Surface and Coatings Technology 165 (2003) 107–118

Characterisation of PI3 and RF plasma nitrided austenitic stainless steels

using plan and cross-sectional TEM techniques
D.R.G. Mitchell*, D.J. Attard, G.A. Collins, K.T. Short
Materials Division, ANSTO, PMB 1, New Illawarra Road, Menai, NSW 2234, Australia

Received 3 December 2001; accepted in revised form 27 September 2002

Abstract

Type 304 and 316 austenitic stainless steels treated with plasma immersion ion implantation (PI3 娃) and RF plasma nitriding
have been studied with transmission electron microscopy (TEM). A range of TEM specimen preparation techniques have been
used to enable characterisation of the nature of the treated surface layers. Plan view TEM specimens, prepared by thinning from
the back, highlighted the removal by sputtering of original surface features in steels during PI3 processing, while the less energetic
RF plasma nitriding retained the original surface features. All treatments resulted in the formation of an austenite phase heavily
expanded by the high levels of interstitial nitrogen. Decomposition of this expanded austenite into CrN and a Fe occurred at
higher treatment temperatures, and was found to nucleate at the grain boundaries preferentially. Conventional cross-sectional TEM
specimens also showed the importance of the surface as a nucleation site for this transformation. The transformation process and
the products of expanded austenite decomposition were the same regardless of the treatment process used. The expanded austenite
layer was aligned with the underlying steel, with no orientational difference across the interface observed. Focused ion beam
milling has the ability to consistently section treatment depths of several micrometers, although further work is necessary to
produce through-section specimens thin enough for EELS and EFTEM analysis.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Transmission electron microscopy; Plasma nitriding; Plasma immersion ion implantation; Austenitic stainless steel

1. Introduction structure w2–6x, sometimes describing it as expanded

In recent years, there has been a growing interest in
the nitriding of austenitic stainless steels at temperatures
below 450 8C for application in areas such as food
processing, chemical engineering, aerospace and biom-
aterials which cannot tolerate the loss of corrosion
resistance that occurs following nitriding at higher tem-
peratures. In this lower temperature range, a metastable
phase is produced in which the nitrogen remains in solid
solution, instead of removing Cr from the austenitic
structure by precipitation of CrN. This metastable phase,
named S-phase by Ichii et al. w1x, has been the subject
of intense scientific study, not only because of its
excellent wear and corrosion resistance, but because its
exact nature is not yet known. While the majority of
workers believe it to have a supersaturated fcc or fct
*Corresponding author. Tel.: q61-2-9717-3456; fax: q61-2-9543-
7179.
E-mail address: drm@ansto.gov.au (D.R.G. Mitchell).
austenite because its X-ray diffraction (XRD) patterns
show peaks shifted to lower Bragg angles than those for
austenite, it has also been associated with a bct structure
w7,8x.
Even more intriguing is that there seems to be no
restriction as to the surface engineering processes that
may be employed for its formation. Ion implantation at
elevated temperatures (350–400 8C) using both conven-
tional accelerators w9x and high-dose, high flux ion
thruster technology w10x has produced this phase. Plasma
immersion ion implantation (PI3 娃), which involves both
the implantation and diffusion of nitrogen, seems to
particularly favour its production in the temperature
range 300–450 8C w11–14x. Even reactive sputtering in
Ar–N2 mixtures has produced stainless steel coatings in
which the phase can be identified w4,15x.
As part of an ongoing program of development of the
PI3 process, extensive characterisation of various treated
austenitic stainless steels has been performed, using

