Int. J. Appl. Ceram. Technol.

, 7 [1] 89–103 (2010)

DOI:10.1111/j.1744-7402.2008.02329.x

Ceramic Product Development and Commercialization

Wear Mechanisms of TiB2 and TiB2–TiSi2 at Fretting

Contacts with Steel and WC–6 wt% Co
Golla Brahma Raju and Bikramjit Basu*
Laboratory for Advanced Ceramics, Department of Materials and Metallurgical Engineering, Indian
Institute of Technology, Kanpur, India

Unlubricated fretting wear tests on TiB2 and TiB2–5 wt% TiSi2 ceramics against two different mating materials (bearing
grade steel and WC–6 wt% Co balls) were performed with a view to understand the counterbody-dependent difference in
friction and wear properties. The fretting experiments were conducted systematically by varying load (2–10 N) at an oscillating
frequency of 4 Hz and 100 mm linear stroke, for a duration of 100,000 cycles. Adhesion, abrasion, and three-body wear have
been observed as mechanisms of material damage for both the TiB2/steel and TiB2/WC–Co tribosystems. The third body is
predominantly characterized as tribochemical layer for TiB2/steel and loose wear debris particles for TiB2/WC–Co tribocou-
ple. An explanation on differences in tribological properties has been provided in reference to the counterbody material as well
as microstructure and mechanical properties of flat materials.

