Tribology Letters Vol. 11, No.

2, 2001 127

Structural characterization of wear debris produced during friction

between two austenitic stainless steel antagonists
C. Brin, J.-P. Rivière ∗ , J.-P. Eymery and J.-P. Villain
Laboratoire de Métallurgie Physique, UMR 6630 CNRS, Université de Poitiers, Bâtiment SP2MI, Téléport 2, Boulevard Marie et Pierre Curie,
BP 30179, F-86962 Futuroscope-Chasseneuil Cedex, France
E-mail: jpriviere@univ-poitiers.fr

Received 19 December 2000; accepted 6 June 2001

Ball-on-flat friction experiments between two austenitic stainless steel antagonists in sliding contact are carried out under very low
loads and in two liquid environments, namely demineralized water and methanol. The wear debris produced during long-duration tests are
characterized by different techniques such as X-ray diffraction, transmission electron microscopy and Mössbauer spectroscopy. Martensite
is observed as a dominant phase in the wear debris but other phases have been also identified. In the debris produced under demineralized
water, there is significant contribution of a second phase, which is poorly crystallized and which was identified as the hydrous iron oxide
called ferrihydrite. In the debris produced under methanol, there is a remaining amount of austenite that is not transformed into martensite,
and the presence of ferrihydrite has been also detected in very small quantities. The formation of the martensitic debris which occurs from
the beginning of the wear tests supports the fact that under our experimental conditions the main damaging mode is abrasive wear by hard
particles.
KEY WORDS: AISI 304 stainless steel; X-ray diffraction; Mössbauer spectroscopy; wear debris; ferrihydrite

1. Introduction The objective of this paper is to present the results of a

detailed microstructural analysis of the wear debris formed
Austenitic stainless steels are widely used materials be- during those mild friction tests of AISI 304 stainless steel
cause of their very good corrosion resistance in various ag- samples in order to obtain a more complete understanding
gressive environments. However, they exhibit a relatively of their role in wear processes.
low hardness (∼2–3 GPa) and poor tribological properties.
One of the most representative alloys of this category is cer-
tainly AISI 304 stainless steel. Its wear behaviour has been 2. Experimental procedure
extensively studied [1–3] and it is now well established that,
2.1. Friction experiments
whatever the friction conditions, it has a very low wear re-
sistance both in dry sliding and under lubricated conditions. Wear tests were carried out at room temperature using
Severe adhesive and abrasive wear has been observed, as- a conventional pin-on-disc machine. For the experiments,
sociated with significant mass losses. Even after short du- AISI 304 stainless steel discs, 32 mm in diameter and 8 mm
ration tests, Fayeulle et al. [4,5] have observed severe abra- in thickness, rotate in a horizontal plane, while the immobile
sive wear and plastic flow of the material during friction ex- counterpart pin is a cylindrical sample (AISI 304L), 10 mm
periments, while strain-hardening, twinning and martensitic in diameter and 35 mm in length, exhibiting a spherical-
transformation were identified by transmission electron mi- ended extremity of large radius (∼120 mm). The chemical
croscopy. As a result, a hard superficial layer is formed but compositions of both disc and pin are given in table 1. The
its consequences on the wear rate strongly depend on differ- pins and discs were mechanically polished before the tests,
ent factors, such as the nature of both counterparts, applied until a mean roughness of 0.02 µm was reached. Hardness
load, sliding velocity and environmental conditions. measurements performed before testing gave values in the
Most of the previous friction experiments with AISI 304 2.2–2.5 GPa range. The rotational speed selected for these
stainless steels have been carried out under high applied experiments was 60 turns per minute, which corresponds to
loads producing elevated initial Hertzian pressures exceed-
Table 1
ing the elastic limit of the material (∼280 MPa). In recent
Chemical composition (wt%) of disc and pin alloys (304 and 304L stainless
works [6,7], we have investigated the sliding-wear behav- steels, respectively).
iour of AISI 304 stainless steel in a ball-on-flat configura-
C Si Mn S P Ni Cr Fe
tion under Hertzian pressures at least four times lower than
the elastic limit of the alloy. Disc 0.042 0.39 1.16 0.0016 0.021 8.74 18.53 Balance
Pin 0.016 0.65 1.69 <0.003 0.019 10.46 18.54 Balance
∗ To whom correspondence should be addressed.

