Residual stress measurement of low

temperature plasma surface alloyed layer

using X-ray diffraction techniques
S. Thaiwatthana*1, N. Jantaping2 and P. Limthongkul2
X-ray diffraction (XRD) techniques including stress measurement were applied to untreated, low
temperature plasma nitrided and low temperature plasma carburised AISI 304 austenitic stainless
steels treated at 425uC for 12 h in H2/N2 and H2/CH4 gases respectively. Relationships between
surface microhardness and XRD peak broadening were established. The results also showed that
both surface treated layers were under a compressive residual stress. The compressive residual
stresses of the low temperature plasma nitrided and the low temperature plasma carburised
layers were 2?19 and 1?58 GPa.
Keywords: Residual stress, X-ray diffraction, Low temperature plasma nitriding, Low temperature plasma carburising, Expanded austenite, S phase

Introduction centred cubic (fcc) austenitic structure, but the peak

The application of austenitic stainless steels is restricted
by their relatively low surface hardness and hence their
limited fatigue and wear resistance. However, the intro-
duction of interstitial atoms such as nitrogen (N) and/or
carbon (C) into the surface of stainless steels can signi-
ficantly increase surface hardness, leading to improved
fatigue and wear performance. Conventional plasma
thermochemical surface engineering processes at high
temperatures (.500uC) generate the formation of hard
iron–chromium nitrides or carbides in the surface layer.
Surface modification processes carried out at low tem-
perature ranges (,500uC) can also improve the surface
mechanical properties but without the formation of
these hard compounds and thus avoiding the depletion
of chromium from the matrix. The surface alloyed layers
produced by treatment in the lower temperature range
therefore not only show improvements in wear and
fatigue resistance but also retain the high corrosion
resistance of stainless steels.1,2
The surface alloyed layers produced at low tempera-
tures appear as dense, white, precipitate free structures
and they are supersaturated with interstitial solid solu-
tion of nitrogen and/or carbon.3 They consist of a single
phase having a unique X-ray diffraction (XRD) pattern
where diffraction peak positions deviate markedly from
the expected theoretical positions of common Bravais
lattices.4 The XRD pattern is similar to that of a face
1
Surface Science and Engineering Laboratory, Materials Reliability
Research Unit, National Metal and Materials Technology Center, 114
Thailand Science Park, Paholyothin Rd., Klong 1, Klong Luang,
Pathumthani 12120, Thailand
2
XRD/XRF X-ray Techniques Laboratory, Materials Characterization
Research Unit, National Metal and Materials Technology Center, 114
Thailand Science Park, Paholyothin Rd., Klong 1, Klong Luang,
Pathumthani 12120, Thailand
*Corresponding author, email sirineet@mtec.or.th
positions are at lower diffraction angles and the reflec-
tions contain both broadening and asymmetry.5 The
crystallographic nature of this phase is open to debate
and hence has been described in a number of ways. The
designations ‘expanded/supersaturated austenite’, ‘cN’
and ‘S phase’ refer to an austenitic (fcc) crystallographic
structure, while ‘m phase’ refers to a body centred
tetragonal structure.4 A face centred tetragonal structure
is also suggested.4 The term ‘low temperature colossal
supersaturation’ has also emerged recently from the
USA.2
Although both nitrogen and carbon occupy the same
interstitial lattice positions, the supersaturation by nitro-
gen is much higher than for carbon.6 However, the
diffusion of carbon is much faster than nitrogen, result-
ing in thicker layers for the same treatment time and
temperature.6 Mechanical properties such as surface
microhardness and fatigue resistance are significantly
improved by both nitrogen and carbon surface alloyed
layers. There are small differences between the micro-
hardness levels of the nitrogen and carbon surface
alloyed layers: the nitrogen tends to give higher surface
hardness with a slightly brittle surface while the carbon
gives slightly lower surface hardness. The levels of plain
and fretting fatigue resistance are quite similar for both
surface alloyed layers.3
Surface modification processes generally increase the
case depth or hardness and may encourage a residual
stress distribution, producing the longest component life.7
Internal stress is an extrinsic property and must be
calculated via a directly measurable property such as
strain, hence the normal method of residual stress deter-
mination is to calculate stress from strain, assuming linear
elasticity,7 using XRD to measure d spacing of suitable
lattice planes in the structure under investigation.
The purpose of this study is to analyse and compare
the residual stresses in the nitrogen and carbon surface

ß 2012 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 19 August 2010; accepted 7 July 2011
DOI 10.1179/1743294411Y.0000000060 Surface Engineering 2012 VOL 28 NO 4 273
Thaiwatthana et al. Residual stress of plasma surface alloyed layer using XRD

alloyed layers produced by low temperature plasma

nitriding and low temperature plasma carburising pro-
cesses on AISI 304 austenitic stainless steels using
the same treatment time and temperature. Microlattice
strains were measured using XRD techniques and the
residual stresses were then calculated.

