Tribology International 104 (2016) 294–302

Contents lists available at ScienceDirect

Tribology International
journal homepage: www.elsevier.com/locate/triboint

The tribological properties of Ti3SiC2/Cu/Al/SiC composite at elevated

temperatures
Wentao Dang a,b, Shufang Ren a,n, Jiansong Zhou a,n, Youjun Yu a, Lingqian Wang a
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
b
Graduate School of Chinese Academy of Sciences, Beijing 100039, PR China

art ic l e i nf o a b s t r a c t

Article history: Dense Ti3SiC2/Cu/Al/SiC composites (TCASc) were successfully produced by powder metallurgy/spark
Received 14 June 2016 plasma sintering (SPS). The composition and microstructure of the composites were analyzed by X-ray
Received in revised form diffractometry and scanning electron microscopy equipped with energy dispersive spectroscopy. The
18 August 2016
tribological properties of the TCASc sliding against Si3N4 ball at temperatures ranging from room tem-
Accepted 5 September 2016
perature (RT) to 800 °C were investigated in comparison with those of Ti3SiC2 (TSC). The tribology tests
Available online 6 September 2016
were conducted on dry sliding tribometer by ball-on-disk configuration. The wear mechanisms were
Keywords: discussed in detail. The results show that the main phases of the composite include TSC, AlCu, SiC, and
Sliding wear Al2O3. The incorporation of Al could inhibit the decomposition of TSC. The hardness and flexural strength
Ceramic-matrix composite
of the composite are slightly lower than those of TSC. The tribological properties of TCASc and TSC are
Tribochemistry
intensively dependent on temperature. The tribological properties of TCASc are better than those of TSC
High temperature
at room and medium temperatures (wear rate, WR, of TSC at RT and 200 °C: (8.63 70.37)
10  4 and
(2.15 7 0.18)
10  3 of TCASc (5.31 7 0.55)
10  4 and (1.12 70.02)
10  3 mm3/N  m, respectively),
while the wear properties of TCASc are not better than that of TSC at 400–800 °C (WR at 600 °C, for
example, for TSC: (9.7 71.4)
10  5 and TCASc (2.27 70.15)
10  4 mm3/N  m, respectively). Abrasive
wear dominates the wear mechanisms at RT and 200 °C for TCASc. The incorporated phases of AlCu, SiC,
and Al2O3 reinforce the bonding of TSC grains and nail the surrounding soft TSC matrix under the cyclic
stress. At high temperature, dynamic-equilibrium tribo-oxides layers show the lubricating and wear-
reduction effects contributing to the decreasing friction and wear for both TSC and TCASc. The adhesive
wear resulting from the plastic flow is one of the reasons of the higher WR of TCASc than that of TSC.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Because of the combined merits of both ceramics and metals, a
remarkable ternary lamellar ceramic TSC has attracted extensive at-
tentions [1–3]. Like metals it is relatively soft (Vickers hardness: 4 GPa),
easily machinable, electrically (conductivity: 4.5
106 Ω  1 m  1), and
thermally (thermal conductivity: 34 W/m K) conductive, and behaves
plastically at high temperature. Like ceramic it is oxidation resistant
(Resistance to oxidation kw ¼ 2
10  8 kg2 m  4 s  1 (Comparative to
Cr)), has high melting point (3000 °C), and, most importantly, it
maintains its strength at high temperature that render the best su-
peralloys available today unusable. In addition, TSC has high Young's
modulus (343 GPa), high fracture toughness (7–9 MPa m1/2), moderate
tensile or flexural strength (200 and 600 MPa, respectively) [4–6]. Like
graphite and MoS2, TSC has a hexagonal structure belonging to a space
group of P63/mmc. Myhra and Crossley [7,8] studied its tribological
n
Corresponding authors.
E-mail addresses: sfren@licp.cas.cn (S. Ren), jszhou@licp.cas.cn (J. Zhou).
properties using a lateral force microscope with a Si3N4 tip and re-
vealed that the basal planes of Ti3SiC2 (the lamellar cleavage faces) had
ultra-low coefficient of friction, COF, (2–5
10  3); however, the COF of
non-basal planes was much higher (0.1–0.3). The consecutive studies
on the tribological properties of TSC show that TSC is not an excep-
tional solid lubricant. On the contrary, TSC is generally subjected to
severe friction (COF40.6) and wear (WR is in the order of
10  2  10  3 mm3/N m) especially at medium and low temperature
(RT) [9–15]. Under some special harsh conditions, such as high tem-
perature (higher than 600 °C), high speed (higher than 5 m/s), or with
some special mating material, polycrystalline TSC exhibits the relatively
low friction (COF: 0.1–0.5) and wear resistance (WR in the order of
10  5  10  6 mm3/N m). Nevertheless, this lubrication and wear re-
sistance should be fundamentally attributed to the tribo-oxidation
transfer layers formed on the sliding surface [13–17]. In fact, once the
tribo-oxidation layer cannot be formed on the worn surface, three-
body abrasive wear that derives from the fracture and pulling-out of
TSC grains will dominate the wear mechanisms for TSC.
Therefore, many researchers focus on the reinforcement study
of polycrystalline TSC by incorporating metal and/or ceramic to