0257-8972/03/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 2 . 0 0 7 4 1 - 7
108 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
techniques such as scanning electron microscopy and
secondary ion mass spectrometry (SIMS) w16x, hardness
w17x and wear and corrosion testing w12x. However, to
understand the detailed composition and structure of
these expanded austenite layers we have also applied a
range of transmission electron microscopy techniques to
this system. The major difficulty has been the prepara-
tion of appropriate specimens, since the treated layers
are many micrometers thick and are of course metallic.
Fig. 1.
This paper describes the types of specimen prepara-
tion techniques we have used, and the insights into the
nature of the plasma nitrided layers which have resulted
from transmission electron microscopy (TEM)
investigations.
2. Experimental
Steel disks f2.5 cm diameter and f3 mm thick,
were cut from bar stock and then ground and polished
to a 1-mm diamond finish. These were processed using
the PI3 facilities at ANSTO. RF plasma nitriding was
carried out in the same apparatus but without any
substrate negative pulse biasing applied. Treatment times
and temperatures were varied and are indicated in the
text. Specimens were examined using JEOL 2000FXII
and 2010F TEMs, the latter being fitted with a Gatan
imaging filter (GIF). Specimens were prepared using a
range of techniques as follows.
2.1. Plan view specimens
The specimen processing route is shown schematically
in Fig. 1a. A foil f250 mm thick was cut parallel to
the treated surface, using a slow speed diamond bladed
saw. The treated surface of the foil was then affixed to
a grinding stub with thermal wax, and mechanically
ground to a thickness of f100 mm. The foil was then
removed and TEM disks 3 mm in diameter were
punched from it. Protective mica windows were prepared
by repeatedly cleaving mica to produce wafers as thin
(and light transparent) as possible. Using a TEM punch
3 mm disks were then punched from these wafers.
Lacquer was diluted with the solvent, and a minute drop
applied to the mica window in order to adhere it to the
treated surface of the TEM disk. The purpose of the
mica window was to protect the treated side of the steel
from the electrolyte during electropolishing. This tech-
Fig. 1. Schematic diagram showing the processing route for: (a) Prep-
aration of plan view specimens using electropolishing; (i) wafers are
cut parallel to the treated surface; (ii) these are ground to f100 mm
and disks punched from them; (iii) the treated surface is protected by
attaching a mica window; (iv, v) the specimen is single sided jet
polished from the rear of the treated surface. (b) Preparation of cross-
sectional specimens using the conventional PIPS-based process; (i)
wafers are cut and the treated surfaces are butted together to allow
spark cutting of a core; (ii) this core is glued into a brass tube and
(iii) wafers are cut from it; (iv) wafers are ground, dimpled and then
ion milled (PIPS) to electron transparency. (c) Preparation of cross-
sectional specimens using a focused ion beam mill (FIB); (i) wafers
are cut parallel to the treated surface and abutted; (ii) these are pre-
cision ground to f20 mm thickness; (iii) one wafer from (ii) is
mounted on a halved copper slot grid, with the treated surface over-
hanging the slot; (iv) a gallium ion beam perpendicular to the treated
surface mills out two blocks of material to leave a thin membrane
between them which forms the TEM specimen.
 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
nique has the advantage over simply using a coating of
lacquer, since when used alone, the lacquer must be
quite thick to ensure no pinholes are present, and its
light transparency then suffers. Using the mica window
gives excellent sensitivity to the point of breakthrough
during electropolishing, which is sensed with a light
transmission detector. Jet electropolishing was per-
formed on a Struers Tenupol 3 device, using a 10%
perchloric acidy90% acetic acid solution at room tem-
perature, with a polishing current of 30 mA.
Cross-sectional TEM specimens were prepared using
several different techniques.
2.2. Conventional TEM cross-sectioning
The specimen processing route is shown schematically
in Fig. 1b. Wafers approximately1.5 mm wide were cut
from the disk, and the treated surfaces were clamped
together as shown in Fig. 1b. Cores were then spark
eroded from the interface, using a 3.05 mm i.d. brass
tube as the cutting tool. The cores were ultrasonically
cleaned in acetone before being glued into a 3.05 mm
i.d. brass tube using high strength epoxy resin. Once
cured, a thin bladed, slow speed diamond saw was used
to wafer specimens approximately 300 mm thick. These
were mounted on stubs and ground to f80 mm, using
successively finer grades of SiC paper. One side of the
specimen was polished to a 0.5 mm diamond finish. The
other side was dimpled using a Gatan dimpler (model
656) with cubic boron nitride abrasive, to leave a final
thickness of f20 mm. Thinning to electron transparency
was achieved using a Gatan precision ion polishing
system (PIPS娃). Polishing conditions used were: 5-keV
Arq ions, 68 initial thinning angle, 48 final angle with
polishing in sector control mode, so that ion milling
only occurred from the rear of the surfaces of interest.
2.3. Tripod polishing
Tripod polishing is a precision mechanical grinding
technique which can be used for producing electron
transparent foils directly, without the need for ion mill-
ing. In the present work, foils tended to break up, once
they approached electron transparency, presumably due
to high residual stress levels. Tripod polishing was
therefore used only as a replacement for dimpling, prior
to ion beam milling with the PIPS.
2.4. Focused ion beam milling (FIB)
The specimen processing route is shown schematically
in Fig. 1c. Cross-sectional wafers approximately 1.5=2
mm were prepared as shown, and two were glued to a
grinding stub with the treated surfaces butted against
each other. The material was carefully ground and
polished to minimise edge rounding and burring. The
109
Fig. 2. Secondary electron image of a specimen near the final stages
of milling (in situ image from the FIB). The view is perpendicular to
the treated surface.
wafers were then flipped over, and ground and polished
in a similar manner to a final thickness of f20 mm.