Experimental
AISI 304 austenitic stainless steel [Fe–18?95Cr–9?39Ni–
1?56Mn–0?68Si–0?03P–0?04S (wt-%)] disc samples, 6 mm
in thickness, were cut from 25?4 mm diameter bar sup-
plied in the hot rolled condition. The flat surfaces of the
disc samples, top and bottom, were manually ground
with silicon carbide grinding papers (120, 360, 600, 800
and 1200 respectively), then degreased with degreasing
agent, water rinsed, cleaned with acetone and dried with
hot air. The samples were divided into three groups of five
discs and marked as untreated, nitrogen (for low tem-
perature plasma nitrided) and carbon (for low tempera-
ture plasma carburised). The untreated samples were kept
for characterisation without any further treatment. The
low temperature plasma nitrided samples were put in
sample holders and treated in a 75%H2/25%N2 gaseous
atmosphere using an automatically controlled 60 kW
Klöckner DC plasma nitriding unit at 425uC for 12 h.
The plasma carburised samples were also put in the
sample holders but processed in a 98%H2/2%CH4 gas
mixture utilising a manually controlled 40 kW Klöckner
DC plasma unit at 425uC for 12 h. The half circular shape
sample holders of 6 mm in thickness AISI 304 stainless
steel with five drilled holes of 25?4 mm in diameter were
designed to position each set of five disc samples in a 1 X-ray diffraction pattern of untreated, carbon and nitro-
perpendicular position relative to the plasma unit floor in gen surface alloyed layers
order to treat both of the flat sides of the sample surfaces
and to eliminate the nitriding ring effect. Treatments were according to ASTM E1426-98 were used to determine
conducted in separate vacuum/plasma units in order to the effective elastic parameter for XRD measurements
avoid contamination of surface alloying elements. No of the residual stresses.
further mechanical polishing was performed after the Surface microhardness was measured on the surface of
treatments. both coated and uncoated AISI 304 samples using a
Phase identification, peak shift and peak broadening Vickers microhardness tester with an applied load of 10 g.
analysis were performed on both untreated and treated
samples using the focused beam XRD method on a Results and discussion
18 kW Rigaku TTRAX III X-ray diffractometer at
50 kV and 300 mA (15 kW) with a standard attach- Phase identification
ment, a copper Ka (Cu Ka) radiation (wavelength: Figure 1 shows the XRD patterns of untreated and
1?540562 Å) rotating anode and a nickel (Ni) filter. treated AISI 304. A typical set of fcc peaks of austenite
The diffraction pattern was obtained via a scanning axis phase c was obtained for the untreated AISI 304 sample.
of 2h/h with a continuous scan mode, a scan speed of Two similar patterns but with broad peaks that were
1u min21 (of 2h) and start–stop angles of 20–100u. displaced to lower Bragg (2h) angles relative to the
Residual stress measurements of the samples were also corresponding peaks for the untreated sample were
obtained using the 18 kW Rigaku TTRAX III X-ray obtained from the nitrogen and carbon alloyed surface
diffractometer operated at 50 kV and 300 mA (15 kW) layers. The structure of these layers has been variously
fitted with a stress measurement attachment (the multi- described as expanded austenite,6,8 supersaturated aus-
purpose attachment 3 for stress), a Cu Ka rotating anode tenite or S phase.9 The two sets of peaks were designated
and a Ni filter by application of the parallel beam XRD as cN and cC respectively. The degree of peak shift is
and residual stress (side inclination) methods. By this higher for nitrogen. Peak asymmetry and a decrease in
means, samples could be tilted to set y angles for the peak intensity were observed. A study by Sun et al.9
inclined measurement. The applied y angles were 0, 5 suggested that the low temperature nitrided layer has an
and 10u. Continuous scan mode measurement was used fcc structure, which is highly disordered and distorted,
with a scan speed of 1u min21 (of 2h) and start–stop due to the formation of stacking faults (confirmed later
angles of 82–96u. Strains in the crystal lattice were then by Christiansen and Somers4) with high compressive
used to calculate the surface residual stresses by assum- residual stresses in the nitrided layer. The presence of
ing bulk and a linear elastic distortion of the crystal stacking faults in fcc lattices can influence not only the
lattice.7 Elastic modulus E and Poisson’s ratio n ob- profiles (peak broadening) but also the positions (peak
tained from four point bending tests of AISI 304 sheet shift) of the XRD peaks.9 The residual stress in the