1023-8883/01/0800-0127$19.50/0  2001 Plenum Publishing Corporation

128 C. Brin et al. / Wear debris between austenitic steel antagonists

a linear velocity of 0.065 m s−1 . The wear debris were pro-

duced during friction tests under applied loads of 4 and 8 N.
The corresponding calculated initial Hertzian pressures, 58
and 75 MPa, respectively, are much lower than the elastic
limit of the starting stainless steel (∼280 MPa). Under our
experimental conditions, it must be noticed that there is a
significant increase in contact area during the wear test due
to the wearing of the spherical pin extremity. Consequently
there is also a considerable decrease in the pressure applied
by the pin onto the disc. For instance, under a 8 N normal
load and after a sliding distance of 0.6 km, the calculated
pressure falls to 0.5 MPa. A special stainless steel vessel
has been designed to perform friction experiments in liq-
uid media such as demineralized water and methanol [6],
and the debris generated during sliding were collected for
structural analyses. The production of the amount of debris
necessary for X-ray diffraction and Mössbauer spectroscopy
experiments has required very long tests (∼2–4 weeks) cor-
responding to sliding distances of the order of 100 km.

2.2. Characterization methods

The wear debris were first analysed by X-ray diffrac-

tion (XRD) using Cu Kα radiation (λ = 0.15406 nm) and
a Siemens D5000 diffractometer equipped with a graphite
monochromator. Mössbauer spectra were recorded at room
temperature in transmission mode using a constant acceler-
ation spectrometer. As a source of γ -rays, the 57 Co in Rh
matrix was used. Isomer shifts are given relative to the cen-
troid of the spectrum of α-Fe at 293 K. The spectra were
fitted to Lorentzian lines by using the least-squares mini-
mization method. Transmission electron microscopy (TEM)
observations were performed at 200 kV in a Jeol 200CX mi-
croscope after depositing the wear debris onto a carbon grid.
The morphology of the wear tracks was also monitored by a
JSM 5300 scanning electron microscope. Figure 1. Scanning electron micrographs showing the worn surface near
the main wear track, after a sliding distance of 3 km under a 4 N load
in water environment. The initial and final extremities of a lateral groove
are indicated by A and B, respectively. The arrow indicates the sliding
3. Experimental results direction.

