Decomposition of expanded austenite in

AISI 316L stainless steel nitrided at 723K

F. A. P. Fernandes1, L. C. Casteletti1, G. E. Totten2 and J. Gallego*3
Expanded austenite (cN), which can be produced during plasma nitriding of austenitic stainless
steels, provides high levels of strength, toughness and corrosion resistance by comparison with
traditional nitride layers. However, expanded austenite properties can be lost due to
decomposition caused its thermodynamic metastability. In the present work, austenitic stainless
AISI 316L steel was plasma nitrided at 723 K for 5 h at 500 Pa and microstructurally
characterised by X-ray diffraction (XRD), and optical and transmission electron microscopy
(TEM) which confirmed the presence of fcc expanded austenite with a lattice parameter up to
9?5% larger than untreated austenite. TEM analyses of thin foils showed that fine nitrides were
formed in the cN layer and some areas were observed with a singular lamellar morphology very
similar to the pearlite colonies found in carbon steels. Selected area electron diffraction (SAED)
analysis suggests that these areas are composed of bcc ferrite and cubic chromium nitrides
produced after a localised decomposition of the expanded austenite layer. Amorphous expanded
austenite was observed in some areas of the investigated samples. The occurrence of cN
decomposition was associated with microsegregation of ferrite stabilisers (Cr, Mo) and depletion
of an austenite stabiliser (Ni) in localised regions of the expanded austenite layer.
Keywords: Austenitic stainless steel, Plasma nitriding, Expanded austenite, Decomposition, Nitride formation, Amorphous regions, Transmission electron
microscopy, EDS microanalysis

Introduction (chemical composition in Table 1). Polished surfaces for

AISI 316L austenitic stainless steel provides excellent
corrosion resistance due to higher amounts of chro-
mium, nickel and molybdenum combined with lower
carbon content. However, its hardness and wear
resistance are relatively poor, limiting some applications.
Low temperature nitriding can improve both hardness
and wear resistance with the formation of expanded
austenite (cN)1–5 which has higher strength, toughness
and corrosion resistance compared to the traditional
nitride white layers. However, expanded austenite layer
properties are negatively affected by decomposition
resulting from thermodynamic metastability.6,7 The
aim of the present work is to investigate microstructural
changes in expanded austenite produced by nitriding at
723 K.
Experimental procedure
Discs of approximately 3 mm thickness were machined
from a commercial round AISI 316L stainless steel bar
1
Department of Materials Engineering, São Carlos School of Engineering,
University of São Paulo, São Paulo, SP, Brazil
2
Department of Mechanical and Materials Engineering, Portland State
University, Portland, OR, USA
3
Department of Mechanical Engineering, Univ Estadual Paulista – UNESP
at Ilha Solteira, Ilha Solteira, SP, Brazil
*Corresponding author, email gallego@dem.feis.unesp.br
nitriding were prepared after wet grinding with sandpa-
per (up to 1500 grit) and final mechanical polishing with
1?0 mm alumina. Sputtering in a 500 Pa argon atmo-
sphere for 0?5 h at 673 K was followed by direct current
plasma nitriding at 723 K for 5 h at the same pressure.
The nitriding atmosphere was composed of 80 vol.-%H2
and 20 vol.-%N2.
Small pieces were cut from the nitrided layers for
preparation of conventional cross-sectional metallo-
graphic samples, which were examined using a Zeiss
Axiotech optical microscope. After bakelite mounting
and the preparation described above, the samples were
etched in a fresh solution containing 75 mL hydro-
chloric acid and 25 mL nitric acid.
The phase constituents in the substrate and plasma
nitrided layer were analyzed using a Rigaku Geirgerflex
difractometer (Bragg-Brentano configuration) at Cu Ka1
radiation (154?05 pm) and a graphite monochrome
device. The diffracted intensity was recorded between
30u and 100u, at a sweep speed of 2u min21. X-ray
diffraction (XRD) patterns were compared with crystal-
lographic information files available from the Inorganic
Crystal Structure Database.8
A plan-view section of the nitrided layer, where the
treated surface of the thin foil is normal to incident
electron beam, was inspected by transmission electron
microscopy (TEM). The substrate side of nitrided
samples was carefully ground to 150 mm when 3?0 mm

