in
the modified layer on AISI 304 (cN fi CrN + a),
whereas only little a is developing upon decomposition
of the expanded austenite in the modified layer on AISI
316L (cN fi CrN + c, see above in sections B and C). It
is well-known that the diffusivity of interstitials in
bcc-like a-Fe is much larger than in fcc-like c-Fe,[54]
suggesting rapid N/C transport through the CrN-rich
regions in the case of AISI 304 but not in the case of
AISI 316L.** In turn, observation of the outcome of
**It is thus likely not diffusion enhanced by defects/interfaces which
might also be considered as relevant for enhanced N + C transport
through the CrN-rich regions.
this rapid transport, which must have happened at the
treatment temperature, implies that the a-ferrite being
responsible for that rapid transport existed already at
the treatment temperature and was not (only) formed
upon cooling.
It remains a question why the different compositions
of the two steels (mainly the Ni, Cr and Mo contents)
lead to different stabilities of the expanded austenite
with respect to CrN formation. Explanations put
forward in the past ascribed the differences to a special
role of the higher Mo content added to AISI 316L as
compared to AISI 304 (Table I).[47,55,56] Although the
present authors do not want to argue against these, it is
suggested here that the accelerated decomposition of the
expanded austenite in AISI 304 may alternatively/
additionally be related to the a-ferrite phase being
product of the decomposition. This phase may, once
formed, act as medium for transport of N/C but perhaps
also of substitutional elements in an autocatalytic
fashion. In any case, in Reference 34 the activation
energy for decomposition of expanded austenite had
been found to be substantially smaller for AISI 304 than
for AISI 316L, which speaks against an only gradual
effect due to a modified composition of the steels.
IV. CONCLUSION
Comparative studies of the phase states, phase trans-
formations and growth/decomposition kinetics for the
generated modified surface layers on AISI 316L and 304
treated by active screen plasma nitrocarburizing in the
temperature range of 380 C to 480 C (653 K to 753 K)
with an active screen made of solid carbon source (CFC
in this work) were conducted. It was revealed that AISI
316L has a lower tendency to form CrN as compared to
AISI 304 during ASPNC with a CFC-AS which can be
primarily related to the contents of the alloying ele-
ments. Similar to conventional plasma nitrocarburizing,
although increasing the treatment temperature is the
most effective approach to produce a thick modified
layer during ASPNC, there is an upper threshold limit of
the applied temperature to generate single phase
expanded austenite without CrN precipitates. This
threshold temperature, however, strongly depends on
the steel grade. The different microstructures of the
CrN-containing expanded austenite layers for the two
different steels were attributed to the pronounced
formation of a-ferrite phase upon CrN formation in
the case of the AISI 304 (contrasting the formation of
Cr-depleted austenite in the case of AISI 316L), which
enhances diffusion of N/C but possibly also substitu-
tional diffusion leading to formation of the CrN itself.
Some irregularity in the amount of CrN formation in
the modified surface layer on AISI 304 might be related
with a varying degree of pre-deformation of the steel
prior to treatment, which should be better controlled in
future studies.
ACKNOWLEDGMENTS
The authors appreciate the German Research Foun-
dation (DFG) for financial support under the Project
Number 506499554. Parts of this work were financed
through public funds from the Federal Ministry of
Education and Research and the State of Saxony.
FUNDING
Open Access funding enabled and organized by Pro-
jekt DEAL.
CONFLICT OF INTEREST
On behalf of all authors, the corresponding author
states that there is no conflict of interest.
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