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Joint Second Prize
LOW TEMPERATURE PLASMA NITRIDING OF
316 STAINLESS STEEL NATURE OF S PHASE
AND ITS THERMAL STABILITY
X. Y. Li
Conventional plasma nitriding of stainless steels (at stainless steel. To achieve these tasks, systematic low
temperature plasma nitriding of austenitic stainless approximately 550C) confers signicant hardening of
steel has been carried out. The structure of the S phase the treated case but at the expense of the corrosion
was systematically investigated. The thermal stability resistance. Attempts have been made in the past decade
of the low temperature plasma alloyed layers on
to achieve combined improvements in wear and cor-
stainless steel was studied employing both long term
rosion resistance of austenitic stainless steels (ASS)
isothermal annealing and TEM in situ heating
via low temperature thermochemical processes.
observations. SE/394
However, varying degrees of success have been achieved
in applications, which may be largely attributed to the
T he author is in the Surface Engineering Group, School
lack of scientic understanding of the nature of the
of Metallurgy and Materials, The University of
S phase and its thermal stability. T he present work
Birmingham, Edgbaston, Birmingham B15 2T T, UK.
concerns two aspects of low temperature plasma
Contribution to the 2000 Bodycote International Paper
nitriding of austenitic stainless steel: the study of the
Competition.
nature of the S phase and the thermal stability of the
low temperature plasma nitrided layers on austenitic 2001 IoM Communications L td.
INTRODUCTION ition is given in Table 1. Cylindrical discs, 68 mm in
Stainless steels are widely used in corrosive industrial thickness, were cut from bars of 25 mm diameter.
environments, such as the chemical, food, and o- Plasma nitriding was carried out using a 60 kW
shore industries. However, the low hardness and poor Klo cner direct current (dc) plasma unit at 570 V with
wear performance of stainless steels has limited their a current density of 30 A m2 in a 25%N
2
+75%H
2
potential tribological applications. Conventional atmosphere at 5 mbar.
plasma nitriding (at approximately 550C) has been
used for many years to modify the surface of stainless
Isothermal annealing and TEM in situ heating
steels to improve their surface hardness and tribolog-
observation
ical properties.1,2 However, the treated materials
Plasma nitrided AISI 316 specimens, heat treated at
are characterised by the precipitation of chromium
400C for 20 h and 450C for 32 h, were used for
nitrides, which confer signicant hardening of the
isothermal annealing and TEM in situ heating
treated case at the expense of corrosion resistance
observations, respectively. Before annealing, the
owing to the depletion of chromium in the matrix.3
plasma nitrided (400C/20 h) specimens were checked
Attempts have been made in the past decade to
by TEM. No precipitates within grains or at grain
achieve combined improvements in wear and cor-
boundaries were found. Two sets of annealing
rosion resistance of austenitic stainless steels (ASS)
experiments were designed to investigate the eects
via low temperature thermochemical processes.46 A
of temperature and time on the stability of the
hardened surface layer, the so-called S phase layer,
nitrogen S phase. The detailed isothermal annealing
can be produced on austenitic stainless steel without
treatment conditions are given in Table 2.
deteriorating its corrosion resistance. However, vary-
In situ heating and cooling experiments were
ing degrees of success have been achieved in appli-
performed in the TEM chamber with a purpose built
cations, which may be largely attributed to the lack
facility. The in situ heating experiments consisted of
of scientic understanding of the nature of the S phase
heating the specimen to 600C with ve successive
and its thermal stability. Clearly, this will be a barrier
temperature rises of 100C. At each temperature, the
to the wider use of the low temperature plasma
specimen was held for 40 min before it was heated to
nitrided austenitic stainless steel in many industrial
a higher temperature (Fig. 1). Microstructure and
sectors. To this end, the present work concerns two
phase changes were monitored continuously through-
aspects of low temperature plasma nitriding of
out the experiment.
austenitic stainless steel: (1) the study of the nature
of the S phase and (2) the thermal stability of the
low temperature plasma nitrided layers on austenitic
Table 1 Composition of AISI 316 austenitic stainless steel,
stainless steel.
