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Wear 265 (2008) 286–291

Tribological properties of pressureless sintered advanced alumina

matrix ceramic materials improved by Al–Ti–B and diopside
Changxia Liu a,b,1 , Jianhua Zhang a,∗ , Junlong Sun b , Xihua Zhang c
a
Department of Mechanical Engineering, Shandong University, Jinan 250061, Shandong Province, PR China
b School of transportation, Ludong University, Yantai 264025, Shandong Province, P.R. China
c Department of Materials Science and Engineering, Shandong University, Jinan 250061,Shandong Province, P.R. China

Received 26 December 2006; received in revised form 29 August 2007; accepted 22 October 2007
Available online 4 March 2008

Abstract
Al–Ti–B master alloys and diopside were incorporated into alumina matrix and advanced alumina matrix ceramic materials were fabricated
by pressureless sintering technology. The mechanical properties of this new composite as well as its wear behaviours, coupled with carbon steel
ring in unlubricated conditions at room temperature, were investigated systemically. SEM technology was adopted to observe the worn surfaces of
specimens and wear mechanisms were simultaneously discussed. Analysis of the experimental data and observations on the worn surfaces revealed
that the improvement in the wear resistance of the composites might be attributed mainly to the strong toughening effect due to the introduction
of Al–Ti–B master alloys and diopside in the alumina matrix.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Alumina; Diopside; Al–Ti–B master alloys; Pressureless sintering; Friction and wear

1. Introduction environment on the tribological behaviour of alumina matrix

Due to the virtues of low weight, high stiffness, corrosion
resistance, wear resistance, low coefficient of thermal expan-
sion and friction coefficient, advanced alumina matrix ceramic
materials offer a great potential in the fields of fine measuring
implement, fine sliding way, working platform and high-speed
bearing, etc., where high precision durability and long work-
ing life are required. The introduction of diopside into alumina
matrix can decrease the manufacturing costs, shorten the pro-
duction cycle and improve the mechanical properties [1]. Low
price of Al–Ti–B master alloys permits its widespread applica-
tions to the refining technology of Al and its alloys [2,3]. There
are few articles, however, reporting the tribological properties of
Al–Ti–B master alloys and diopside reinforced alumina matrix
ceramic composites.
There have been numerous investigations exploring the
influence of test conditions contact geometry, additives and
∗
Corresponding author. Tel.: +1 412 576 8099.
E-mail addresses: hester5371@gmail.com (C. Liu),
jhzhang@sdu.edu.cn (J. Zhang).
1 Tel.: +86 531 82266727.
ceramics due to their growing importance for high wear resis-
tance application [4–9]. In this paper, the authors investigated
the influence of liner speed and load values on the friction and
wear behaviour of advanced alumina matrix ceramic materials
toughened by Al–Ti–B master alloys and diopside. The object
of this research is to show the potential of the fabricated alu-
mina matrix ceramic composites, reinforced by Al–Ti–B master
alloys and diopside, as friction materials for applications such as
fine measuring implement, fine sliding way, working platform,
etc.
2. Experimental procedure
2.1. Materials and specimens
Commercial high purity (99.99%) and small grain size
(0.5–1 ␮m) of Al2 O3 powder was selected as the starting mate-
rials. Al–Ti–B master alloys and diopside (MgCa (SiO3 )2 )
were adopted as additives. Al–Ti–B master alloys are devel-
oped by the Department of Materials Science and Engineering,
Shandong University, China. This alloy has the composition
of Al–5%Ti–1%B. Diopside is composed of SiO2 (55 wt.%),

0043-1648/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2007.10.016
 C. Liu et al. / Wear 265 (2008) 286–291 287

Table 1
Physical characteristics of Al–Ti–B and diopside
Raw materials Grain size (␮m) Density (g/cm3 ) Impurities (mass fraction, %)<

Al–Ti–B Fe Si Cu V Mn
<100 2.75 0.140 0.107 0.002 0.100 0.009
Al2 O3 Ni Ti Fe Na
Diopside <50 3.30 2.000 0.200 0.200 0.550 0.050