One wafer was then glued to a halved copper slot grid
as shown in Fig. 1c. This was then placed in a FEI
200=P FIB system, with the treated surface uppermost.
Using 30-keV Gaq ions two adjacent square blocks
(10=10 mm) were milled out of the treated surface, to
leave a thin membrane which formed the TEM speci-
men. A plan view (perpendicular to the treated surface)
of the near-finished FIB specimen is shown in Fig. 2.
3. Results
3.1. Plan view specimens
These specimens enabled the treated surface to be
examined with the electron beam perpendicular to the
treated surface. Since TEM is a projection technique,
only the top f100 nm of the treated surface could be
satisfactorily examined, since at greater specimen thick-
nesses, inelastic scattering begins to dominate, and
imaging and analysis becomes increasingly difficult.
One possible concern with jet electropolishing is that
back thinning along the original surface can occur. This
happens where localised breakthrough of the anodic
dissolution process of jet electropolishing, does not trip
the optical auto-stop detector on the Tenupol apparatus
sufficiently early. Instead, localised corrosion runs up
the interface between the lacquer and the surface mate-
rial, removing some of the surface of interest. The
presence of a thick and relatively opaque layer of lacquer
can exacerbate this problem. However, the mica window
technique used here permits excellent light transparency,
and therefore excellent sensitivity to the point at which
110 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
Fig. 3. TEM plan view of the untreated foil (jet electropolished).
Scratches and residual surface damage are present from the original
metallographic preparation of the bulk disk.
the foil first perforates is obtained. It is at the point of
first breakthrough that the area of electron transparent
foil is at a maximum. Fig. 3 shows a plan view of the
near-surface region of the untreated steel. The presence
of scratches and mechanical polishing damage, from the
preparation of the bulk disk specimens, shows that loss
of the surface of interest has not occurred. This is of
critical importance when examining transformed
expanded austenite (see later), which has very poor
corrosion resistance compared with the expanded aus-
tenite. The inset diffraction pattern (Fig. 3) was obtained
by tilting away from a strong zone axis, and showed
spacings typical of this type of stainless steel.
RF plasma nitrided steel (316 stainless steel, 400 8C,
3 h) (Fig. 4) showed similar features in plan view to
those of the as-received steel. Metallographic cross-
sectional characterisation (not shown) indicated an
expanded austenite layer depth of f1.5 mm. As well as
the surface scratches and dislocation stemming from
metallographic preparation, (Fig. 4a), extensive twin-
ning was also observed (Fig. 4b). Extensive surface
deformation is a consequence of this treatment, with
grain structure and twinning topography evident on
treated surfaces (which were previously smooth), where
relaxation of the compressive stress from treatment
occurs. Also apparent were regions where the expanded
austenite had begun to decompose (Fig. 4c). In these
regions dendritic growths of decomposition product
could be seen emanating from a grain boundary,
although nucleation of this decomposition product was
also noted within some grains (not shown). Selected
area diffraction patterns (SADPs) from regions contain-
ing significant amounts of this decomposition product,
such as that shown in Fig. 4c, indicated a strong ring
pattern superimposed on a weak spot pattern from the
expanded austenite phase (Fig. 4d left). This pattern
indicated CrN and a Fe to be the decomposition
products of expanded austenite. Within a single austenite
grain apparently containing little such decomposition
product, a single crystal pattern was obtained (Fig. 4d
right) and which also showed very weak diffraction
rings. The single crystal pattern was due to expanded
austenite with an expansion of 3.5%, while the weak
rings were due to CrN and a. This showed that nucle-
ation of the decomposition product was also taking place
within grains.
Plan view examination of a PI3 treated steel (316
stainless steel, 420 8C, 5 h) showed that much of the
surface preparation damage had been removed as a
consequence of treatment (Fig. 5a). Metallographic
cross-sectional characterisation (not shown) indicated
an expanded austenite depth of f7 mm. Very extensive
decomposition of the expanded austenite layer had
occurred, with many, but not all, grain boundaries
decorated with the decomposition product. Although
nucleation at the grain boundaries dominated, there was
also evidence for nucleation within grains. Detailed
examination of the decomposition product (Fig. 5b)
showed its dendritic nature. The dendrites were com-
prised of clusters of lamellae, with interlamellar spacings
of f5 nm. Electron diffraction of the various phases
(not shown) showed them to be identical to the respec-
tive phases encountered in the RF plasma nitrided steel.
The lattice expansion measured for the PI3 produced
expanded austenite was 2%. Scoring and sub-surface
dislocation stemming from the original metallographic
preparation prior to plasma treatment was noticeably
absent, compared with the RF plasma nitrided steel (Fig.
4a).
Energy dispersive analysis of X-rays (EDX), which
could not detect nitrogen, indicated an expanded austen-
ite composition identical to that of the untreated steel.
Regions which had transformed to CrNya were quite
chromium-rich (f40 wt.%), even though the surround-
ing untransformed regions showed no compositional
change. This was most likely due to selective dissolution
of the Fe-rich a phase by the electropolishing solution.
Overall, the decomposition product was very similar in
appearance and structure to that observed in the RF
plasma nitrided steel.
3.2. Cross-sectional specimens
3.2.1. PIPS
Conventional cross-sectioning using ion milling in a
PIPS can produce excellent results with ceramic mate-
rials. However, for metallic materials containing layers
or structures more than a few micrometers below a
surface, the technique becomes very challenging. Fig.
6a shows a cross-section of a RF plasma nitrided steel
(shown earlier in plan view in Fig. 4a–d), with a f1.5
 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118 111