wt-%
EXPERIMENTAL
C Cr Ni Mo Mn Fe
Materials and plasma nitriding
AISI 316 austenitic stainless steel was used in the
006 1923 1126 267 186 Bal.
present work as the substrate. The chemical compos-
147 Surface Engineering 2001 Vol. 17 No. 2 ISSN 02670844
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148 L i Low temperature plasma nitriding of 316 SS
1 TEM in situ heating parameters for 400C/20 h plasma
nitrided specimen
2 Optical microstructure of 400C/20 h plasma nitrided
specimen 200
Microstructure and property characterisation
The chemical compositions of the specimens were
analysed using glow discharge spectroscopy (GDS,
Leco GDS750 QDP). The optical metallographic
microstructures of plasma nitrided specimens were
revealed using a 25 vol.-%HNO
3
, 50 vol.-%HCl, and
25 vol.-%HO
2
etchant. XRD analysis was conducted
using a Phillips X-ray XPert diractometer with
Cu K
a
radiation. A Jeol 4000FX TEM was employed
to identify the phase composition and to study the
decomposition process of the S phase during in situ
heating observations.
The TEM specimens were prepared either parallel
to the surface (planar section) or perpendicular to
the surface (cross-section). In both cases the specimens
were mechanically thinned, dimpled, and nally ion
3 GDS nitrogen composition depth proles of plasma
beam thinned.7 The hardness and depth of the
nitrided specimen (400C/20 h)
modied layer was measured in the sectioned speci-
mens using a Leitz microhardness tester. The electro-
RESULTS
chemical behaviour of the nitrided specimens was
Characteristics of nitrogen S phase in
investigated using a dc anodically potentiodynamic
316 stainless steel
polarisation technique. The electrolyte used in the
A typical cross-sectional optical microstructure of a
test was a 35 vol.-%NaCl solution in deionised water.
400C/20 h nitrided ASS specimen is shown in Fig. 2.
It can be seen that the nitrided layer appears
unaected by the etchant used, resulting in a white
Table 2 XRD results of change in d spacing and phase
layer, which is referred to as the nitrogen S phase
response with annealing temperature and time
layer. GDS composition analysis (Fig. 3) showed that
the surface layer is heavily supersaturated with Annealing conditions
d spacing, nm Peak intensity* nitrogen (up to about 22 at.-%) as opposed to the
Temperature, Time,
maximum nitrogen solid solubility in fcc c-Fe
S
111
S
200
(CrN)
111
c a
110 C h
(87 at.-%). Figure 4 demonstrates the hardness depth
proles of plasma nitrided AISI 316 specimens. It can
400 (as nitrided) 20 02182 0194 . . . . . . . . .
be seen that the nitriding temperature signicantly
200 20 02182 0194 . . . . . . . . .
300 20 02182 0194 . . . . . . . . . aects the surface hardness. Very high microhardness
350 300 02125 0183 . . . . . . . . .
values (~1700 HK001) can be produced when ASS
350 600 0212 0183 vw . . . vw
was plasma nitrided at temperatures below 550C.
350 1200 0212 0182 w . . . w
However, the surface hardness was gradually reduced
350 1800 0212 0182 w . . . w
to 800 HK001 when the nitriding temperature was 350 3000 0121 0182 . . . . . . . . .
400 20 0214 0190 . . . . . . . . . higher than 550C.
400 60 0214 0190 . . . . . . . . .
The polarisation curves, as shown in Fig. 5,
400 100 0214 0184 vw . . . . . .
represent the corrosion resistance of the untreated
450 20 0214 0183 . . . . . . . . .