http://dx.doi.org/10.1016/j.triboint.2016.09.008
0301-679X/& 2016 Elsevier Ltd. All rights reserved.
 W. Dang et al. / Tribology International 104 (2016) 294–302
improve its tribological properties. Hibi et al. [18] investigated the
friction and wear properties of TSC/SiC composites against itself in
dry sliding, water, and ethanol. Under dry sliding conditions and in
water, titanium oxide and silicon oxide were formed by tribo-
oxidation. The formation of these oxides caused oxidative and
abrasive wear. However, in ethanol, the friction and wear was low
because tribo-oxidation was insignificant and fractural abrasion
did not occur. Hu et al. [12] prepared Al2O3-reinforced TSC com-
posites and they found the COF's of TSC and TSC/Al2O3 varied from
0.3 to 0.5 under the applied load of 2.5–10 N when sliding against
AISI-52100 bearing steel. The WRs of TSC/Al2O3 composites were
much lower than that of TSC. The enhancement of wear resistance
was attributed to the fact that the Al2O3 particles nail the soft TSC
matrix and decentralize the shear stresses under the sliding ball.
Yang et al. [19] investigated the friction and wear properties of
(TiB2 þ TiC)/TSC composites and they found the COF of the com-
posites was higher than that of TSC. The TiB2 and TiC could nail the
surrounding soft matrix and decentralize the shear stresses. Shi
et al. [20] investigated tribological behavior of TSC/(WC-10Co)
composites against GCr15 steel and found the composite with
3 wt% WC-10Co showed the relatively good tribological properties,
whose COF was in the range of 0.40–0.48 and WR varied from
0.6 to 1
10  4 mm3/N m. When relatively high load and slide
speed, the glazes were formed which could act as solid lubricant
and contribute to the decreased COF. The wear mechanisms in-
cluded micro-cutting and abrasive wear of TSC/(WC-10Co), oxi-
dation wear of GCr15 steel, as well as adhesive wear caused by the
glaze flaking. Zhai et al. [21] investigated the tribological behaviors
of TSC with 2 and 20 vol% TiC using a low carbon steel disk as the
counterpart at RT. The pure TSC exhibited relatively low COF (0.53–
0.09) and WR (0.6–2.5
10  6 mm3/N m) under the sliding speed
of 5–60 m/s due to the presence of a frictional oxide layer of
amorphous mixture of Ti, Si, and Fe oxides on the sliding surfaces.
However, as for the TSC-TiC composites, the TiC impurities caused
both of the COF (0.3–0.6) and the WR to increase remarkably due
to an interlocking action and the pulling-out of TiC grains.
Copper is commonly used as the cable, electrical and electronic
components, and building materials because of its some excellent
properties, such as thermal and electrical conductivity, good
ductility, and excellent mechanical properties [22]. So it was
meaningful and feasible to combine good properties of Cu with
TSC. The objective of this paper was to prepare TSC/Cu/SiC com-
posites and investigate the mechanical and tribological properties
of the composite. Many researchers reported the chemical re-
activity between Cu and TSC [23,24]. Zhou and his coworkers [23]
found TSC reacted with Cu above 900 °C. When the low content of
TSC or below 1000 °C, Cu(Si) solid solution and TiCx were formed,
whereas at high temperature or high content of TSC, Cu-Si inter-
metallic compounds like Cu5Si, Cu15Si4, and TiCx were formed. In
our previous work [24] we found the incorporated Cu reacted with
TSC to form Cu3Si and TiCx. At the process of preparing TSC, many
researchers [25,26] reported incorporating moderate Al con-
tributed to formation of TSC and improve its productivity. So in
this paper, the metal Al was incorporated to the TSC/Cu composite
to inhibit the reactivity between TSC and Cu. In addition, the
ceramic reinforced phase SiC was incorporated to improve the
wear resistance.
2. Materials and methods
2.1. Samples preparation
The commercially available TSC (purity: 99.8%, particle size:
200 mesh, YueHuan New Material Technology Co., Ltd.), Cu (pur-
ity: 99%, particle size: 200 mesh, Sinopharm Chemical Reagent Co.,
295
Ltd), Al (purity: 99%, particle size: 200 mesh, Sinopharm Chemical
Reagent Co., Ltd), and SiC (purity: 98.5%, particle size: 200 mesh,
Sinopharm Chemical Reagent Co., Ltd) were used in this study.
Four kinds of starting powders were mixed 3 h with a speed of
150 rpm through high energy ball-milling machine (Pulverisettes
4, Germany). The percentage of powders was 75:10:5:10 (TSC:Cu:
Al: SiC, wt%). The mixed powder was weighed 20g and sintered at
1050 °C in vacuum (o 15 Pa) under a pressure of 30 MPa at a cy-
lindrical graphite mold with a 25 mm diameter by SPS (SPS-20T-