Fig. 4. TEM plan view of the RF plasma nitrided steel: (a) Extensive scratching and near surface dislocation from the original metallographic
preparation is apparent. (b) Large-scale twinning is present, to a much greater degree that the as-prepared steel, as a consequence of relaxation
of compressive stress. (c) Region of a grain boundary where a dendritic CrN and a Fe decomposition product has grown outwards from the grain
boundary. (d) SADPs from: (left) region shown in (c), showing the rings from the CrNya Fe product superimposed on the expanded austenite
spots; (right): region of expanded austenite shown in (a). The single spot pattern due to expanded austenite has very weak CrNya Fe rings
superimposed.

mm expanded austenite layer at the surface. The speci-
men shows the interface between the expanded austenite
and underlying steel to be clearly delineated by the
dislocation contrast. The expanded austenite layer has a
very high density of line and point defects, while the
underlying steel has a lower density of mainly line
defects. Our experience with ion milling of other metal-
lic materials shows that very extensive ion damage
occurs in such foils. Therefore, some of the dislocation
contrast seen is almost certainly due to ion milling
effects. Also apparent is the increasing thickness of the
foil on moving away from the surface. Below approxi-
mately 3 mm from the surface, the foil becomes too
thick to do useful imaging. This specimen represents
one of the better foils produced, and it is apparent from
this that cross-sectioning metallic materials with treat-
ment depths greater than a few micrometers is likely to
be quite difficult with this technique.
In order to see the interface, it is necessary to produce
appropriate, strong, two-beam diffraction conditions to
highlight dislocation structures. In the absence of these
conditions, the interface can be very hard to locate
owing to the absence of a crystallographically discrete
boundary (see later). In the RF plasma nitrided material
a surface layer f50 nm wide was located, and the
bright fieldydark field pair (Fig. 6b) shows a detail of
it. Diffraction (Fig. 6b inset) showed that this was a
layer of CrNya decomposition product, and that nucle-
ation had occurred at the surface.
Characterisation of the orientation relationship across
the expanded austeniteyaustenite interface was possible
with cross-sectional specimens. The absence of interfa-
cial contrast, except under appropriate two beam dif-
fraction conditions, indicated that the interface was not
a discrete boundary, such as a high angle grain boundary.
Fig. 7a and b are taken from the expanded austenite
112 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118

The diffraction patterns shown in Fig. 7 do not illustrate

this particularly clearly, since the underlying steel was
very much thicker that the expanded layer due to the
wedge-shaped profile of the foil (see Fig. 6a).
In the case of the PI3 steel (shown in plan view in
Fig. 5a,b) the degree of transformation appeared to be
far more extensive (Fig. 8a) than that in the RF plasma
nitrided steel (Fig. 6a,b). The PI3 treatment was carried
out at a slightly higher temperature (420 vs. 400 8C),
and for a longer time (5 h vs. 3 h). The growth pattern
of the dendritic decomposition product showed that
nucleation occurred at the surface, followed by inward
growth at up to 1 mm into the expanded austenite layer,
which in this case was f7 mm thick. Surface regions
which had transformed to CrNya were considerably

Fig. 5. TEM plan view of PI3 steel: (a) While much of the surface
damage from metallographic preparation appears to have been
removed, very extensive decomposition of the expanded austenite has
occurred, with many grain boundaries decorated with the CrNya.
Some nucleation within grains has taken place also. (b) Detail of (a)
showing the dendritic growth of the CrNya Fe product and its lamellar
structure.

layer and the underlying steel, respectively, of the

regions shown in Fig. 6a. The orientation is identical in
both regions. Additional aligned spots are present in
both diffraction patterns, and these are most likely due
to aligned oxide films on the upper and lower surfaces
of the TEM foils. Lattice expansion in the expanded
austenite was determined to be 3.6%. The nature of the
pattern changed on crossing the interface, although these
effects were somewhat complicated by the wedge-
shaped profile of the foil. Kikuchi lines were generally Fig. 6. RF plasma nitrided steel: (a) Cross-section showing the inter-
absent from even quite thick regions of expanded aus- face with the underlying steel. The two regions can be differentiated
tenite, this being an indication of a high level of damage. by their dislocation contrast. Also present is a f50 nm surface layer.
(b) Bright fieldydark field pair of the surface layer in (a). The dark
Also, for a given thickness, the diffraction spots tended field image (right) is formed with additional spots in the diffraction
to be more diffuse in the expanded austenite layer, this pattern (b inset) identified as coming from the CrN decomposition
again being a consequence of the higher damage level. product.
 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118 113

w z
Fig. 7. RF plasma nitrided steels. y1̄12~ SADPs taken from (a)
x |

expanded austenite layer, and (b) underlying steel. Identical orienta-

tions are found in both regions, although the expanded austenite shows
a 3.6% expansion of the lattice relative to the underlying steel.