and the as plasma nitrided 316 steel for 15 h at 450C
450 40 0210 0182 vvw . . . vw
450 60 0210 0182 w . . . w and 550C. As can be seen from Fig. 5, the anodic
450 100 0210 0182 ms . . . v
curve for the untreated specimen shows passivation
500 20 0295 0182 w vw? w
at a low potential and pitting occurred at a potential
600 20 0207 0180 s vs s
of about 04 V. The 450C plasma nitrided specimen
showed similar characteristics to those observed for
* w weak; vw very weak; vvw very very weak; s strong;
ms medium strong. the untreated specimen but a much higher pitting
Surface Engineering 2001 Vol. 17 No. 2
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L i Low temperature plasma nitriding of 316 SS 149
4 Surface hardness as function of plasma nitriding
temperature for specimens plasma nitrided for 15 h at
given temperatures
6 Comparison of XRD patterns of S phase produced after
nitriding at given temperatures for 20 h
and no precipitates were found at the grain bound-
aries. A typical microstructure of the S phase is
shown in Fig. 7a, and a high density of dislocations
is also evident. The selected area diraction pattern
5 Anodic polarisation curves generated f rom untreated and
indicates that the layer has a distorted face centred
nitrided specimens in 35 vol.-%NaCl solution
cubic (fcc) structure with substantial diuse scattering
at each spot ( Fig. 7b).
potential was obtained relative to the untreated
material. In contrast, the polarisation curves obtained Annealing response of nitrogen S phase
Some changes in the microstructures of low temper- from a 550C plasma nitrided specimen exhibited
both the lowest corrosion potential and highest ature plasma nitrided specimens were observed
following annealing treatments at dierent temper- corrosion current density among all the specimens
tested, without passivation. It is clear that at low atures. Figure 8 demonstrates the morphological
evolution of the white layer formed on the nitrided temperatures (<450C) plasma nitriding can maintain
or even increase the corrosion resistance of austenitic (400C/20 h) ASS as a function of annealing temper-
ature. No metallographic etching eect was identied stainless steel, particularly the pitting corrosion
resistance in chloride solutions. for the nitrided layer after annealing at temperatures
lower than 450C. Even after longer annealing times X-ray diraction patterns of AISI 316 specimens
nitrided for 20 h at temperatures of 380500C are (400C/100 h and 350C/1200 h), the white layer
feature still remained in the cross-sectional micro- shown in Fig. 6. It can be seen that only two main
peaks, designated S1 and S2, were detected. Both S1 structure under the optical microscope ( Fig. 8a).
However, signicant changes in etching eects were and S2 peaks appeared at a much lower angle than
the corresponding c
111
and c
200
peaks. Signicant observed when the annealing temperature reached
500C (Fig. 8b). It was found that the white layer/ peak broadening was observed for all the S peaks.
The degree of broadening varied systematically with substrate interface moved inward and the outer part
of the nitrided case was sensitive to etching and nitriding temperature: increasing the process temper-
ature reduced the degree of peak broadening. The became darkened. This is a clear indication of
impaired corrosion resistance. When the annealing phases produced by low temperature plasma nitriding
of AISI 316 austenitic stainless steel cannot be temperature was increased further, the darkened layer
became thicker and the interface grew inward. matched to any of the phases given in the existing
ASTM X-ray Diraction Index Cards (see Fig. 6). Some slight changes in surface colour and morph-
ology were observed for 350C/1800 h annealed Cross-sectional TEM observations revealed that
the nitrided layer exhibits a single phase micro- specimens. It was found that the outmost surface and
nearby grain boundaries were sensitive to the etching structure for specimens nitrided at temperatures
below 450C or at 450C for less than 15 h. The same (Fig. 9a). After an annealing time of 3000 h, the dark
etched area was developed and a thin dark layer of grain size was observed as for the untreated material
Surface Engineering 2001 Vol. 17 No. 2
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150 L i Low temperature plasma nitriding of 316 SS
a
b
a
b
9 Optical microstructures of nitrided layer (400C/20 h)
7 a TEM micrograph and b typical SAD pattern of S phase
after long term annealing at 350C for a 1800 h and
taken f rom specimen nitrided at 400C for 20 h
b 3000 h showing surface decomposition
about 051 mm was observed ( Fig. 9b). It was
observed that no structural change in the S phase
layer occurred over a period of 35 years at room
temperature.
The inuence of annealing temperature and time
on the surface hardness of plasma nitrided
(400C/20 h) layers is shown in Fig. 10. For a constant
annealing time of 20 h, the surface hardness was
found to rst reduce slowly with annealing temper-
atures up to 450C, and then drop sharply. When
annealed at 450C the hardness decreased gradually
to ~1250 HK001 within 60 h and then remained
constant for longer annealing times (>60 h). For the
specimens annealed at 350C for longer times, after
a sudden drop to about 1200 HK001, the surface
hardness decreased slightly with annealing time. GDS
composition analysis revealed that the annealing
treatments alter the depth distribution of nitrogen.