Introduction The other damaging aspect of the fretting is fretting

Fretting wear refers to the phenomena of small am-
plitude (r300 mm) relative reciprocatory displacement
sliding motion. Basically, fretting is a form of adhesive
or abrasive wear, where the normal load causes adhe-
sion between asperities and oscillatory movement causes
rupture, resulting in the formation of wear debris.1,2
*bikram@iitk.ac.in
r 2008 The American Ceramic Society
fatigue. These forms of damage can arise in any assem-
bly of engineering components/machinery, if a source
of vibration is present. For example, fretting occurs in
all quasi-static-loaded assemblies, such as keys, bearing
races, shafts, orthopedic implants, turbine blade roots,
electrical contacts, nuclear reactor components, and
power plant machinery, etc. Among the various modes
of fretting contacts, mode I fretting wear, that is, under
tangential displacement conditions has been broadly
studied for various engineering materials.1–4
90 International Journal of Applied Ceramic Technology—Brahma Raju and Basu
The use of ceramics for many tribological applica-
tions increased considerably because of their unique
combination of properties such as low density, low ther-
mal expansion, high hardness, and corrosion resistance.
Titanium diboride (TiB2) belongs to this group of
materials and is well known for its high hardness, high
melting point, good electrical and thermal conduc-
tivities.4 The potential applications of TiB2 materials
include cutting tools, impact resistant armor, wear re-
sistant parts, and electrodes for electrodischarge ma-
chining. However, densifying TiB2 at lower sintering
temperatures without compromising much on its un-
ique combination of properties remains as a challenge.5
Considerable research efforts have been directed toward
obtaining dense TiB2-based materials, possessing better
properties, via various sintering techniques and incor-
poration of different metallic as well as nonmetallic
additives.5–10
The tribological performance of the materials de-
pends on various parameters (fracture toughness, hard-
ness, elastic modulus, microstructural characteristics),
operating parameters (load, test environment, test du-
ration, etc.) as well as counterbody material. Extensive
research has been carried out to understand the tribo-
logical behavior of hard materials like ceramics and cer-
mets11–21 with limited tribological work on TiB24,22–26
The fretting wear behavior of TiB2 containing compos-
ites under dry sliding conditions against bearing steel is
reported and a tribochemical wear model is formu-
lated.4 Basu et al.22 studied the mechanisms of material
removal of TiB2-based composites after fretting against
ball bearing steel in lubricating medium. During the
fretting tests against steel in paraffin oil significant re-
duction in friction (coefficient of friction [COF] around
0.08–0.12) could be observed when compared with that
in water for all the investigated materials. Wasche
et al.26 investigated the influence of relative humidity
(RH) on friction and wear behavior of pressureless sin-
tered TiB2 ceramic against SiC and Al2O3 balls under
unlubricated conditions at room temperature. TiB2 ex-
hibited low wear rates (o1  106 mm3/N m), that is,
high wear resistance. While reviewing the existing liter-
ature, it was noted that the tribological properties of
TiB2 coatings were also investigated to some extent.27–32
The use of hard TiB2 coating is reported to increase the
wear resistance by a factor of 10 than that of bulk TiB2.30
The present investigation is carried out to under-
stand the tribological performance of the newly devel-
oped TiB2 ceramics against widely used engineering
Vol. 7, No. 1, 2010
materials such as steel and WC-based cermets. It also
needs to be mentioned here that till now there are no
studies on the tribological behavior of TiB2/cemented
carbide tribocouple. In the present study, an attempt has
been made to investigate the load (P: 2, 5, 10 N) de-
pendent wear mechanisms for hot-pressed TiB2 and
TiB2–5 wt% TiSi2 ceramics.
Experimental Procedure
Materials
In a recent study,33 we reported that an optimal
combination of density, hardness, and toughness can be
obtained in TiB2–5 wt% TiSi2 and accordingly, the
same ceramic composition is selected for the present
study. Monolithic TiB2 is chosen as a baseline material
for comparison. Both TiB2 and TiB2–5 wt% TiSi2 ma-
terials were processed from commercially available
TiB2 (Grade F, H.C. Starck, Goslar, Germany) and
TiSi2 (Goodfellow Cambridge, Huntingdon, U.K.)
powders. An approximate amount of powder mixtures
were hot pressed at a temperature of 16501C for 1 h,
with an applied pressure of 30 MPa, in a flowing argon
atmosphere. The binderless TiB2 could be densified to
around 95% theoretical density (rth), while almost full
densification (B99% rth) was achieved with the TiB2–
5 wt% TiSi2 via the liquid-phase sintering. Microstruc-
tural investigation of the polished surfaces was per-
formed by means of a scanning electron microscope
(SEM) (Quanta FEI 200, Eindhoven, The Nether-
lands), attached with energy-dispersive spectroscopy
(EDS). A representative SEM–EDS image of etched
TiB2–5 wt% TiSi2 is presented in Fig. 1. The micro-
structure reveals the presence of equiaxed TiB2 grains
(gray) and intergranular Ti5Si3 (bright) phase; the cor-
responding EDS analysis of the phases evidences the
presence of Ti, B, and Si. The average grain size of TiB2
is about 3.5 mm. Vickers hardness of the dense TiB2
samples were measured using an indent load of 50 N.
The fracture toughness evaluations were done by crack
length measurement of the radial crack patterns formed
around Vickers indents according to the formulation
proposed by Anstis et al.34 Elastic modulus (E) was de-
termined using dynamic elastic properties analyzer,
which works on the principle of resonance frequency.
The details of starting powders, microstructural charac-
terization, densification mechanism, and properties of
the materials are described elsewhere.33
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2
Fig. 1. Scanning electron microscope image of the polished and
chemically etched (unworn) surface of TiB2–5 wt% TiSi2. The
energy-dispersive spectroscopy analysis indicating TiB2 (dark)
phase: Legend 1 and Ti5Si3 (bright) phase: Legend 2.
Wear Tests
The fretting experiments were performed using a
computer-controlled fretting machine (DUCOM
TR281-M, Bangalore, India), which produces a linear
relative oscillating motion with ball-on-flat configura-
tion. By a stepper motor, the flat sample is made to os-
cillate with a relative linear displacement of constant