274 Surface Engineering 2012 VOL 28 NO 4

 Thaiwatthana et al. Residual stress of plasma surface alloyed layer using XRD

2 Plots of hardness (HV0?01) versus breadth and FWHM

material can also result in a peak shift for which the respectively. The peak breadth data of untreated, car-
degree of peak shift depends on the stress level s and the burised and nitrided AISI 304 are in ascending order
elastic constant S of the diffracting plane.9 Stacking (untreated,carburised,nitrided) for all reflections. There
faults in fcc lattices also lead to a decrease in the peak is a relationship between microhardness and peak half-
intensity of the XRD patterns and their effects have width [full width at half maximum (FWHM)], as FWHM
been explained with respect to deformation a and twin data of untreated, carburised and nitrided AISI 304 are
stacking fault densities b using fault induced scatter- also in ascending order (untreated,carburized,nitrided).
ing geometry in diffraction in an imperfect crystal by Plots of surface microhardness versus peak breadth and
Warren’s theory and Wagner’s method.5 FWHM measured at (222) are shown in Fig. 2.
Peak shift and broadening evaluation Residual stress calculation
As mentioned earlier in the section on ‘Phase identifica- According to Fitzpatrick et al.11 and Cullity,12 different
tion’, peak shift and broadening of untreated and crystallographic planes vary in their deformation mecha-
treated AISI 304 can be identified in the XRD patterns nisms and give different responses for both elastic
shown in Fig. 1. Line broadening data related to peak (residual stress) and inelastic strain (line broadening),
shift and broadening of untreated and treated AISI 304 thus measurements made on different crystallographic
are listed in Table 1. Breadth is expressed as the total
planes or made with different radiations are generally
area under the peak divided by diffraction peak height.
not comparable. It is suggested that the reflection with
Breadth provides information on the size (distribution)
the highest multiplicity should be selected if the sample
of diffraction domains and the content of crystalline
is textured or has a large grain size as this may reduce
defects such as dislocations and stacking faults.10 The
oscillation in the sin2 y plot.
breadth of the X-ray line often correlates with the
In this study, the highest multiplicity plane within the
hardness of the material. The surface microhardness
limit of the XRD equipment used was (222). There was no
values of untreated, carbon treated and nitrogen treated
surface alloyed layers were 200, 700 and 1200 HV0?01 further information at 2h values .100u for the treated
samples. Residual stresses can be calculated from
Table 1 Peak broadening data of untreated, carbon and measured data of lattice strain for the (222) plane at
nitrogen alloyed surface* different angles y by the XRD residual stress method and
by assuming that the errors due to instrument effects are
(hkl) (111) (200) (311) (222) eliminated. Linear plots of d222 versus sin2 y along with
linear plots of 2h versus sin2 y of nitrogen and carbon
Untreated AISI 304
2h/u 43.561 50.697 90.550 95.844 alloyed surface are presented in Figs. 3 and 4 respectively.
d spacing/nm 0.208 0.180 0.108 0.104 Slopes (Fig. 3) and stress constant (Table 2) are used in
FWHM{/u 0.231 0.373 0.631 0.546 the following equations for residual stress calculation12
Breadth/nm21 0.323 0.548 0.839 0.689
Carbon s1 ~(m=d0 )½E=(1zn) (1)
2h/u 42.654 49.270 88.036 93.542
d spacing/nm 0.212 0.185 0.111 0.106 where sø is the residual stress, m is the slope of linear plot
FWHM{/u 0.403 0.620 1.261 1.024 of (222) plane versus sin2 y, d0 is the stress free lattice
Breadth/nm21 0.519 0.833 1.671 1.338 spacing of the (222) lattice planes, E denotes Young’s
Nitrogen modulus and n denotes Poisson’s ratio. Equation (1) is
2h/u 40.262 45.755 81.328 87.011
d spacing/nm 0.224 0.198 0.118 0.112
based on the fundamental relationship between lattice
FWHM{/u 0.688 0.643 1.766 2.438 spacing and stress given in equation (2)12
Breadth/nm21 1.011 0.99 2.569 3.531
d1n ~fd0 ½1zn)=Es1 sin2 yg{
*Equipment resolution50?0001.
{FWHM is the width at half the height of the diffraction peak. ½d0 (n=E)(s11 zs22 )zd0 (2)

Surface Engineering 2012 VOL 28 NO 4 275

Thaiwatthana et al. Residual stress of plasma surface alloyed layer using XRD

3 Linear dependence of d222 upon sin2 y for carbon and nitrogen surface alloyed layers

4 Linear dependence of 2h versus sin2 y for carbon and nitrogen surface alloyed layers

where the lattice døy. is a linear function of sin2 y, d0 is
stress free lattice spacing and s11 and s22 are principal
stresses in the plane of the surface without stress acting
perpendicular to the surface.7
Finally, the residual stress levels in the nitrogen treated
and carbon treated layers were determined as 2?19 and
1?58 GPa respectively. These results are in agreement
with Sun and Chin13 whose results showed that the
carbon S phase layers are under a compressive residual
stressed condition, to a level between 1?5 and 3?5 GPa.
residual stress levels of 2?19 and 1?58 GPa on the surface
of nitrided and carburised AISI 304 respectively.
Acknowledgements
The authors are thankful for the financial support
provided by the National Metal and Materials
Technology Center, Thailand (MT-B-52-MET-07-218-
I) and the revision of the XRD experimental results and
manuscript draft by Mr Suparoek Henprserttae and Dr
John Thomas Harry Pearce.

Conclusion References
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compressive residual stresses in the surface of AISI 304
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276 Surface Engineering 2012 VOL 28 NO 4

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