Both higher annealing temperature and longer
annealing time promotes a smoother overall distri-
bution of nitrogen and increases the thickness of the
nitrided layer.8
X-ray diraction patterns obtained from the as
nitrided ( 400C/20 h) surfaces and specimens sub-
sequently annealed for 20 h at dierent temperatures
are shown in Fig. 11. It can be seen that the XRD
patterns for both the as nitrided and the low
temperature (<500C) annealed specimens exhibit S1
and S2 peaks, indicating that the S phase generated
a
b
a 450C; b 500C in the nitriding process was still present in the
annealed specimens. However, the positions of the 8 Optical micrographs of S phase layer (nitrided at 400C
for 20 h) after annealing at given temperatures for 20 h
peaks for annealed specimens shifted to higher 2h
angles than those for the as nitrided specimens. The
Surface Engineering 2001 Vol. 17 No. 2
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L i Low temperature plasma nitriding of 316 SS 151
a b c
a 15C; b 430C; c 650C
12 SAD patterns taken f rom S phase area during in situ
heating at given temperatures, showing decomposition
process of S phase: B=112
(a)
(b)
13 Isothermal transformation diagram of nitrogen S phase
10 EVect of a annealing temperature and b time on hardness
at 350500C
of S phase layer
the S phase are shown in Fig. 12. The SAD pattern
of the as nitrided specimen (Fig. 12a) exhibited typical
diuse spots, which are characteristic of the S phase
pattern. When the temperature was increased to
430C, the pattern became more diuse (Fig. 12b)
compared with that for the as nitrided specimens.
The pattern did not get any clearer until the in situ
heating temperature reached 650C, when two sets of
fcc patterns (with the same orientation) were clearly
distinguishable (Fig. 12c).
DISCUSSION
Nature of nitrogen S phase
Based on the experimental results presented above,
the nature of the S phase formed during low
temperature plasma nitriding can be deduced.
11 XRD patterns taken f rom specimens annealed for 20 h
Morphologically, cross-sectional TEM (XTEM)
at given temperatures
examination has conrmed that there is no distinct
boundary between the surface nitrided case and the
substrate. In fact, austenite grain boundaries continue extent of peak shift was found to be temperature
dependent. When annealed at 500C, the XRD from the substrate into the S phase layer, and no
signs of new grains could be identied even at a very patterns showed peak broadening. Detailed TEM
analyses revealed that this broad peak was composed high magnication. Clearly, the S phase is essentially
a diusion zone on plasma nitrided austenitic stainless of peaks for S1, CrN
200
, and a
11O
. When the annealing
temperature was increased to 600C, the XRD pattern steels without an intrinsic interface.
The S phase has been found to be drastically revealed sharp peaks for CrN, c, and a. Based on the
data collected from the XRD spectra, the detailed supersaturated with nitrogen (up to about 22 at.-%)
as opposed to the maximum solid solubility of fcc phases and d spacing values corresponding to the
annealing temperature and time were calculated (see c-Fe (87 at.-%). The presence of a high concentration
of chromium in the fcc structure has facilitated the Table 2).
To study the mechanism involved in the annealing formation of high nitrogen solubility without causing
the precipitation of any compound owing to the process of low temperature plasma nitrided austenitic
stainless steel, in situ heating TEM observations were strong CrN bond ( high negative enthalpy) and very
low diusivity of chromium ( high activation energy).8 conducted and the decomposition characteristics of
Surface Engineering 2001 Vol. 17 No. 2
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152 L i Low temperature plasma nitriding of 316 SS
Therefore, from a composition point of view, the temperatures,11 a prolonged incubation time of
several thousand hours is needed. S phase could be dened as a nitrogen supersaturated
(>87 at.-%) high chromium solid solution. This IT diagram may be used to predict the
suitability of low temperature plasma nitrided com- Structurally, nitrogen atoms are randomly distrib-
uted in the interstitial octahedral positions of fcc c-Fe ponents under specic circumstances (temperature
and time) by extrapolating the existing curve to the (CrNi ) because no diraction spots corresponding to
the superlattice plane in c-M
4
N could be identied low temperature end. Thus, the incubation times for
the S phase can be calculated based on the trendline in the majority of the S phase layer. This nding
strongly opposes the popular supposition that S phase equation when used at dierent temperatures.