stroke and frequency. An inductive displacement trans-
ducer monitors the displacement of the flat sample and
a piezoelectric transducer is used to measure the friction
force. The variation in tangential force is recorded and
the corresponding COF is calculated on-line with the
help of a computer-based data acquisition system. A fret-
ting loop gives the evolution of the tangential force as a
function of the displacement amplitude during each cycle.
The COF is further evaluated from the average of the two
plateau values of the tangential force in the fretting loop.
The use of the same testing set-up has been made in our
research on various ceramics and composite systems.13,24
A schematic representation of the test configuration is
presented in Fig. 2. The TiB2 flat samples were fretted
against two different counterbodies (bearing grade steel
91
Fig. 2. Schematic of the fretting test set-up. The testing conditions:
constants-stroke length 100 mm, oscillation frequency 4 Hz and
cycles (100,000); variables—normal load (P: 2, 5, and 10 N).
and WC–6 wt% Co balls of 10 mm diameter). The TiB2-
based ceramics were mechanically held on a translation
table, which was made to oscillate at a preset relative
linear displacement of constant stroke and frequency.
The flat specimens (TiB2 and TiB2–5 wt% TiSi2)
for fretting tests were cut from the hot-pressed disks and
machined into bar shapes with dimensions of 3 mm 
4 mm  20 mm. The samples were polished to a surface
roughness of RaB0.20 mm by standard ceramographic
techniques. The surface roughness of the samples was
measured by using laser surface profilometer. The me-
chanical properties of all the TiB2-based ceramics and
the counterbodies are presented in Table I. It can be
noted that TiB2–5 wt% TiSi2 exhibited superior hardness
(Hv5B25 GPa), indentation toughness (B6 MPa m1/2)
and elastic modulus (B518 GPa), when compared with
monolithic TiB2. As per the suppliers data, the bearing
grade steel ball (commercial SAE 52100 grade) pos-
sessing a hardness of HvB7 GPa and WC–6 wt% Co
(cemented carbide) balls are characterized by a hardness
of B18 GPa and toughness of B14 MPa m1/2.
Before the fretting tests, all the flats and balls were
ultrasonically cleaned in acetone. The displacement
stroke, normal load, frequency, and number of fretting
cycles are the external variables associated with the fret-
ting machine. The fretting experiments were performed
at an oscillating frequency of 4 Hz and 100 mm linear
92 International Journal of Applied Ceramic Technology—Brahma Raju and Basu
Table I. Mechanical Properties and Surface Roughness of the Flat TiB2 Ceramics as Well as the Bearing Grade
Steel and WC–6 wt% Co Counterbody Materials
Vickers hardness, Elastic modulus
Material HV 5 (GPa)
TiB2 18.3
TiB2–5 wt% TiSi2 25.2
Bearing grade steel ball 7.0
WC–6 wt% Co ball 18.0
Data are supplied by the commercial supplier.
stroke, for a duration of 100,000 cycles. The influence
of varying the load (P: 2, 5, 10 N) on the friction and
wear response of all the materials were investigated. It
must be mentioned that the combination of these test-
ing parameters resulted in the gross slip fretting con-
tacts. All experiments were conducted in an ambient
atmosphere at room temperature (301721C) with RH
of 4575%.
Characterization of the Worn Surfaces
After the test, detailed characterization of the worn
surfaces of the TiB2–TiSi2 flat and counterbody samples
were done using SEM. The compositional analysis of
the worn surfaces and wear debris is carried out using
EDS. The wear scar profiles on each sample were obtained
using a computer-controlled laser surface profilometer
(Mahr-Perthometer PGK 120, Göttingen, Germany).
The wear volume was calculated by integrating the
surface area of each 2D profile (extracted from different
locations on 3D profile) over distance for the flat sample.
From the measured wear volume, the specific wear rates
[wear volume/(load  distance)] were calculated.
Results
Friction and Wear Behavior Against Steel
Counterbody
The frictional behavior of both the monolithic
TiB2 and TiB2 reinforced with 5 wt% TiSi2 flat sam-
ples were investigated during fretting against bearing
steel at varying load from 2 to 10 N. During the fretting
test the other variables (100,000 cycles, 100 mm ampli-
tude and 4 Hz frequency) are kept constant. The COF
against number of cycles for different ceramics are plot-
ted in Fig. 3. In general, both the TiB2 ceramics exhibit
Vol. 7, No. 1, 2010
Fracture toughness Surface roughness
(GPs) (MPa m 1/2 ) (R a, lm)
434.9 3.8 0.20
517.9 5.8 0.20
210.0 — 0.02
630.0 — 0.02
very similar behavior. In particular, COF against steel
increases with an increase in load; while less variation in
COF is noticed in case of cemented carbide counter-
body. The increase in COF with load (up to 5 N) for
both the TiB2 ceramics against steel can be attributed to
the abrasion-induced continuous material removal from
steel counterbody. However, COF at 10 N load is al-
most comparable or even less than that of at 5 N. The
reduction in COF at higher loads of 10 N is due to the
establishment of the contact between the tribochemical
layers, instead of the virgin surfaces of the contacting
materials. It is also evident that the COF plot consists of
many fluctuations during fretting at lower loads up to
5 N, while it reduces considerably at 10 N load (Fig. 3a).
Such characteristic frictional behavior is also noticed
with the TiB2–5 wt% TiSi2. However, the COF values
are relatively higher at all loads when compared with
monolithic TiB2 (see Fig. 3b).
The wear volumes of TiB2 ceramics were estimated,
using laser surface profilometry. A typical 3D profile of
worn surface of TiB2–5 wt% TiSi2 is shown in Fig. 4a.
A closer look at Fig. 4a reveals the characteristic peaks
at the worn region, instead of depths, which are com-
posed of various 2D profiles. Such observations impli-
cate the negative wear phenomena of the TiB2 samples,
when fretted against steel counterbody (see also Fig. 4b).
This essentially indicates that on 2D profiles, if taken
at various places of worn surface, hills instead of valleys
are commonly observed/recorded for worn surfaces. In
contrast, the fretted surfaces on ceramics, after testing
against WC–Co, show regular 3D or 2D profiles, as
typically observed for worn material. Therefore, the
wear volumes were calculated for such cases, where
2D profiles show pronounced valley and accordingly,
the area/maximum depth of profile could be measured.
Furthermore, the measured wear volumes are normal-
ized with respect to load and total sliding distance
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2 93