10, Shanghai Chen Hua Technology Co., Ltd). The sintering tem-
perature was manipulated from room temperature to 1050 °C with
a rough rate of 100 °C/min and held for 5 min, then cooled down
by circulative water. The as-prepared TCASc was polished down to
60, 360, 800, 1200, and 1500 mesh silicon carbide waterproof
abrasive papers. The monolithic bulks were prepared under the
same sintering condition as TCASc. The specific mean surface
roughness, Ra for TCASc was 0.069 mm and TSC 0.065 mm. The
density of sintered TCASc was measured by Archimedes principle.
2.2. Mechanical testing methods
The Vickers hardness was measured by the MH-5-VM micro-
hardness tester under the applied load of 10 N load with the dwell
time of 5 s and the hardness value was calculated by averaging at
least eight measurements. The three-point bending test was con-
ducted to obtain the flexural strength through a universal material
tester (SANS-CMT5205, MTS china) and the samples were cut to
3
4
20 mm3. The cross head speed was 0.5 mm/s and the span
was 16 mm.
2.3. Friction and wear tests
The friction and wear tests were conducted on high-tempera-
ture tribometer (HT-1000, made by Zhong Ke Kai Hua Corporation)
with a ball-on-disk configuration. The disk was TCASc or TSC
which rotated with a constant speed of 0.188 m/s over a period of
45 min. The counterpart was commercial Si3N4 ball with a dia-
meter of 6.43 mm. The normal load was 5 N and the rotation ra-
dius was 5 mm for all tests. The test temperature for TCAScs or TSC
was RT, 200, 400, 600, and 800 °C. The COF was recorded auto-
matically by the computer of friction tester during the test. The
friction and wear test for every specimen was repeated three
times. The mean COF of the tribo-pairs and WR of the disks were
the mean values from three tests under the same conditions. The
wear volume of the disk specimens was calculated by the fol-
lowing formula [27]:
V=AL (1)
3
where V is the wear volume (mm ), A is the cross-sectional area
(mm2) of the wear tracks on TSC-based disks measuring by optical
microscopy and surface profilometry, and L is the perimeter of
wear track (mm). The WR was determined by the following for-
mula [28]:
W = V /PS (2)
3
where W is the wear rate, V is the wear volume (mm ), P is the
applied load (N), and S is the total sliding distance (m).
2.4. Characterization
Phase compositions of TCAScs were analyzed by an X-ray dif-
fractometry (XRD, D/MAX-2400 Rigaku, Japan) with Cukɑ radiation
in wavelength λ ¼0.1540598 nm. The microstructure observation
and elemental analysis of TCAScs were conducted by Scanning
Electron Microscopy (SEM, JEOL-5600LV) equipped with energy
296 W. Dang et al. / Tribology International 104 (2016) 294–302
dispersive spectroscopy (EDS). The chemical states of some typical
elements on the worn surfaces were determined by a PHI-5702
X-ray photoelectron spectroscope (XPS) using Al Ka radiation as
the excitation source and the binding energy of carbon
(C1s:284.8 eV) as the reference.
3. Results and discussion
3.1. Phase composition and microstructure
The XRD pattern of the TCASc is shown in Fig. 1. It can be seen
that the main phases of TCASc are TSC, AlCu, SiC, and Al2O3. The
TSC was relatively stable and did not decompose during the sin-
tering preparation of the composite. The AlCu intermetallic com-
pound originated from the chemical reaction of the incorporated
Al and Cu and the Al2O3 derived from the autoxidation of Al. As far
as the authors know, the TSC exhibits high reaction activity when
contacting with metal phases [22–24,29–32]. On the one hand, the
high reaction activity is closely related with the special TSC crys-
talline structure. The crystalline structure of TSC can be described
as a layer of Si intercalating into the {111} twin boundary of TiC
and the chemical bonding between Si atom and the other atoms,
such as Ti and C is relatively weak compared to the strong Ti-C
bonding [14,22]. The Si atoms are inclined to release from the
sandwich structures under some extreme conditions, such as high
temperature, corrosive liquid, and so on. On the other hand, if the
metal phases that contact with TSC can form Si-containing solid
solution or react with Si element to form intermetallic compounds,
the contacted metal phases can act as accelerant to aggravate the
decomposition of TSC with Si atoms releasing from the sandwich
structures. So it is difficult to prepare TSC/metal composites
without any decomposition of TSC. That is the reason why the
reported studies about TSC/metal compounds are relatively much