rougher in cross-section than untransformed regions of

expanded austenite. These regions bowed out from the
surface, suggesting a volume increase on transformation.
The expanded austeniteyaustenite interface was located,
but could not be satisfactorily imaged due to excessive
thickness here. In another region of the same specimen
(Fig. 8b,c) the ion milling had eroded the original
surface back approximately 2 mm into the expanded
austenite layer. Here (Fig. 8b) it was possible to image
Fig. 8. PI3 steel in cross-section showing: (a) Region where decom-
the interface and underlying regions at up to 20 mm position of the expanded austenite has nucleated at the surface and
below the original surface. Fig. 8b,c shows the same grown into the expanded austenite layer for a depth of f1 mm. (b)
region before and after tilting through a small angle (- Region where the original surface has been ion milled away f2 mm.
0.58). It is apparent that only under suitable two beam Here the foil is electron transparent up to f20 mm below the original
diffraction conditions (Fig. 8b) is the expanded austen- surface. Two beam diffraction conditions make the expanded austen-
iteyaustenite interface visible. (c) Same region as (b) tilted away from
iteyaustenite interface made visible by the dislocation strong two beam diffraction conditions. Grain boundaries have not
contrast. Tilting to remove this contrast causes the moved significantly, but the expanded austeniteyaustenite interface
interface to become invisible (Fig. 8c) showing that the has disappeared.
114 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118

Table 1 Fig. 4d). Despite this, very considerable expansion of

Diffraction data from various orientations of a single grain of RF the lattice due to the incorporation of interstitial nitrogen
˚
plasma nitrided austenite (untreated steel aos3.591 A)
was evident. The expanded austenite region studied
dyÅ h k l ˚
aoyA Exp’ny% retained its cubic structure, and within the accuracy of
the technique there was no tetragonality or systematic
2.23 1 1 1 3.87 7.8
2.27 1 1 1 3.93 9.4 lattice distortion.
2.26 1 1 1 3.91 8.9 The measured lattice expansion corresponded to
1.97 2 0 0 3.93 9.4
8"1.5%. This agreed reasonably well with the result
1.89 2 0 0 3.78 5.3 determined from X-ray diffraction (not shown) of
f10%.
1.39 2 2 0 3.93 9.4
1.33 2 2 0 3.75 4.4
1.36 2 2 0 3.86 7.5 3.2.2. Tripod polishing
1.18 1 1 3 3.91 8.9 Fig. 9 shows the underlying substrate steel approxi-
1.16 1 1 3 3.86 7.5 mately 20 mm below the original PI3 treated surface.
1.18 1 1 3 3.92 9.2 The depth of the treatment layer on this steel (not
1.17 1 1 3 3.88 8.0 shown) was f3.7 mm, so the region in Fig. 9 was
0.89 3 3 1 3.89 8.3 unaffected by the PI3 treatment. Following tripod polish-
0.89 3 3 1 3.89 8.3 ing to a foil thickness of f20 mm the specimen was
Average 3.88 8.0 ion milled to final electron transparency. The structure
S.D. 0.055 1.5 of the underlying steel was very heavily damaged with
extensive twinning and a high level of dislocations. This
was much greater than that experienced with the con-
crystallographic orientation across the interface is essen- ventional technique, based on slow speed dimpling with
tially identical. Also apparent in Fig. 8b is the effect of a brass wheel to similar foil thicknesses prior to ion
foil thickness on the clarity of the interface. In the upper milling. This suggests that the mechanical damage from
part of the figure the interface is sharp and well defined, tripod polishing is more severe than that of dimpling.
while in the lower half it is more diffuse. This is a
consequence of the pile up of features in projection. In 3.2.3. Focused ion beam milling (FIB)
the thinner parts of the foil (lower half of Fig. 8b) there The FIB processed foil is shown in plan view in Fig.
are fewer dislocations to delineate the interface. Fur- 2. The thin membrane buckled slightly once milled to a
thermore, in the thinner parts of the foil, a far greater thickness below f100 nm. This distortion was a result
proportion of the foil is near the upper and lower of relief of the high residual stresses, and was eliminated
surfaces of the foil, where dislocations can escape to by FIB milling several slots in the membrane, whilst it
the surface. was still quite thick ()100 nm). Rotation of the FIB
Diffraction patterns (not shown) were obtained from
a single crystal region of an untreated steel and an RF
plasma nitrided type 304 stainless steel. Patterns from
different zone axes of the same grain enabled several
lattice spacings to be determined. The presence of the
same reflections (e.g. {111}) in different zone axis
patterns (e.g. N123M and N110M) permitted multiple
determinations of the same spacing. The lattice param-
eter determined for the untreated steel, agreed extremely
well with values reported for type 304 stainless steel in
the JCPDS diffraction data base (File no 33–397, aos
˚ The measured spacings from the RF plasma
3.591 A).
nitrided steel allowed the lattice parameter to be calcu-
lated by assuming a cubic structure. Comparison with
the lattice parameter of the untreated steel enabled the
expansion to be estimated. The results are shown in
Table 1. The TEM camera length was calibrated using
a gold film. The values reported for the expanded
austenite (Table 1) show some scatter, even for the Fig. 9. TEM cross-section of a PI3 steel after tripod polishing. This
region is of the underlying steel of f20 mm below the original sur-
same lattice spacing. This was a consequence of less face, and has not been modified by the PI3 process. The extensive
than optimum quality of the diffraction patterns due to twinning and dislocation is a consequence of the deformation induced
the effects of stressydamage and foil thickness (see, e.g. by the tripod polishing technique.
 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118 115