(a) 1.0 (b) 1.0

TiB2 vs. Steel TiB2 -5 wt.% TiSi2 Vs. Steel
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
COF

COF
0.5 0.5
0.4 0.4
0.3 0.3
0.2 2N 0.2 2N
0.1 5N 0.1 5N
10N 10N
0.0 0.0
0 20000 40000 60000 80000 100000 0 20000 40000 60000 80000 100000
No. of cycles No. of cycles

(c) 1.0 (d) 1.0

TiB2 Vs. WC-6 wt.% Co TiB2 -5 wt.% TiSi2 Vs. WC-6 wt.% Co
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
COF
COF

0.5 0.5
0.4 0.4
0.3 0.3
0.2 2N 0.2 2N
0.1 5N 0.1 5N
10N 10N
0.0 0.0
0 20000 40000 60000 80000 100000 0 20000 40000 60000 80000 100000
No. of cycles No. of cycles

Fig. 3. The evolution of coefficient of friction (COF) versus number of cycles for various investigated tribocouples at different loads. Fretting
conditions: 2–10 N load, 4 Hz frequency, 100,000 cycles, and 100 mm stroke length.

(number of cycles  displacement stroke  2) in order to
obtain normalized specific wear rates. The wear volume
measurements and corresponding wear rates of the TiB2
ceramics are shown in Fig. 5. The wear volume increases
with the load for both the materials. The TiB2–5 wt%
TiSi2 ceramic exhibited the highest wear rate (5.2 
106 mm3/N m), while the monolithic TiB2 exhibited
lower wear rate (2.8  106 mm3/N m).
It must be mentioned here that wear volume is a
measure of the amount of material removed during in-
teractive relative motion, whereas specific wear rate gives
an idea of the severity of material loss with load and
sliding distance. In other words, such wear rates pro-
vide an idea of the probability of removal of a material
fragment during a given asperity encounter. Archard35
related wear volume and load by the following ex-
pression:
v ¼ KPx=H ð1Þ
where v is the wear volume, P is the normal load, x is the
sliding distance, H is the hardness of the material under
investigation, and K is the probability of formation of a
wear particle during a particular asperity interaction.
Equation (1) can be rewritten in another form
K =H ¼ v=xP ð2Þ
It must be noted that right hand side of Eq. (2)
gives the wear volume per unit sliding distance per unit
load (or the specific wear rate). Hence, the left hand
term (K/H), which is a measure of the probability of
94 International Journal of Applied Ceramic Technology—Brahma Raju and Basu Vol. 7, No. 1, 2010

Fig. 4. Three-dimensional topographical view of the worn surface of TiB2–5 wt% TiSi2/steel at 10 N load (a), the maximum wear peak
profiles obtained at various loading conditions of the TiB2 composite after fretting against steel counterbody (b), three-dimensional
topographical view of worn surface of the TiB2–5 wt% TiSi2/WC–6 wt% Co at 10 N load (c), and the maximum wear depth profiles obtained
at various loading conditions of the TiB2 composite after fretting against WC–6 wt% Co counterbody (d). Fretting conditions: 4 Hz frequency,
100,000 cycles, and 100 mm stroke length.

wear particle formation normalized by hardness,
signifies the estimated wear rate. Although in general,
the amount of material removed is expected to increase
with increase in load, yet depending upon the
operative wear mechanisms, the probability of further
material removal (specific wear rate) may not increase
accordingly.
Friction and Wear Behavior Against WC–Co
Counterbody
Figures 3c and d reveal that the COF of TiB2 ce-
ramics varies insignificantly with the load, when fretted
against WC–Co-cemented carbide ball. It can be ob-
served that TiB2–5 wt% TiSi2 exhibits better frictional
properties than that of monolithic TiB2. The average
COF of the TiB2 ceramics are shown in Table II.
Among all the tribocouples, lowest COF of B0.49 is
noticed with the TiB2–5 wt% TiSi2 against cemented
carbide. It has to be mentioned here that much fluctu-
ations in the frictional response could be observed for
both the tribocouples. Such characteristic features can
be attributed to the third body (wear debris) presence
during fretting. A common observation is that the COF
values of the TiB2 ceramics are relatively low after fret-
ting against WC-cemented carbide, when compared
with the steel counterbody (Table II).
A typical 3D profile of worn surface of TiB2–5 wt%
TiSi2 is shown in Fig. 4c. The wear depth profiles at
various loads are presented in Fig. 4d. It can be noted
that maximum wear depth with wider area is observable
at a highest fretting load of 10 N. Figure 5b represents
the effect of load on the wear volume and wear rates of
the TiB2 ceramic fretted against cemented carbide. The
wear volume of both the materials increases with in-
creasing load. However, highest wear volume (B3 
104 mm3 at a load of 10 N) is measured for the mono-
lithic TiB2. Among all the material combinations,
TiB2–5 wt% TiSi2 exhibited lowest wear rate of 1.2 
106 mm3/N m at 10 N load. The above observations
indicate that different frictional behavior is operative,
when the TiB2-based materials are fretted against the
two counterbodies (steel and WC–Co-cemented car-
bide). The plausible reasons behind such contrasting
behavior will be critically analyzed in the subsequent
sections.
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2 95

6.5 6.5
(a) Filled symbols: Wear volume
6.0 Monolithic TiB2 6.0
5.5 TiB2-5 wt.% TiSi2 5.5

Wear rate (–1 x 10–6 mm3 / Nm)

Wear volume (–1 x 10–4 mm3)

5.0 Unfilled symbols: Wear rate 5.0

TiB2
4.5 TiB2-5 wt.% TiSi2 4.5
4.0 4.0
3.5
3.5
3.0
3.0
2.5
2.5
2.0
2.0
1.5
1.5
1.0
1.0
2 4 6 8 10
Load (N)