ß 2012 IHTSE Partnership

Published by Maney on behalf of the Partnership
DOI 10.1179/1749514812Z.00000000025 International Heat Treatment and Surface Engineering 2012 VOL 6 NO 3 103
Fernandes et al. Decomposition of expanded austenite at 723K

1 a optical cross-section of plasma nitrided AISI 316L at 723 K showing 15 mm thick homogeneous expanded austenite layer
and b XRD patterns of substrate and nitrided layer

Table 1 Chemical composition (wt-%) of AISI 316L stainless electron beam was adjusted to give a detecting dead time
steel between 30 and 40%. Crystallographic parameters were
determined from selected area electron diffraction
C Mn Si Cr Ni Mo N Cu Fe patterns (SAEDs), using a standard calibrated camera
length.
0.019 1.47 0.40 16.26 10.50 2.02 0.067 0.47 Bal.

Results and discussion

Table 2 Lattice expansion D calculated for each
reflection of XRD results The microstructure of the AISI 316L sample was
composed of equiaxed austenitic grains with 40 mm
cN Lattice average size and typical annealing twins, as shown in
reflection 2h angle/u parameter/Å D expansion/% Fig. 1a. Optical microscopy indicates that plasma
{111} 41.2 3.79 5.3 nitriding at 723 K results in a homogenous and
{200} 46.0 3.94 9.5 uniform layer without significant nitride formation.
{311} 83.4 3.84 6.7 Small, but perceptible, changes in layer thickness were
noted, probably due to anisotropic nitrogen diffusion
diameter discs were punched with an appropriate device. into austenite grains with different crystallographic
A transparent thick lacquer protective layer was applied orientations.
to the nitrided surface to prevent degradation during The XRD patterns obtained from untreated and
TEM sample preparation. Thin foils were obtained by nitrided AISI 316L steel are shown in Fig. 1b. The
jet electropolishing of one side where a 5 vol.-% substrate presents diffraction peaks at 43?7u, 50?8u,
perchloric acid–95 vol.-% acetic acid solution (by 74?7u, 90?7u and 95?9u 2h scattering angles, which are
volume) at room temperature was used with a polishing consistent respectively with {111}, {200}, {220}, {311}
potential/current of 40 V/40 mA respectively. The TEM and {222} reflections of c austenite. Small intensity of
observations were performed using a Philips CM120 {220}c reflection was attributed to texturing by rolling.
microscope operated at 120 kV (l53?35 pm) and After plasma treatment at 723 K some of these c
equipped with an energy dispersive X-ray spectroscopy reflections, such as {111} and {200}, were observed
(EDS) microanalysis device. EDS counting was per- with low relative intensity, while others reflections are
formed during 100 s live time where the spot size of the not well defined. Diffraction peaks were observed at

a selected spots near (002); b selected spots near (131)

2 Dark field TEM images showing two sets of stacking faults bundles in same area of cN thin foil sample

104 International Heat Treatment and Surface Engineering 2012 VOL 6 NO 3

 Fernandes et al. Decomposition of expanded austenite at 723K

3 Thin foil TEM images showing a fine chromium nitride precipitation and b amorphous region (A) near decomposed cN
area (D)