to be varied between the various regions. Fig. 10a shows

strong dislocation contrast in the underlying steel. Dis-
location damage here appears more severe than similar
materials produced using conventional ion milling, even
allowing for foil thickness effects. This is probably a
consequence of FIB milling using 30 keV Gaq ions,
compared with 5 keV Arq ions used in conventional
PIPS milling. As with conventional ion milling the
dislocation damage in the expanded austenite layer
comprises a high density of point and line defects,
whereas a lower density of predominantly line defects
prevails in the underlying steel.
It was hoped to be able to use FIB to produce
parallel-sided TEM foils, with a thickness of -100 nm,
and extending to depths greater than the treatment depth
(3.7 mm in this case). The aim was to use energy
filtered TEM (EFTEM) in conjunction with electron
energy loss spectroscopy (EELS) to measure the depth
profile of the nitrogen. The thickness profile of the
specimen (Fig. 10b inset) shows that the foil rapidly
thickens from approximately 35 nm at the outer surface
to approximately 300 nm at the interface. These thick-
nesses are far too great to allow meaningful EFTEMy
EELS analysis. EELS was carried out at the thin leading
edge of the foil, corresponding to the original surface
of the steel. Fig. 11 shows the second derivative EELS
spectrum from this region, indicating peaks due to N,
Cr, Fe and Ni. Quantification of the spectrum using the
standard procedures suggested by Gatan, indicated a
surface nitrogen concentration of approximately 20 at.%.
Work on optimising FIB milling of these steels is
currently ongoing.

4. Discussion

TEM examination of metallic materials is generally

relatively routine, since jet electropolishing can be read-

Fig. 10. TEM cross-section of a PI3 steel after FIB. (a) The FIB has
milled to a depth of )5 mm below the original surface. The substrate
steel shows very severe dislocation, as a result of ion beam damage
from 30 keV Gaq ions. An oblique twin cuts through both regions.
(b) Same region as (a) after tilting. The expanded austenite layer is
extremely defective and contains a higher density of point and line
defects than the steel. These originate from both PI3 treatment and
FIB milling. (Inset is the foil thickness profile along the line
indicated.)