6.0 6.0
(b) Filled symbols: Wear volume
5.5 5.5
Monolithic TiB2
5.0 TiB2-5 wt.% TiSi2 5.0

Wear rate (x 10–6 mm3 / Nm)

4.5 Unfilled symbols: Wear rate
Wear volume (x 10–4 mm3)

4.5
TiB2
4.0
TiB2-5 wt.% TiSi2 4.0
3.5
3.5
3.0
3.0
2.5
2.5
2.0
1.5 2.0

1.0 1.5

0.5 1.0
0.0 0.5
2 4 6 8 10
Load (N)

Fig. 5. Variation of wear volume and wear rate of the investigated TiB2 ceramics as a function of load after fretting against steel counterbody
(a) and WC–6 wt% Co counterbody (b). Fretting conditions: 2–10 N load, 4 Hz frequency, 100,000 cycles, and 100 mm stroke length.

SEM Observations of Worn Surfaces
In order to understand the wear mechanisms, the
topographical observations of the worn surfaces was
made using SEM, and simultaneously, compositional
analyses of the observed features have been performed
using EDS, attached with SEM (Figs. 7–10). In the
following, specific observations are mentioned with ref-
erence to two different counterbodies.
Figure 6 shows SEM images of monolithic TiB2
after fretting against steel counterbody at various loads
of 2, 5, and 10 N. The secondary electron images (Figs.
6a, c, and e) reveals the topography of the worn surfaces
covered with adherent tribolayer. The corresponding
BSE images (inset in Fig. 6) provide evidences of the
formation of a thin adherent tribolayer on the surface
even at a lower load of 2 N. However, a thick protective
layer formation can be clearly noticed with increasing
load. Similar microstructural features are also observed
with TiB2–5 wt% TiSi2/steel tribocouple (not shown).
A representative wear scar of the TiB2 composite after
fretting at 10 N load is shown in Fig. 7a. The corre-
96 International Journal of Applied Ceramic Technology—Brahma Raju and Basu Vol. 7, No. 1, 2010

Table II. Summary of the Average COF, Wear Volume, and Wear Rate of the Different Investigated
Tribocouples as a Function of the Load
Wear volume of TiB 2 flat Wear rate of TiB2 flat
Average COF materials (mm 3 )  10 4 materials (mm 3 /N m)  10 6

Tribocouple 2N 5N 10 N 2N 5N 10 N 2N 5N 10 N
TiB2 versus steel 0.58 0.69 0.63 1.87 2.98 4.15 4.67 2.98 2.07
TiB2–5 wt% TiSi2 0.62 0.70 0.67 2.09 3.62 5.48 5.22 3.62 2.74
versus steel
TiB2 versus WC–Co 0.56 0.55 0.56 1.64 2.34 3.02 4.10 2.34 1.51
TiB2–5 wt% TiSi2 0.51 0.49 0.56 1.15 2.28 2.53 2.88 2.28 1.26
versus WC–Co
The presented data is an average of at least two test results.
COF, coefficient of friction.

sponding EDS analysis of tribolayer (magnified image)
reveals strong peaks of Fe and O along with weak Ti and
B elements. Figure 7c shows the worn surface of steel
ball at 10 N load. It reveals the presence of tribolayer
and severe abrasion grooves. The EDS analysis of the
worn surface (inset of Fig. 7d) indicated primarily Fe
and O peaks. In order to further understand the tribo-
chemistry of the layer, EDS analysis is carried out on the
worn surface of TiB2–5 wt% TiSi2 after fretting at 2, 5,
and 10 N loads (see Fig. 8). Although the presence of O,
Ti, and Fe are detected after testing at 2 N load; much
pronounced peaks of O and Fe can only be noticed at
5 and 10 N load. It is possible that TixOy, FexOy or their
mixed oxides form during fretting of the TiB2 ceramics
against steel.
The topographical features of the wear scars of the
monolithic TiB2 after fretting against the cemented car-
bide are shown in Fig. 9. The worn surfaces are much
different from those obtained during fretting against
steel. The mild abrasive scratches, along with brittle
fracture induced pull-outs near the edges of wear are
observed for monolithic TiB2 (see insets of Figs. 9b
and d). The worn surfaces along with the corresponding
EDS of the TiB2 flat after fretting at a load of 10 N is
shown in Fig. 10. The presence of wear debris near the
edge of the wear scar is observed on TiB2 sample (see
Fig. 10a). It reveals the presence of very fine debris along
with agglomerated particles. Mild abrasion along with
the minute particle pullouts are noticed and the forma-
tion of tribochemical layer on the worn surfaces was not
observed. EDS spectrum obtained from the abraded
area of TiB2 indicates the predominant presence of Ti
and minute O and no evidence of transferred W can be
found (inset of Fig. 10b). EDS analysis of wear debris
reveals the presence of titanium and oxygen (Figs. 10c
and d). In case of TiB2–5 wt% TiSi2/cemented carbide
tribosystem, similar morphology of worn surfaces, like
monolithic TiB2, is noticed (see Figs. 11a and b). Figure
11 compares the worn surfaces of both the TiB2–5 wt%
TiSi2 and WC–Co counterbody after fretting at a load
of 10 N. The size of wear scar (B451 mm) for both the
TiB2 composite and the WC–Co ball remains almost
same. SEM observation of the worn surface of WC–Co
ball shows the occurrence of very mild abrasion wear,
with grain pull-out. The corresponding EDS spectrum
obtained from the abraded area of cemented carbide ball
indicates the predominant presence of W and minute
Co and O. No evidence of transferred Ti can be found
(inset of Fig. 11d). Further discussion regarding the
wear mechanisms responsible for different tribological
responses of the TiB2-based materials will be presented
in the following section.
Discussion
Based on the experimental results and SEM–EDS
investigation of worn surfaces of both the TiB2 ceramics
and counterbodies, we will now make an attempt to
discuss the underlying material removal mechanisms
during fretting. It can be realized that variation of
load and counterbody material notably affects the fric-
tion and wear behavior of TiB2-based materials.
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2 97