less than that of TSC/ceramic compounds. In terms of TSC/Cu
composites, Cu can form Cu(Si) solid solution or react with Si
element to form CuxSiy intermetallic compounds [33]. So when
preparing TSC/Cu composites at high temperature, Cu(Si) solid
solution, CuxSiy intermetallic compounds, and the decomposed
products of TiCz were commonly detected by researchers [22–24].
In this study, the TSC did not react with the incorporated Cu,
which is mainly attributed to the function of Al. Through XRD we
detected the presence of AlCu intermetallic, therefore, we can
deduce that the incorporated Cu preferentially reacted with Al to
produce AlCu intermetallic, so that the TSC is left. In addition,
some researchers have found that the moderate Al element can
Fig. 1. The XRD pattern of TCASc.
contribute to the formation of TSC and enhance the productivity of
TSC during the process of fabricating TSC [25]. In sum, the in-
corporated Al can play a role in protecting TSC from decomposi-
tion. It is interesting that we detected the presence of Al2O3 in the
TCASc. The Al2O3 is the reaction product of the incorporated Al and
the residual O2 in sintering furnace. The relevant chemical reac-
tions are described as follows:
Cuþ Al-AlCu (3)
Alþ O2-Al2O3 (4)
The microstructure of TCASc was observed by SEM and the
distributions of elements was analyzed by the mapping of ele-
ments as shown in Fig. 2. We can observe three distinct regions in
the backscattered electron image (BEI) of TCASc: flake-like black
region and threadlike white region distribute in the gray matrix.
According to the mapping of elements, flake-like black region is
rich in Si, Al, and O elements, the white region is rich in Cu and Si,
and the gray region is rich in Ti, Si, and Cu. So we deduced that the
black region is SiC and Al2O3 particles, white region is AlCu in-
termetallic compound and the gray region is TSC matrix con-
sidering the XRD result. The specific distribution of the different
phases are denoted in Fig. 3.
3.2. Mechanical properties
The density, Vickers hardness, and flexural strength of TCASc
and TSC are listed in Table 1. We can see the densities of TCASc and
TSC are 3.95 g/cm3 and 4.44 g/cm3, respectively. The Vickers
hardness of TCASc is comparable to that of TSC and their Vickers
hardness values are 518 Hv and 520 Hv, respectively. The SiC and
Al2O3 in the TCASc belong to ceramics and are conducive to the
improvement of Vickers hardness, while the AlCu which belongs
to intermetallic compounds has low hardness of 444 Hv [34]. The
Vickers hardness of TCASc is the comprehensive result of SiC,
Al2O3, AlCu and TSC. The flexural strength of TCASc is found to be
lower than that of monolithic TSC. The fracture surface of mono-
lithic TSC (Fig. 4a) is characterized by intergranular and transgra-
nular fracture (as denoted in Fig. 4a), the transgranular fracture
which is conducive to the improvement of the flexural strength is
the main fracture mechanism for TSC. In addition, the multiple
energy-absorbing mechanisms including diffuse microcracking,
delamination, crack deflection, grain push-out, grain pull-out, and
the buckling of individual grains are found to be responsible for
the high flexural strength of monolithic TSC [35,36]. The SEM
image of the fracture surface of TCASc is shown in Fig. 4b. It can be
seen that many fine equiaxed grain particles distribute on the
large grains. From the size of the phases (Fig. 3), the SiC and Al2O3
is big, and threadlike AlCu intermetallic compound is small. So the
fine equiaxed grains in microstructure belong to AlCu, while the
large size particles assign to TSC, SiC, and Al2O3 grains. Apart from
intergranular and transgranular fracture, we can see some pores
and cracks which may be caused by the poor compatibility (e.g.
wettability) of the TSC matrix and SiC, Al2O3, and AlCu. The mis-
match between the thermal expansion coefficients (for example:
TSC: 9.1
10  6, SiC: (3.7–4.8)
10  6, and Al2O3: 7.8
10  6 °C  1)
of different phases easily leads to the weak bonding between
grains, micro-pores and micro-cracks at the process of sintering.
The micro-pores and micro-cracks could degrade the flexural
strength. Another important reason for the decrease of fracture
strength of the TCASc is that the phases of SiC, Al2O3, and AlCu
distributed among the TSC grains partly obstacle multiple energy-
absorbing mechanisms, which makes fracture occur between the
fine impurities grains. In addition, the intermetallic compound
AlCu is brittle and could degrade the mechanical properties [34],
 W. Dang et al. / Tribology International 104 (2016) 294–302 297