3.1. Morphology and structure of the worn surfaces
The analysis of the worn surfaces [6,7] suggests that, at
the very beginning of our tests, the initial wear mechanism
is mainly due to adhesion. Effectively, even if the roughness
of both surfaces in contact is very low, there are always sur-
face asperities at which the real contact pressure is very high
and then adhesion takes place between them. The relative
motion of the two surfaces induces severe plastic deforma-
tion and rupture of these deformed junctions, thus producing
hard wear debris. After this transient period, scanning elec-
tron microscopy observations show that the wear tracks are
formed of very fine, smooth and parallel grooves [6,7]; they
are typical of an abrasive wear process of a ductile mater-
ial caused by the ploughing action of hard particles. During
the experiments, the width of the main wear track progres-
sively increases, so it is possible to continuously observe the
formation of new lateral grooves during the tests, as is illus-
trated in figure 1 for a test performed in water environment
under a 4 N normal load and after a sliding distance of 3 km.
In figure 2 we present at a higher magnification the initial
and final extremities of the A–B groove shown in figure 1.
This groove exhibits highly deformed lateral regions, indi-
vidual debris, and at its final extremity a significant agglom-
eration of wear debris. This process of agglomeration could
then explain the formation of large grooves by an abrasive
mechanism. When the tests are performed in methanol envi-
ronment, the morphology of the wear tracks remains nearly
the same, although the friction coefficient is lowered by a
factor of two and the wear rate is also reduced.
A typical XRD pattern of the employed stainless steel,
taken before starting the friction tests, is presented in fig-
ure 3. It only exhibits the diffraction peaks of the γ fcc
austenite, which are located at 2θ = 43.6◦, 50.7◦, 74.6◦,
 C. Brin et al. / Wear debris between austenitic steel antagonists
Figure 2. Scanning electron micrographs showing at a higher magnification
the extremities of the A–B groove in figure 1: (a) initial extremity A and
(b) final extremity B. The arrow indicates the sliding direction.
Figure 3. X-ray diffraction pattern taken from the starting 304 stainless
steel, before the friction tests. Only the peaks from the γ austenite phase
are visible.
129
Figure 4. X-ray diffraction pattern taken from a steel pin after a friction test
performed under a 8 N load in water environment. Note the appearance of
the α  martensite phase.
90.5◦ and 95.9◦, respectively, as expected from the JCPDS-
ICDD powder diffraction database (PDF-2). The struc-
tural characterization of both worn counterpart surfaces has
clearly shown that, whatever the applied load or environ-
ment and since the beginning of the friction tests, austenite is
transformed into martensite in the surface layers. The XRD
pattern of the worn pin surface after a test in water environ-
ment under a 8 N load is shown in figure 4 and illustrates
this behaviour. It is important to emphasize that there are no
additional diffraction peaks that might indicate the presence
of other phases. The pattern in figure 4 was used to calculate
the lattice parameter of the martensite phase. The derived
value, a = 0.2878 nm, is in good agreement with that ob-
tained from neutron scattering experiments (a = 0.2875 nm)
by Herjo et al. [8]. The crystallite size (D) of both γ and α 
phases was also estimated by using the method described
in [9]. This method is well suited, since it takes into ac-
count the line broadening caused by the lattice strain. Before
the friction tests, the D value for the austenitic phase along
the [111] direction is measured to be ∼40 nm. The structural
changes brought about by the tests resulted in lowering the
latter D value by a factor of two, for both γ and α  phases.
3.2. X-ray diffraction experiments on wear debris
The XRD pattern of the wear debris formed during test-
ing under demineralized water is presented in figure 5. The
most intense peaks can be unambiguously identified to α 
martensite, but the presence of two additional peaks, which
are broad and weak, can be noticed at 2θ = 35.6◦ and 62.7◦;
the associated distances are d = 0.252 and 148 nm, respec-
tively. The corresponding phase is not well crystallized, and
it is not possible to identify it only on the basis of the latter
XRD pattern. Mössbauer experiments were carried out in
order to identify this second phase.
In the case of the debris formed in methanol environ-
ment under a 8 N load, the XRD pattern presented in fig-
ure 6 is different, since the contribution of three different
130 C. Brin et al. / Wear debris between austenitic steel antagonists
Figure 5. X-ray diffraction pattern taken from wear debris produced in
water environment under a 4 N normal load. The arrows indicate the peak
positions for ferrihydrite.
Figure 6. X-ray diffraction pattern taken from wear debris produced in
methanol environment under a 4 N normal load. The arrow indicates the
position of the main ferrihydrite peak.
phases can be noticed. The first and dominant phase still
remains α  martensite and the diffraction peaks attributed
to the unidentified phase are here practically not detectable;
only the 2θ = 35.6◦ peak slightly emerges from the back-
ground. Moreover, the presence of the (111) diffraction
peak of austenite is visible, superimposed to the α  marten-
site (110) peak. These results suggest firstly that the debris
formed under methanol are not completely transformed into
martensite, and secondly that there is a smaller contribution
of a new phase which is to identify.
3.3. TEM observations
The TEM observations of the debris collected either un-
der water or under methanol have shown that they are es-
sentially formed of martensite since the contribution of the
other phases could not be detected in the electron diffraction
patterns. In figure 7 we present a TEM micrograph and the
corresponding diffraction pattern of the ultimate wear debris
Figure 7. TEM micrograph of wear debris produced in water environment
under a 4 N load (upper image) and corresponding electron diffraction pat-
tern (lower image).
produced in a water environment after a long sliding distance