Fig. 6. Overview and details of as-fretted surfaces (scanning electron microscope [SEM] images) of monolithic TiB2 after 2 N (a, b),
5 N (c, d), and 10 N loads (e, f). (a), (c), and (e) represent the topography of worn surfaces (SE SEM images), while (b), (d), and (f) indicate
the magnified view of worn surfaces (BSE SEM images). Fretting conditions: 4 Hz frequency, 100 mm stroke length, and 100,000 cycles:
counterbody: bearing steel (arrow marks indicate the fretting direction, inset diagrams are BSE images of the worn surfaces).

Negative Wear Phenomena of TiB2 Ceramics
Against Steel
It is known that during initial stages of fretting, the
deformation or fracture of surface asperities of mating
bodies result in the formation of wear debris. The fric-
tional heat, generated at the sliding contacts, oxidizes
the debris particles at ambient testing conditions and
leads to the tribochemical reactions. Both the TiB2 ce-
ramics exhibits almost similar trend of increasing COF
with increasing load. The direct contact of hard TiB2
ceramic with the steel counterbody causes the adhesion
and subsequent fracture of asperities of mating surfaces
and leads to the wear debris formation. At 2 N load,
fluctuations in COF curve is mainly due to the forma-
tion of wear debris and constant adhesion/abrasion of
the contact surfaces. During the test, the wear debris
particles are compacted to form a tribolayer under load
and atmospheric conditions. When the load increases to
5 or 10 N, this takes place more promptly.
98 International Journal of Applied Ceramic Technology—Brahma Raju and Basu Vol. 7, No. 1, 2010

(a) (b)

(c) (d)

Fig. 7. Worn surfaces of TiB2–5 wt% TiSi2 (a), the magnified image of the worn surface along with the energy-dispersive spectroscopy (EDS)
reveals the tribochemical layer (b), the corresponding worn surface of steel ball (c), and the magnified image of the worn surface along with the
EDS (d). Fretting conditions: 10 N load, 4 Hz frequency, 100 mm stroke length, and 100,000 cycles: counterbody: bearing steel (arrow marks
indicate the fretting direction).