Fig. 2. Backscattered electron image (BEI) and Mappings of elements of TCASc.

Fig. 3. BEI of TCASc denoted with the specific phases.

Table 1
Physical and Mechanical parameters of TSC and TCASc.

Materials Density (g/cm3) Vickers hardness (Hv) Flexural strength (MPa)

TSC 4.44 70.4 520 7 22 434 7 14

TCASc 3.95 7 0.7 5187 46 395 7 31

thus further aggravates the flexural strength of TCASc.

3.3. Tribological properties

The real-time COFs (COFrs) as a function of sliding time of TSC/

Si3N4 and TCASc/Si3N4 tribopairs at elevated temperatures are
shown in Fig. 5a and b, respectively. The COFrs of TSC/Si3N4 Fig. 4. SEM images of the fractured surface of (a) TSC and (b) TCASc.
298 W. Dang et al. / Tribology International 104 (2016) 294–302
Fig. 5. The coefficients of friction and wear rates: the real-time COF curves versus sliding time for (a) monolithic TSC and (b) TCASc; and their (c) mean COFs and (d) WRs for
monolithic TSC and TCASc at elevated temperatures.
tribopair fluctuate relatively larger than those of TCASc/Si3N4 tri-
bopair at all the temperatures except 200 °C. The mean COFs
(COFms), the mean value of three COFs deriving from three friction
tests under the same testing condition, of TSC/Si3N4 and TCASc/
Si3N4 tribopair at elevated temperatures are shown in Fig. 5c. The
trends of COFms for both TSC/Si3N4 and TCASc/Si3N4 tribopairs
with the temperature increasing are similar: the COFms at RT are
the lowest among all the temperatures (0.60 for TSC/Si3N4; and
0.46 for TCASc/Si3N4); and the COFms at 200 °C are the highest
(0.91 for TSC/Si3N4; and 0.80 for TCASc/Si3N4); then the COFms
decrease with the temperature increasing from 200 to 800 °C. At
each temperature, the COFm of TCASc/Si3N4 tribopair is lower than
that of TSC/Si3N4 tribopair except at 800 °C at which the COFms for
both the tribopairs are equal (0.6).
The WRs for both the TSC and TCASc at elevated temperatures
are shown in Fig. 5d and the corresponding sectional skeleton
maps for the wear tracks are shown in Fig. 6. The trends of WRs for
both the TSC and TCASc are similar to their COFms with the tem-
perature increasing: the WRs increase from RT to 200 °C; reach the
highest value at 200 °C among all the temperatures
(2.15
10  3 mm3/N m for TSC, and 1.12
10  3 mm3/N m for
TCASc), and then decrease with the temperature increasing to
800 °C. Different from the COFms, the WRs of TCASc are lower than
those of TSC at RT and 200 °C, while at 400, 600, and 800 °C the
WRs of TCASc are higher than those of TSC (Fig. 5d). Interestingly,
negative WR (  9.53
10  5 mm3/N m) which could not be
marked in the histogram (Fig. 5d) was found for TSC at 800 °C.
From the sectional skeleton maps for the wear tracks on TSC
(Fig. 6a), it can be seen the skeleton line of the wear scar for TSC at
800 °C is almost horizontal with medium salient points. The tri-
bological mechanisms will be discussed in the next part.
3.4. Tribological mechanisms
The SEM images of the worn surface of TSC and TCASc at ele-
vated temperatures are shown in Fig. 7. At RT, a great deal of wear
debris scattered on worn surface of TSC with several dark island
regions (Fig. 7a). It's worth noting that loose cracks and pores
distributed on the worn surface, which is originated from the
spalling and decoherence of the grains. This phenomenon is in
agreement with our previous report [14]. This is derived from the
week bonding between TSC grains, which results in the fracture
and pulling out of TSC grains. So at RT, abrasive wear is the main