of 100 km under a 4 N load. The diagram is formed of con-
centric rings of weak intensity which are characteristic of
the crystalline structure of α  martensite with fine and dis-
oriented grains. The diffuse background in the central part
of the diagram is the contribution of the amorphous carbon
grid supporting the debris. The bright field image in figure 7
indicates that most of the debris range from 50 to 500 nm in
size. However, some of the observed particles are probably
agglomerates formed by clustering of smaller particles.
3.4. Mössbauer spectroscopy experiments
Mössbauer spectroscopy can provide valuable informa-
tion on the nature of iron compounds because it is very sen-
sitive to their magnetic properties. It is well known that
martensite is ferromagnetic at room temperature and that
austenite is not; as a consequence these compounds exhibit
quite different Mössbauer spectra. The spectra from the de-
bris formed in a water environment under 4 and 8 N loads
were recorded in the −8 to +8 mm/s velocity range, and
the former is presented in figure 8. In this spectrum, there
is a major contribution of a ferromagnetic sextuplet with
average hyperfine field Hhf = 26.9 ± 0.2 T and isomer
shift δ = −0.03 ± 0.02 mm/s. These values are in very
 C. Brin et al. / Wear debris between austenitic steel antagonists
Figure 8. Transmission Mössbauer spectrum for wear debris produced in
water environment under a 4 N load. The S and D subspectra are attributed
to martensite and ferrihydrite, respectively.
good agreement with the Mössbauer data corresponding to
martensite [10]. The second contribution to the experimen-
tal spectrum is very different since it consists of a doublet
with equal components, which is the signature of a para-
magnetic compound. The values derived for the isomer shift
and quadrupole splitting are δ = 0.345 ± 0.02 mm/s and
131
Figure 9. Transmission Mössbauer spectrum for wear debris produced in
methanol environment under a 8 N load. The S, D and L subspectra are
attributed to martensite, ferrihydrite and austenite, respectively.
the relative contributions of the two phases are different, i.e.,
48% of iron atoms belong to the martensite and 52% to the
ferrihydrite.
The Mössbauer spectrum of the debris formed in a
methanol environment under a 8 N load is presented in fig-
ure 9. Its shape differs from that of the two previous spectra
 = 0.83 ± 0.01 mm/s, respectively. In order to identify
the corresponding compound and since the friction exper-
iments were performed under water during long duration
tests, we have focussed the investigations towards iron ox-
ides, hydroxides and hydroxyoxides. We have compared
our data with the Mössbauer parameters of the above com-
pounds [11] and found a very good agreement with the pa-
rameters of a paramagnetic hydrous iron oxide known as
ferrihydrite and whose chemical formula can be written as
Fe5 O7 (OH)·4H2 O. This compound is either a mineral or a
synthetic product, but it often exhibits a poorly crystallized
structure; its X-ray diffraction pattern is composed of either
two or six broad peaks, depending on the degree of crystal-
lization [12,13]. In the case of the poorly ordered forms, two
peaks are generally observed with Cu Kα radiation, appear-
ing at 2θ ≈ 35.5◦ ((100) reflection) and 2θ ≈ 62◦ ((115)
and (106) reflections) [13], which fairly well corresponds to
the positions of the unidentified peaks in our diffraction pat-
terns (see figures 5 and 6). The values of the quadrupole
splitting found in previous studies for ferrihydrite with two
XRD peaks are in the 0.83–0.85 mm/s range [13], and the
isomer shift is 0.35 mm/s, which is in very good agreement
with our results. From the ratio of the sextuplet area over
the total spectrum area, we have estimated the percentage of
iron atoms involved in the martensitic phase as 61.5 ± 2%,
so the remaining Fe atoms (38.5 ± 2%) may be ascribed to
the ferrihydrite phase.
The spectrum taken from the debris produced in a water
environment under a higher load of 8 N (not shown here) is
similar to that in figure 8, but here the component lines of
the sextuplet are less resolved, thus indicating that the size
of the martensite particles is smaller. It is still possible to
obtain a good fit with a ferromagnetic sextuplet and para-
magnetic doublet having the same Mössbauer parameters as
those measured from the spectrum in figure 8. In that case,
since the components of the central doublet do not have the
same intensity, thus suggesting the possible contribution of a
third component with a single line. We have fitted this spec-
trum by the superimposition of three contributions, namely
a single central peak, a doublet and a sextuplet. The single-
line component can be ascribed to γ austenite which is para-
magnetic with an isomer shift δ = −0.05 ± 0.02 mm/s.
The Mössbauer parameters of the two other components, at-
tributed to martensite and ferrihydrite, respectively, have the
same values as for the previous spectra. The percentage of
iron atoms in the three different phases are 73% for marten-
site, 13.5% for ferrihydrite and 13.5% for austenite. This
result is qualitatively in good agreement with the XRD pat-
tern in figure 6, suggesting the minor contribution of both
ferrihydrite and austenite phases. The Mössbauer parame-
ters of the different components deduced from the analyses
are listed in table 2.
4. Discussion and conclusion
The above structural analysis has shown that marten-
site is the dominant phase in the wear debris formed dur-
ing long duration friction tests under demineralized water or
methanol. This result is not surprising, since it is well known
that martensitic transformation of 304 stainless steel can be
induced by plastic deformation [14]. Under the present ex-
perimental conditions, the average Hertzian pressure is much
lower than the elastic limit; however the local stress inten-
sities at the level of microasperities are high enough to pro-
duce plastic deformation that could result in strain-hardening
and martensitic transformation.
For the friction experiments performed under water, there
is still austenite in the surface layer of both antagonists in
contact, but this phase is rapidly and completely transformed
132 C. Brin et al. / Wear debris between austenitic steel antagonists