From Table I, it is very clear that the TiB2 samples
are B2.6–3.5 times harder than the steel ball. Hence,
during fretting under the application of load, the steel
body got abraded by TiB2 and subsequently, the wear
debris of steel got compacted and form tribochemical
layer on the mating contact surfaces. Figure 4b indicates
that the tribolayer thickness increases (from 2.5 to
8 mm) with increasing the load from 2 to 10 N. The
topography of the worn surfaces of TiB2 samples further
confirms the increment of the adherent stable tribolayer
with the load (see Fig. 6). Based on the SEM–EDS of
worn surfaces of the TiB2 ceramics as well as steel
counterbody during fretting, it is clear that the oxide
debris are formed mainly from steel surface. The worn
surfaces of steel body clearly evidences abrasive grooves.
However, no such feature can be found on the TiB2
counterbody (see Fig. 7). A closer look at the EDS
spectra of both the worn surfaces of TiB2–5 wt% TiSi2
sample and the steel ball at a load of 10 N reveals the
predominant presence of strong O and Fe peaks. These
observations clearly indicate the formation of iron oxide
layer on the worn surfaces. Figure 8 represents that at a
lower load of 2 N, the tribolayer is composed of Ti–
Fe–O, while traces of Ti along with Fe and O at higher
loads (  5 N). It reflects that with increasing load,
more iron is getting transferred to the counterbody. A
detailed study on tribochemistry of TiB2/steel tribocou-
ple by using Raman spectroscopy and XPS analysis can
be found in our earlier work.4,23 Such studies revealed
that the tribolayer composed of TiO2 and Fe2O3 for the
TiB2/steel-fretting contact. The present experimental
results also identify similar tribochemistry of the worn
surfaces. The possible tribochemical reactions involved
are as follows:
2TiB2 þ 5O2 ! 2TiO2 þ 2B2 O3 ð3Þ
Fe þ ð1=2ÞO2 ! FeO ð4Þ
2Fe þ ð3=2ÞO2 ! Fe2 O3 ð5Þ
3Fe þ 2O2 ! Fe3 O4 ð6Þ
In the present investigation, we observe a new phe-
nomenon of negative wear of TiB2 ceramics under the
present testing conditions. Table II presents that nega-
tive wear volume of the samples systematically increases
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2
Fig. 8. Energy-dispersive spectroscopy compositional analysis of the
worn surfaces of TiB2–5 wt% TiSi2 after fretting at various
loading conditions for a duration of 100 K cycles: Other fretting
parameters include: 4 Hz frequency, 100 mm stroke length,
counterbody: bearing steel.
with the load. However, maximum negative wear vol-
ume of 5.4  104 mm3 is measured with the TiB2–
5 wt% TiSi2 and is attributed to its high density and
high hardness. These observations comprehensively
99
demonstrate that as the TiB2 composite exhibits better
mechanical properties, it wears out the counterbody
more than the monolithic TiB2 and results in higher
values of negative wear. Endo and Maru36 reported that
for cemented carbide/steel-fretting contact, a negative
wear is induced due to the adherence of iron oxide of
the steel body to cemented carbide. It is interesting to
note that wear rate decreases with increasing load (see
Table II). At higher loads, the contact between the
tribolayers of the tribocouples reduces the probability
of further wear of steel counterbody. SEM observations
also reveal the presence of a protective tribolayer at
higher load (10 N).
Wear behavior of TiB2 Ceramics Against WC–Co
Based on the friction and wear data as well as to-
pographical analysis of tribosurfaces, the tribological
behavior TiB2/WC–Co tribocouple under unlubricated
fretting conditions will be discussed in this section. Fur-
ther, the possible wear mechanisms can be understood
in the light of the friction and wear behavior of the
materials.
It has been observed that the frictional behavior of
both the TiB2-based ceramics, during fretting against
the WC–Co-cemented carbide counterbody are nearly
similar. Up to a load of 5 N, the COF curves show
fluctuations during the entire fretting duration. It can
be attributed to the formation of wear debris and their
escape/displacement from the contact zone during fret-
ting. It has to be mentioned here that fretting wear has
the characteristic of forming considerable amounts of
very fine oxide debris and the wear debris particles sub-
sequently govern the wear of the materials.3 Singer37
reported that wear debris can reduce friction by accom-
modating sliding and absorbing the deformation energy
and thereby, also reduce wear. The COF of TiB2/
cemented carbide is relatively lower when compared
with TiB2/steel tribocouple. It is generally recognized
that interactive relative motion of a ceramic against an-
other hard ceramic, as compared with ceramic against
metal, leads to lower friction and wear due to formation
of smaller real contact area. Such a phenomenon is ex-
pected as a result of nonconformity and limited elastic/
plastic deformation between the two surfaces.
Looking at the SEM images, the worn surfaces
are characterized with mild abrasive scratches, grain
pullouts, and polishing of the surfaces (Fig. 9). How-
ever, at certain regions, more material removal and par-
100 International Journal of Applied Ceramic Technology—Brahma Raju and Basu Vol. 7, No. 1, 2010

Fig. 9. Scanning electron microscope images revealing the topography of worn surfaces of monolithic TiB2 at 2 N (a, b) and 5 N loads
(c, d). (a) and (c) represent the wear scars, while (b) and (d) indicate the magnified images of the worn surfaces. Fretting conditions:
4 Hz frequency, 100 mm stroke length, and 100,000 cycles: counterbody: WC–6 wt% Co (double-headed arrow marks indicate the
fretting direction, inset diagrams are representative of highly worn regions at certain region of wear scars: single-headed arrow marks
from (a) and (c)).