41?2u, 46?0u and 83?4u 2h scattering angles after nitriding
at 723 K respectively associated with {111}cN, {200}cN
and {311}cN expanded austenite reflections. The results
in Table 2 confirm the increase in the cN lattice
parameter and its anomalous behaviour relating to
untreated fcc austenite (ao5359?11 pm) due to aniso-
tropic expansion.1
Atomic nitrogen in solid solution occupies an
octahedral interstitial site in the fcc lattice of austenite.
Its presence promotes a decrease in stacking fault
energy. Therefore, higher stacking fault densities and
compressive residual stresses can be expected in the
expanded austenite. The presence of planar defects and
their elastic strain fields have resulted in different shifts
for each cN reflection in the XRD pattern, according to
Warren’s theory.9 Thin foil observations made by TEM
have confirmed a massive formation of stacking faults in
the expanded austenite layer as shown in Fig. 2.
Calculations performed from the SAED patterns indi-
cate that lattice expansion of cN is slightly higher (14%)

4 a TEM image showing regions of expanded austenite (P1) and cN decomposition (P2), and b, c EDS microanalysis
spectra of P1 and P2 positions

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Fernandes et al. Decomposition of expanded austenite at 723K
than those obtained by XRD analysis which is due to the
lower level of compressive residual stress in thin foil
samples.10,11
The TEM investigation showed the microstructure of
the expanded austenite layer to be complex. In some
regions, as shown in Fig. 3a, small rounded particles
(10–15 nm) were readily observable in the thin foils
observed under dark field contrast. The ring type SAED
pattern indicates that there is a larger number of
diffracting particles with some preferential orientation
(texture) related to the substrate (not investigated).
Indexing diffracted rings have shown that these particles
are crystalline and compatible with cubic chromium
nitride (CrN) whose volume fraction is considerably
smaller than the detection limit of the XRD technique.
Amorphous expanded austenite was also observed in
scattered regions of the nitrided layer, as shown in
Fig. 3b. This kind of structure presents typically an
image with monotone contrast and this is crystal-
lographically confirmed by the presence of broad and
diffuse halos in a ring type SAED pattern. The localised
loss of crystallinity can be attributed to the effect of
nitrogen implantation combined with the low diffusivity
of substitutional elements such as chromium.12
Some regions of the expanded austenite layer pre-
sented a peculiar lamellar microconstituent as shown in
Figs. 3b and 4a. SAED analyses showed that the
lamellar regions were composed of bcc ferrite and cubic
CrN. Formation of the aggregate can be considered a
result of expanded austenite decomposition,11,13 con-
sidered harmful to both wear and corrosion resistance of
the nitrided layer. EDS microanalyses confirm that
chemical composition of regions with and without
decomposition are significantly different, as shown in
Table 3. Regions of normal expanded austenite cN as P1
in Fig. 4a usually have lower chromium and molybde-
num content (both bcc ferrite a-iron stabilisers) and
higher nickel (a fcc austenite c-iron stabiliser).14
Nevertheless, decomposed cN regions such as P2,
contain a very high concentration of a stabilisers and
Table 3 Typical range of chemical composition (wt-%)
obtained by EDS from different regions of expanded
austenite cN layer in AISI 316L nitrided steel
cN Cr/wt-% Ni/wt-% Mo/wt-%
normal 18.1–24.3 9.7–16.1 0.5–3.0
decomposed 41.5–53.7 3.7–5.8 3.0–5.9
106 International Heat Treatment and Surface Engineering
lower c stabiliser. This chemical behaviour is probably
related to microsegregation events, which may have
occurred during manufacture of the rolled bar used
as substrate, or during nitriding treatment of the
specimens.
Summary
The investigation of nitrided AISI 316L samples indi-
cates that fine chromium nitride cannot be identified by
XRD analysis, due to its low volume fraction, but can be
identified by TEM. Other evidence of expanded auste-
nite decomposition was found on the nitrided surface.
Scattered regions of the expanded austenite layer were
amorphous. The formation of these decomposed areas is
related to enrichment in both chromium and molybde-
num (ferrite stabilisers) and to depletion of nickel
(austenite stabiliser) from of the expanded austenite.
Acknowledgements
The authors would like to thank Brazilian research
agencies CNPq (LCC and JG) and CAPES (FAPF) for
grants received which supported this work.
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