Table 2
Mössbauer parameters from the wear debris formed during friction tests performed in water and methanol environments under
4 and 8 N loads. Hhf = magnetic hyperfine field, δ = isomer shift relative to iron metal,  = quadrupole splitting, r = relative
area.
Martensite Ferrihydrite Austenite
r Hhf δ r δ  r δ
(%) (T) (mm/s) (%) (mm/s) (mm/s) (%) (mm/s)

Debris formed under water

4N 61.5 26.9 −0.03 38.5 0.345 0.83 – –
8N 48 26.9 −0.03 52 0.34 0.83 – –

Debris formed under methanol

8N 73 26.2 – 13.5 0.34 0.83 13.5 −0.08

into martensite during plastic deformation and removal of
the debris. In the case of experiments under methanol, it
is clear that the transformation of austenite into martensite
in the debris is not complete, and this result can be corre-
lated with the role of methanol as lubricant. The significant
reduction of the friction coefficient (factor of two) can ex-
plain the reduction of the intensity of the associated tangen-
tial shear stresses responsible for the debris removal. As a
consequence, the amount of debris produced under methanol
is less abundant and the plastic deformation less severe, thus
explaining the presence of untransformed austenite in the
wear debris. Under these conditions, there is a reduction
in both abrasive effects and wear rate.
The absence of ferrihydrite at the surface of both antago-
nists strongly suggests that this phase is formed in the debris
only either at the moment of their removal (being promoted
by a local and short temperature increase) or after the debris
ejection during the prolonged stay in water or methanol. Let
us mention that ferrihydrite has been recently detected as a
corrosion product formed on carbon steel after long expo-
sure to the open atmosphere in both polar and subtropical
climates [15]. Under the present conditions, there is how-
ever no experimental evidence, from the morphological and
microstructural characteristics of the worn surfaces, which
indicates that this new phase plays a role in the wear be-
haviour. The principal mechanism by which the degradation
of the two stainless steel surfaces occurs, appears to be of
mechanical origin and related to abrasion produced by hard
martensite particles.
Acknowledgement
This research was supported by Electricité de France un-
der contract No. 780336. The authors would like to grate-
fully acknowledge Dr. R. Cauvin for many helpful discus-
sions.
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