CaO (24 wt.%) and MgO (18 wt.%). The physical characteris-
tics of Al–Ti–B and diopside are listed in Table 1. The purity
of diopside is 97%. The crystal structure is monoclinic, space
group C2/c with a = 0.9746–0.9845 nm, b = 0.8899–0.9024 nm,
c = 0.5251–0.5245 nm, β = 105◦ 38 –104◦ 44 , Z = 4. The melting
point of Al–Ti–B is about 700 ◦ C and that of diopside is 1390 ◦ C,
so the liquid-phase sintering begins as the temperature goes
above 700 ◦ C [10,11]. Simultaneously, Al–Ti–B and diopside
can react with alumina and form AlN, TiN, mullite, anorthite
and CaO·6Al2 O3 during the sintering process. Liquid-phase
sintering and interface reaction all contribute to the promotion
of sintering [1,10,11]. Interface reaction strengthens the grain
bondings and makes the fracture mechanism of the composites
change from intergranular failure to the combination of inter-
granular failure and transgranular failure [1]. The change of
fracture mechanism and the good refining effect of Al–Ti–B
master alloys to alumina [10,11] all contribute to the increasing
in fracture toughness.
The compositions and mechanical properties of pressureless
sintered composites are listed in Table 2. (The suffix in AB0 D0 ,
AB4 D6 and AB4 D10 , respectively represents the volume content
of Al–Ti–B and diopside. For example, AB4 D6 means the con-
tent of Al–Ti–B and diopside are 4 and 6 vol.%, respectively.)
The relative density of the composites is calculated according to
the equation:
ρA
ρR =
ρT
The value of theoretical density ρT depends on the composi-
tions of the composite, and can be calculated as follows

ρT = ρ i Vi (3)
where ρi and Vi are the theoretical density and volume content
of each composition, respectively.
The raw materials were blended together according to cer-
tain proportions and ball milled for 60 h in an alcohol medium to
obtain a homogeneous mixture. Then the slurry was dried in vac-
uum and screened and green bodies (50 mm × 50 mm × 50 mm)
were shaped by isostatic cool pressing technology in rubber
molds. Lastly, these dense green bodies were sintered at 1520 ◦ C
(heating rate: 20 ◦ C/min) for 180 min in N2 atmosphere by pres-
sureless sintering.
2.2. Characterization
The test specimens with nominal dimensions of 3 mm ×
4 mm × 36 mm were cut from the pressureless sintered bodies.
Densities of the specimens were measured by the Archimedes
method. Vickers hardness was measured on polished surface
with a load of 9.8 N for 5 s with a micro-hardness tester (MH-6).
Fracture toughness measurement was performed using inden-
tation method. The indentations on the sample surfaces were
generated in a hardness tester (Hv-120), and the formula pro-
posed by Cook and Lawn [12] was used to calculate the final
fracture toughness.
(1)
2.3. Friction and wear tests

where ρR is the relative density, ρA the actual density of the The friction and wear tests were carried out in a block-on-ring
sintered specimen, ρr the theoretical density of the composite. abrasion apparatus (MRH-3). The contact schematic diagram for
The actual density ρA can be obtained by measuring the mass (M) the frictional couple is shown in Fig. 1. A plain carbon steel ring
and volume (V) of the sintered specimen, and then determined (HRC 38–45) with outer diameter of 50 mm, inner diameter of
by the expression 35 mm and thickness of 10 mm, was used as the counterpart. The
investigated ceramics were cut into specimens with the dimen-
sions of 5 mm × 8 mm × 16 mm. The specimens were ground
M and polished with diamond paste to an average surface roughness
ρA = (2)
V of Ra 0.1 ␮m. Sliding was performed under ambient conditions

Table 2
Compositions and mechanical properties of pressureless sintered alumina matrix ceramics
Specimens Compositions (vol.%) Relative density (%) Hardness (GPa) Fracture toughness (MPa m1/2 )

AB0 D0 100% Al2 O3 88.6 9.14 3.82

AB4 D6 90% Al2 O3 + 4%Al–Ti–B + 6% diopside 96.13 16.02 5.11
AB4 D10 86% Al2 O3 + 4%Al–Ti–B + 10% diopside 96.73 14.64 5.26
288 C. Liu et al. / Wear 265 (2008) 286–291

Fig. 2. Schematic diagram of wear traces on the block specimens.

Fig. 1. Contact schematic diagram for the frictional couple.

of temperature and humidity over a period of 30 min. For all test

specimens, the wear experiments were carried out with varying
loads (50, 100, 150, 200 N) and varying liner speeds (0.2, 0.4,
0.6, and 0.8 m/s).
The friction coefficient is calculated according to the equa-
tion: Fig. 3. Friction coefficient vs. normal load for AB0 D0 specimen with different
M F liner speed.
μ= = (4)
PR P
3. Results and discussion
where μ is the friction coefficient, M the force moment of fric-
tion, R the outer radius of carbon steel ring (25 mm), P refers to 3.1. Tribological behaviour: friction coefficient and wear
the normal load (N), and F refers to friction force (N). P and F rate
can be directly attained from the digital display of the apparatus.
The wear rate is obtained by the following formula The measured friction coefficients of AB0 D0 , AB4 D6 and
AB4 D10 at different normal loads and liner speeds are shown in
V
ω= (5) Figs. 3–5, respectively. It is evident that, a friction reduction for
LP all specimens is measured with increasing the normal load or
where ω is the wear rate (m3 N−1 m−1 ), V the volume loss of liner speed. During the friction and wear tests, the increasing
the test specimens (m3 ), and L refers to the sliding distance (m). of liner speed or normal load conduces to improve the sur-
The volume loss V of the block specimens in formula (5) is face roughness of specimen and enlarge the contact area. The
calculated and determined by the expression [13] higher the liner speed or normal load, the larger the shearing
 