Therefore, low temperature plasma nitrided AISI 316 may have a c-M
4
N-like structure.9 Thus, from a
structural viewpoint the S phase may be further stainless steel may not be recommended for use at
temperatures over 200C if desirable long term dened as expanded austenite. The incompatible peak
shifting, which is a common feature in the XRD performance for more than 10 years is required.
prole for the S phase, is most likely to have resulted
CONCLUSIONS
from the inevitable high residual stresses and the
1. Low temperature plasma nitriding of austenitic
high density of microtwins.10
stainless steel can produce an S phase layer, which
Thermodynamically, the S phase is metastable and
can result in combined improvements in the surface
will return to an equilibrium state by decomposition
hardness and corrosion resistance.
into stable precipitates, CrN and c
N
, provided the
2 The S phase formed by low temperature plasma
kinetic conditions are favourable. It has been found
nitriding of austenitic stainless steel can be dened
that the incubation time varies inversely with the
as a thermodynamically metastable, nitrogen super-
annealing temperature ranging from minutes at 500C
saturated solid solution with an distorted fcc
to years at 300C or below. In conclusion, the S phase
structure.
can be dened as a thermodynamically metastable,
3. The thermodynamically metastable S phase will
nitrogen supersaturated solid solution with an dis-
transform into the stable phases of CrN and c
N
when
torted fcc structure.
thermally annealed at certain temperatures for appro-
priate periods of time.
Isothermal transformation diagram
4. A preliminary isothermal transformation dia-
By combining the information acquired from the
gram has been developed, which provides a basic
XRD analysis, GDS nitrogen depth proling, and
design guideline for the application of low temper-
TEM observations, an isothermal transformation
ature plasma nitrided AISI 316 austenitic stainless
(IT) diagram can be constructed (Fig. 13). The
steel.
temperature chosen for the isothermal annealing
5. Low temperature plasma nitrided AISI 316
study and thus for the IT diagram ranges from 350
stainless steel is not recommended for use at temper-
to 500C. This is because, on one hand, the S phase
atures over 200C if long term performance for more
decomposes within several minutes at temperatures
than 10 years is required.
higher than 500C, and on the other hand, it will not
decompose even after thousands of hours at temper-
REFERENCES
atures lower than 350C. It can be seen that the
1. 1. nrii and x. siN: in Proc. Int. Conf. on Science and
S phase is a metastable phase and it starts to
Engineering, (ed. R.-Z. Zhu), 9; 1995, Beijing, International
Academic Publishers. precipitate stable phases of CrN and thus forms the
2. r. oiiNsxi: Surf. Eng., 1987, 3, 35.
chromium depleted austenite (c
N
) envelope when
3. z. i. zn:Nc and 1. nrii: Surf. Eng., 1985, 1, 131.
thermally annealed at certain temperatures for a long
4. x. siN, x. x. ii, and 1. nrii: Surf. Eng., 1999, 15, 49.
enough time. The incubation time is obviously
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temperature dependent from thousands of hours to
6. x. ciiin:x, . v:N nr :c1, and n. xois1r: Mater. World,
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7. x. x. ii: PhD thesis, The University of Birmingham, UK, 1999.
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8. x.-x. ii. x. siN, and 1. nrii: Z. Metallkd., 1999, 90, 901.
ature decreases, which is typical of a thermally
9. x. icnii and x. riixi:: T ech. Rep. Kansai Uni,, 1986, 27, 135.
activated or diusion controlled transformation. Since
10. x. siN, x. x. ii, and 1. nrii: J. Mater. Sci., 1999, 34, 1.
11. . xrci: and x. s1:Nsxx: Mater. Sci. Eng., 1982, A52, 1. the diusivity of chromium is very slow at low
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