specimen through 908 to bring the membrane horizontal

produces the cross-sectional TEM specimen. Fig. 10a,b
shows such views of a PI3 treated steel (316 stainless
steel, 360 8C, 4 h) with an expanded austenite layer
depth of 3.7 mm. The diffraction conditions needed to
be carefully controlled in order to make the expanded Fig. 11. EELS spectrum (second derivative) taken from the surface
austeniteyaustenite interface visible, with very small of the PI3 steel. A nitrogen content of approximately 20 at.% is
changes in orientation enabling the dislocation contrast indicated.
116 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
ily applied to most metals and alloys. This specimen
preparation technique has a major advantage over most
others, in that it introduces no mechanical damage into
the system, and so permits studies on damage structures.
Also it is generally very quick, with actual thinning
taking only 1 or 2 min. The major limitation is that
while it works very well on single-phase systems,
multiphase systems can be subject to localised dissolu-
tion where strain or chemical gradients exist around
second phase particles. This was apparent in the speci-
mens where decomposition of the expanded austenite
had occurred (Fig. 5a,b, Fig. 8a). Compositional analysis
of CrNya regions showed very high Cr levels, which
cannot be accounted for by long-range diffusion of Cr.
Therefore local dissolution of the a Fe component from
the CrNya decomposition product must have taken
place. It is well known that the corrosion resistance of
expanded austenite layers is lost once CrNya precipi-
tation has occurred w12x.
The plan view microscopy highlighted the residual
damage stemming from metallographic preparation of
the disk prior to treatment. This included surface scratch-
es and dislocation (Figs. 3 and 4a). It is interesting to
note that the RF plasma nitriding process resulted in
retention of much of this damage (Fig. 4a) while the
PI3 process eliminated much of it (Fig. 5a). This can
be attributed to the much higher energies of ionic species
in the latter process. Typical negative bias pulse voltages
of up to 45 kV may be used in the PI3 process w18x,
and so surface sputtering can occur w12x. This is not a
feature of RF plasma nitriding, where the energy of the
ions interacting with the work piece is typically only a
few hundred electrovolts w19,20x. PI3 treated steels have
been described as having a sandblasted appearance w12x,
and this surface peening effect was evident in Fig. 5b.
What is also apparent is that plan views of expanded
austenite layers do not show strong defect contrast (Fig.
5a,b), whereas RF plasma nitrided steels do (Fig. 4a,b).
Since the jet electropolishing does not introduce damage,
this must be a true reflection of the damage structure.
The RF plasma nitrided steels retain metallographic
damage, whereas in the PI3 steels most of it is presum-
ably sputtered away. The low residual damage levels in
the plan views of the PI3 steels (Fig. 5a,b) are in marked
contrast to those in the respective cross-sections (Fig.
8b) prepared with ion beams. It is clear that ion beam
damage from TEM specimen preparation (at room tem-
perature) is a significant contributor to the observed
damage structures.
Plan view microscopy highlighted the nucleation of
the CrNya decomposition product. This transformation
has been described by Li et al. w21x. Xu et al. w22x have
also carried out plan microscopy on heavily transformed
plasma nitrided steels, and have elucidated the orienta-
tion relationships between the various phases. In the
present work, nucleation was observed to occur prefer-
entially at the grain boundaries (Fig. 4c, Fig. 5a),
although nucleation within grains was also seen. Blawert
et al. w23x have seen grain boundary precipitation in
stainless steels PI3 treated at 500 8C, using scanning
electron microscopy. The expanded austenite and the
nucleation and growth processes appeared similar for
both RF plasma nitrided and PI3 treated steels. The
differing extents of the transformation is evidently a
consequence of the different processing parameters,
rather than due to fundamental mechanistic differences.
The formation of expanded austenite (and its subsequent
decomposition) in austenitic stainless steel resulting
from a range of plasma and ion beam processing
techniques has been widely reported w10,20,24–26x. The
actual nature of the expanded austenite has been the
subject of several recent articles w25,27x.
Cross-sectional TEM specimens permitted the nature
of the treated layer as a function of depth to be
determined. While such specimens are potentially far
more useful than plan view specimens, they are also far
more time consuming to prepare, and far less likely to
be of useful quality. The challenge is to produce parallel
sided foils, -100 nm thick, which extend beyond the
treatment depth. This usually requires foil depthythick-
ness ratios of )30, which is very demanding.
The RF plasma nitrided steel showed that transfor-
mation initiated as a thin layer at the surface (Fig. 6a,b).
Li et al. w28x have also carried out cross-sectional TEM
on a plasma nitrided steel. They reported a surface layer
of CrN of approximately 200 nm thick, overlaying a
much thicker expanded austenite layer. Blawert et al.
w29x have also reported transformation initiating at the
surface. In the present work, more extensive transfor-
mation was found in the PI3 steel (a consequence of the
processing parameters), and here too, nucleation
occurred at the surface (Fig. 8a). Subsequent extensive
growth of the decomposition product into the expanded
austenite layer then took place. From the plan and cross-
sectional results it is clear that grain boundaries and the
free surface are the preferred nucleation sites for trans-
formation. It is likely that nitrogen concentrations will
be highest in the grain boundary and near-surface
regions, providing the necessary driving force for trans-
formation. The intra-granular nucleation seen in plan
view (Fig. 4a, Fig. 5a) does not occur within the bulk
of the expanded austenite layer, but in isolated pockets
at the surface. Compressive stress may also be important,
since the present work showed that bulging of the
surface occurred in transformed regions, suggesting a
net volume expansion on transformation. Several authors
w12,13x have observed a macroscopic increase in surface
roughness with the onset of significant transformation
of the expanded austenite layer. Clearly, the free surface
and grain boundary regions will be better able to
accommodate the plastic strain required for
transformation.
 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
The cross-sectional examination highlighted the dif-
ference in the density and the type of defect contrast in
the expanded austenite layer and the underlying steel,
and similar structures have been reported by Li et al.
w28x. Due to the complicating factor of ion beam damage
from specimen preparation, it is not possible to make
comments about the origin of this damage. However,
the fact that the expanded austenite layer has a much
greater defect density than the underlying steel, is not
surprising in view of the extensive plastic deformation
which accompanies its development. Extensive surface
relief is a consequence of expanded austenite formation,
with grain and twin boundaries evident, as well as