BR2 a b
V = a sin−1 + 4R2 − a2 − b sin−1
a−b 2R 2R
  
 2B b2
3/2
− 4R2 − b2 + R2 −
3(a − b) 4
 3/2
a2
− R − 2
(6)
4

where B is the width of the test specimens (m), a and b refers

to the dimensions of the wear traces on the block specimens, as
shown in Fig. 2 and measured with a digital-reading microscope
(JC-10). The average of three replicate test results is adopted in
order to minimize data scattering and decrease the relative error.
Finally, the surfaces of the worn specimens were examined Fig. 4. Friction coefficient vs. normal load for AB4 D6 specimen with different
via optical and scanning electron microscopy (HITACHI S-570). liner speed.
 C. Liu et al. / Wear 265 (2008) 286–291 289

Fig. 6. Wear rates vs. normal load for AB0 D0 specimen with different liner
Fig. 5. Friction coefficient vs. normal load for AB4 D10 specimen with different speed.
liner speed.

stress in contact area. As a result, the temperature of contact

area may increase distinctly, making the plastic deformation of
the specimen easier. Thus the friction coefficient decreases with
increasing the liner speed or normal load. Comparing Fig. 3 with
Figs. 4 and 5, it can be detected that the friction coefficients varies
from 0.54 to 0.77 with pure alumina whereas they varied from
0.44 to 0.65 with advanced alumina matrix ceramic materials
toughened by Al–Ti–B master alloys and diopside. Obviously,
introduction of Al–Ti–B master alloys and diopside decreases
the friction coefficient of pressureless sintered advanced alumina
matrix ceramic composites. This phenomenon may be primely
related to microstructure variations of the composites. It has
been investigated in our previous research that addition of diop-
side can obviously prompt the sintering of the composites and
thus decrease the number of air holes in alumina matrix [1]. Fig. 7. Wear rates vs. normal load for AB4 D6 specimen with different liner
Simultaneously, being one composition of diopside, MgO can speed.
restrain alumina grains from abnormal growing during the sin-
tering process and make the microstructure of the composites ness (as shown in Table 2), and thus leads to better wear
finer and more homogeneous [14–17]. So addition of diopside resistance.
may be the main reason that contributes to decreasing of the It is also can be seen from Figs. 6–8 that the wear rates for
friction coefficient of pressureless sintered advanced alumina all specimens increased with the increasing of normal load. It
matrix ceramic composites. is well known that higher liner speed lowers the wear transition
Wear rates vs. normal load for AB0 D0 , AB4 D6 and AB4 D10 load, the similar trends of higher speed causing higher wear and
specimens with different liner speed when dry sliding against
carbon steel ring in room conditions are plotted in Figs. 6–8.
Experimental results show that, at the range of loads and speeds
studied in this work, the specific wear rate of 10−15 m3 /N m was
observed for pure alumina and that of 10−16 m3 /N m for the fab-
ricated advanced alumina matrix ceramic materials. Evidently,
the introduction of Al–Ti–B master alloys and diopside into
alumina matrix results in significant improvement in wear resis-
tant of the composites. This phenomenon can be apprehended
according to Evans’s equation [18]:
ω ∝ HV −1/2 KIC −3/4 (7)
where ω is the wear rate, HV the hardness of the specimen
mentioned previously, and KIC is the fracture toughness of spec-
imen. Addition of Al–Ti–B master alloys and diopside promotes
the densification rate of the composites, decreases interspaces Fig. 8. Wear rates vs. normal load for AB4 D10 specimen with different liner
or cavities, brings on enhanced hardness and fracture tough- speed.
290 C. Liu et al. / Wear 265 (2008) 286–291