ticle pullouts are observed (see inset Figs. 9b and d).
Even at a higher load of 10 N, the characteristics of the
worn surface remains the same as that of 2 and 5 N.
With increasing load, relatively more abrasive grooves
can be seen (Fig. 10). EDS analysis of the worn surface
reveals strong Ti peak and traces of O. There is no in-
dication of any transfer of material from the cemented
carbide counterbody. From the micrographs, finer and
nearly spherical wear debris particles can be observed on
the surfaces at higher loads (Fig. 10). A large quantity of
wear debris is located around the wear scar and some
amount of compacted debris could be found on the
worn surface. EDS analysis of wear debris also reveals
the presence of Ti and O only (Fig. 10d). It further
confirms that except the third body abrasion, no tribo-
chemical wear takes place for TiB2/cemented carbide
tribocouples.
A representative worn surface of the TiB2 compos-
ite shows mild abrasive grooves and the corresponding
EDS reveals the presence of Ti, B, Si, and O (Figs. 11a
and b). Here it has to be mentioned that the micro-
structure of unworn surface reveals the presence of sec-
ondary Ti5Si3 phase (black contrast), compacted wear
debris and particle pullouts. The worn surface of WC–
Co ball also consists of mild abrasive grooves and EDS
analysis of the worn surface reveals W, Co, and O peaks.
Hence, the primary wear mechanism is abrasion and
no tribochemical effects, except mild oxidation can be
noticed for the TiB2/WC–Co tribosystem. Maximum
wear volume of 3  104 is measured with TiB2/WC–
Co at 10 N load. From Table II, it can be noticed that
both the COF and wear volumes of TiB2 composites are
relatively lower than monolithic TiB2. Hence, a better
wear resistance of TiB2 composites can be attributed to
its higher density and good mechanical properties.
Yang et al.25 investigated tribological performance
of TiB2 against different counterbodies (SiC, Al2O3,
and mullite). The COF varied between 0.63 and 0.77 and
the specific wear rates from (7.1 to 68.5)  105 mm3/
N m with different tribocouples. For TiB2/alumina fret-
www.ceramics.org/ACT Wear Mechanisms of TiB2 and TiB2–TiSi2 101

(a) (b)

(c) (d)

Fig. 10. Scanning electron microscope images revealing the topography of worn surface of monolithic TiB2 along with the wear debris after
fretting against WC–6 wt% Co at 10 N load (a), the magnified image of worn surface along with the energy-dispersive spectroscopy (EDS) (b),
magnified image of wear debris (c), and the corresponding EDS of wear debris (d) Fretting conditions: 4 Hz frequency, 100 mm stroke length,
and 100,000 cycles (double-headed arrow marks indicate the fretting direction).

ting contacts, a steady-state COF of 0.5 and wear rate of
2  106 mm3/N m is reported.23 In the present inves-
tigation, the COF lies between 0.49 and 0.56 and wear
rate measured to be (1.2–4.1)  106 mm3/N m when
the TiB2 ceramics fretted against WC–Co counterbody,
depending on the loading condition. Our experimental
results clearly indicate that the friction and wear proper-
ties of the developed TiB2 ceramics are relatively better or
comparable with the earlier reported TiB2 tribosystems.
The results of the present study therefore reveal the po-
tentiality of the TiB2 materials in contact with the steel
and cemented carbide for wear resistant applications.
Conclusions
The present investigation reports the tribological
performance of TiB2 and TiB2–5 wt% TiSi2, in fretting
contact with two different counterbodies (steel and
WC–Co cemented carbide) under varied load condi-
tions.
(a) In case of TiB2/steel tribosystem, the COF var-
ied between 0.58 and 0.70. However, relatively higher
COF against steel is noticed with TiB2–5 wt% TiSi2 at
all loads, when compared with monolithic TiB2.
(b) Adhesion, abrasion, and tribochemical layer
formation are identified as the major wear mechanism
for TiB2 against steel. The harder TiB2 abrades the steel
counterbody and the transfer/sticking of tribolayer to
the TiB2 surface contributes to negative wear of TiB2
ceramics. Maximum wear rate of 5.2  106 mm3/
N m is measured with the TiB2 composite.
(c) In case of TiB2/WC–Co tribosystem, the COF
varied between 0.49 and 0.56. The COF values of the
TiB2 composites are relatively lower than monolithic
TiB2. The presence of wear debris as third body between
the contacting bodies appears to cause low COF.
(d) Adhesion and mild abrasion are major wear
mechanisms for the TiB2 ceramics when fretted against
cemented carbide. The wear rate varied between (1.2
and 4.1)  106 mm3/N m for both the TiB2 ceramics
and falls with in the mild wear regime. However, rel-
102 International Journal of Applied Ceramic Technology—Brahma Raju and Basu Vol. 7, No. 1, 2010

(a) (b)

(c) (d)

Fig. 11. Worn surfaces of TiB2–5 wt% TiSi2 (a), the magnified image of the worn surface along with the energy-dispersive spectroscopy
(EDS) (b); the corresponding worn surface of WC–6 wt% Co ball (c), and the magnified image of the worn surface along with the EDS
(d). Fretting conditions: 10 N load, 4 Hz frequency, 100 mm stroke length, and 100,000 cycles (arrow marks indicate the fretting direction).

5. B. Basu, G. B. Raju, and A. K. Suri, ‘‘Processing and Properties of Monolithic

atively lower wear rates are measured with the TiB2
composite, when compared with monolithic TiB2. The
better wear resistance of TiB2 composite is attributed
to microstructural difference and better mechanical
properties.
Acknowledgments
G. B. R. thanks Dr. S. J. Cho and his group mem-
bers at KRISS, Korea for extending co-operation during
his stay to hot press some of the ceramic samples, which
are used in the present investigation.
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