widespread slip banding apparent on the surfaces of
treated stainless steels w17,25x. This high level of dam-
age was also apparent in diffraction patterns from the
two regions. Kikuchi lines were either absent or were
very diffuse in the expanded austenite layers, regardless
of foil thickness (Fig. 7a). For a given foil thickness,
Kikuchi line intensity is typically strongest for perfect
(undamaged) crystals, and decreases with increasing
levels of deformation.
The dislocation contrast difference across the expand-
ed austeniteyaustenite interface was used to locate it.
Both diffraction (Fig. 7a,b) and imaging (Fig. 8b,c)
showed that this was not a crystallographically discrete
boundary, such as a high angle grain boundary. While
extensive expansion of the austenite lattice occurs (lat-
tice parameter increases of up to 8% were measured for
the 304 stainless steel data shown in Table 1), the
orientational relationship with the underlying steel is
preserved. The strain of expansion must therefore be
accommodated by the expanded layer and the underlying
steel. Unfortunately, evidence of this strain (dislocation)
is masked by the damage induced by ion beam milling.
There has been much debate in the literature on the
exact nature of expanded austenite w10,25,26,29x. This
has stemmed from X-ray diffraction data which has
indicated that the austenite lattice does not expand
uniformly. Instead, expansion along the (100) direction
is larger by approximately 20% than that along (111)
direction w26x. Attempts to explain this distortion on the
basis of triclinic or tetragonal distortion of the lattice
w25,26x have not fully resolved the question. It was
hoped that electron diffraction in the TEM might shed
some further light on this. Detailed crystallographic
analysis of a number of diffraction patterns obtained
from the same crystal enabled the lattice parameter to
be determined from a number of different planes (Table
1). One of the major difficulties with working with
expanded austenite is that the high level of damage and
stress leads to broad diffuse electron diffraction spots,
in just the same way that X-ray diffraction peaks from
this material tend to be broad w12,13x. Typically, electron
diffraction measurements may have an accuracy of
f1%. In the present case, foils were often thicker than
117
ideal, causing further spot broadening. An average lattice
parameter expansion of 8"1.5% was obtained, while
the equivalent X-ray result indicated an expansion of
10%. An apparent absence of systematic distortion of
the lattice from cubic in the TEM specimen is perhaps
not surprising, since relaxation of some of the residual
compressive tresses can occur once the foil is thinned
below a few hundred manometers, as seen in the FIB
specimen (Fig. 2).
Focused ion beam milling enabled consistent produc-
tion of foils spanning the treatment layer. However, foils
currently produced have a thickness at the expanded
austeniteyaustenite interface of f300 nm which is much
thicker than that required (-100 nm). The section
through the full treatment depth section does permit the
nature of the expanded austenite layer to be seen, and
it is clear that under treatment conditions where trans-
formation does not occur, the expanded austenite layer
is quite uniform. No amorphous layers were found in
any of the steels examined, irrespective of treatment
conditions and processing technique. We have re-exam-
ined specimens previously reported to contain surface
amorphous layers from PI3 treatment w21x, and have
shown them to be TEM specimen preparation artefacts.
The foil thicknesses achieved with FIB were too thick
for chemical analysisyimaging, and further work to
optimise FIB milling of these steels is required. At the
original surface, where the foil was thin enough to
permit EELS analysis, a nitrogen content of f20 at.%
was obtained, which agrees well with values determined
using various spectrometric techniques on similarly
treated steels w10,26,29x
5. Conclusions
Plan view TEM specimens, prepared using jet electro-
polishing, indicated that the more energetic PI3 process
sputters away residual surface damage from initial metal-
lographic preparation, while the less energetic RF plas-
ma nitriding process retains the original surface features.
In materials where transformation of the expanded aus-
tenite layer took place, nucleation of the CrNya Fe
product occurred preferentially at the grain boundaries,
with limited nucleation at surface grains also observed.
Similar behaviour was observed in both PI3 and RF
plasma nitrided steels, the differing extents of transfor-
mation being due to differing processing parameters,
rather than mechanistic differences. Cr enrichment of
transformed regions was an artefact caused by prefer-
ential dissolution of the less corrosion resistant a Fe
component by the jet electropolishing solution to leave
CrN behind.
Cross-sectional imaging showed an increase in surface
roughening upon transformation that appeared to be a
consequence of a volume expansion. It also showed that
the free surface was a preferred site for the nucleation
118 D.R.G. Mitchell et al. / Surface and Coatings Technology 165 (2003) 107–118
of transformation product, presumably as it is better able
to accommodate the transformation strain than the bulk.
Only ion beam-based thinning techniques could be
successfully applied to specimen preparation, and dis-
location structures were complicated by the presence of
(TEM specimen preparation) ion beam damage, which
was not present in the jet electropolished plan view
foils. The expanded austeniteyaustenite interface showed
no orientation difference across it, indicating that the
expanded austenite retains the crystal structure and
orientation of the underlying steel. This interface is
effectively invisible, unless appropriate two beam dif-
fraction conditions are produced to highlight the dislo-
cation contrast differences across it. The expanded
austenite layer contains very high levels of point and
line defects, while the underlying steel contains a lower
concentration of mainly line defects. Kikuchi line con-
trast and diffraction spot broadening also indicated
severe damage in the expanded austenite layer. Charac-
terisation of the lattice parameter of a single grain using
selected area diffraction (within the limits of accuracy
of the technique), showed no evidence for the non-
isotropic lattice distortion reported in X-ray diffraction
measurements. However, stress relaxation has been
observed in thin TEM foils and so meaningful compar-
ison with bulk XRD data is compromised.
Tripod polishing has been shown to be unable to
produce electron transparent foils directly, as the high
residual stresses causes them to break up. Furthermore,
extensive damage from the technique was found in foils
which were subsequently ion milled to electron trans-
parency. Focused ion beam milling has permitted con-
sistent production of cross-sections, which enable
imaging through the entire treated depth. However, these
foils are currently too thick to permit analysis of the
nitrogen profile using EELS-based techniques, and fur-
ther work is required to refine our technique.
Acknowledgments
The authors wish to thank C. Blawert for assistance
with RF plasma nitriding treatments and Dr Paul Munroe
and his staff of the EM Unit, UNSW for assistance with
the FIB work.
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