lower wear transition load were observed for AB4 D6 specimen

(Fig. 7). As shown in Fig. 7, a jump of wear rate was found as
normal load varied from 150 to 200 N at low liner speed (0.2
and 0.4 m/s), and at high liner speed of 0.6 and 0.8 m/s, the jump
of wear rate occurred as the normal load increased from 50 to
100 N. It can be generally concluded that the larger the normal
load applied, the earlier the wear transition occurs and the more
severe the wear will be, and also, the higher the temperature, the
lower the wear transition loads. This conclusion is similar with
that drawn by Wang [19].
It can be observed from Figs. 7 and 8 that the wear rate of
AB4 D6 specimen is lower than that of AB4 D10 . On the one hand,
the value of wear rate mainly depends on the hardness of the
composites. Higher hardness brings on lower wear rate and they
are inverse ratio. The hardness of diopside is 5–7 GPa, lower
than that of pure alumina. So the hardness of the composites
will decrease as the volume content of diopside increases [1].
On the other hand, 10 vol.% diopside addition makes higher
content of glass phases in AB4 D10 specimen than that in AB4 D6
specimen. So the softening of glass phases in AB4 D10 specimen
will be easier to emerge and thus results in thermal activation
conglutination [20]. Under the cooperation of frictional shearing
Fig. 9. SEM micrographs of wear track on AB0 D0 specimen under dry sliding
stress and thermal stress, plastic deformation of the adhesive conditions.
surface film may occur. Simultaneously the contact points may
be adhered and separated alternatively. With the shearing process
of adhesion points, micro-fracture and grain pull-out may easily directly to the fact that AB4 D6 and AB4 D10 specimens have
occur for AB4 D10 specimen and results in higher wear rate of a larger value of fracture toughness compared with pure alu-
AB4 D10 specimen than that of AB4 D6 specimen. mina (as shown in Table 2). It can be concluded from the above
analysis that the dominant wear mechanism of the fabricated
3.2. Tribological behaviour: wear mechanisms composites includes mechanical interlocking and plastic defor-
mation combined with a little micro-fracture.
SEM micrographs of wear tracks on AB0 D0 , AB4 D6 and
AB4 D10 specimens under dry sliding conditions at the highest
normal load value of 200 N and liner speed of 0.8 m/s are shown
in Figs. 9–11, respectively. As shown in Fig. 9, the worn area of
pure alumina was fairly rough, patches of fine debries strongly
smeared and plastically deformed on the surface were visible.
With the function of surface tangential stress and compressive
stress, microcracks may occur and interact on each other to result
in their intergranular extending. Therefore, small particles with
weaken grain bondings may firstly pull out from the matrix [21],
and also due to the characteristics of high hardness and low frac-
ture toughness, brittle fracture and grain pull-out may be easy
to occur for pure alumina [22]. Simultaneously, high load value
of 200 N and liner speed of 0.8 m/s may contribute to high tem-
perature in contact area and thus result in plastic deformation.
From Figs. 10 and 11, we can see that the worn surfaces of pres-
sureless sintered advanced alumina matrix ceramic composites,
toughened by Al–Ti–B master alloys and diopside, are relatively
smooth and covered with continuous dense layers, which may be
formed by the agglomerate of wear debris and the attaching to the
sliding surface of the specimen. As the sliding test being carried
on, some of these layers were plastically deformed, broken away
and sometimes transferred between the counterbodies, making
the sliding steady and protecting the counterbodies against wear.
There is no distinct evidence of surface cracks but only a lit- Fig. 10. SEM micrographs of wear track on AB4 D6 specimen under dry sliding
tle micro-fracture in Figs. 10 and 11, which may be attributed conditions.
 C. Liu et al. / Wear 265 (2008) 286–291
Fig. 11. SEM micrographs of wear track on AB4 D10 specimen under dry sliding
conditions.
4. Conclusion
Advanced alumina matrix ceramic materials were fabricated
by pressureless sintering technology. The friction and wear
behaviour of this new material were investigated. Experimental
results showed that the friction coefficient values and wear rate
of alumina matrix ceramic composites toughened by Al–Ti–B
master alloys and diopside were lower than that of pure alumina.
The wear rate of pure alumina was in the order of 10−15 m3 /N m
while that of alumina matrix ceramic composites toughened by
Al–Ti–B master alloys and diopside was 10−16 m3 /N m. In con-
clusion, introduction of Al–Ti–B master alloys and diopside
into alumina decreases its wear rate and coefficient of friction,
and the wear rate increases with the increase in load value.
The dominant wear mechanism of the fabricated composites,
toughened by Al–Ti–B master alloys and diopside, includes
mechanical interlocking and plastic deformation combined with
a little micro-fracture.
Acknowledgements
The work described in this paper is supported by the Ministry
of Education, PR China (No. 103101), the Outstanding Young
Scientist Rewards of Shandong Province (No. 03BS103) and
(No. 2005BS04008). The authors are grateful to Caiyun Duan
for assistance with the preparation of the manuscript.
291
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