wear mechanism for TSC. As for TCASc, the worn surface was re-
latively smooth with a little scattered debris, but without the loose
cracks and pores (Fig. 7b). So it can be deduced that the threadi-
ness phase AlCu, which distributed around the TSC grains, plays an
important role in reinforcing the bonding of TSC grains, then
consequently restraining the spalling and decoherence of TSC
matrix. Additionally, the hard reinforcement phases of SiC and
Al2O3 can nail the surrounding soft TSC matrix and decentralize
the shear stresses under sliding ball. That is the reason why the
WR of TCASc is lower than that of TSC at RT.
The temperature of 200 °C was an inflection point at which the
friction and wear for both the TSC and TCASc reached the highest
values (Fig. 5c and d). Compared to the worn surface at RT, the
detached wear debris on the worn surface of TSC at 200 °C (Fig. 7c)
dramatically increased, which indicates the abrasive wear was
 W. Dang et al. / Tribology International 104 (2016) 294–302
Fig. 6. The sectional skeleton maps for the wear tracks on (a) TSC and (b) TCASc at
elevated temperatures.
significantly intensified. While, the worn surface of TCASc was
relatively smooth with less wear debris scattered. Differently, the
spalling and decoherence of tribolayers occurred on the worn
surface of TCASc (as denoted in Fig. 7d), because of which the WR
at 200 °C is the highest among all the testing temperatures.
The worn surface of TSC at 400 °C is shown in Fig. 7e. Apart
from the wear debris, laminated flaky tribolayers covered on the
worn surface, which may be the result of plastic flow of TSC. As is
well known, TSC possesses the merits of both the metal and
ceramic, which means it can exhibit not only the brittleness of
ceramic, but also the ductility of metal. In fact, its ductility usually
present at the temperature higher than 1100 °C [1,9]. Evidently,
the friction process, at which the instantaneous flash temperature
between the contacting asperities of the two relatively moving
materials may reach 3000 °C [37], makes the brittle-ductile tran-
sition temperature of TSC decrease. The plastic flow, to a certain
extent, retard the abrasive wear of TSC, so the WR of TSC at 400 °C
exhibits an obvious decrease compared to those at RT and 200 °C.
As for TCASc, the worn surface was characterized by the typical
plastic of metal (Fig. 7f), which indicates that the incorporation of
Al and Cu could enhance the ductility of TSC. The ductility of TSC is
related to the friction heat. If the friction material is a good ther-
mal conductor, the friction heat is fast transferred to the whole
friction materials. Then the temperature on the friction surface is
not too high. On the contrary, if the friction materials is not a good
thermal conductor, the friction heat is focused on the fiction sur-
face and not transferred away, which leads to the temperature on
the friction surface increase. The higher the temperature on the
friction surface, the more plastic the friction surface. The TSC is
good thermal conductor with the thermal conductivity of 34 W/
299
m K. The incorporation of Al and Cu produce the formation of
AlCu, SiC, and Al2O3. These phases are ceramic or intermetallic
compound with the poor thermal conductivity, which make the
temperature on the friction surface high, then enhance the duc-
tility of TSC. However, plastic flowing resulting from the enhanced
ductility and the flaking off of plastic flowing layers contributed to
the higher WR of TCASc than that of TSC at 400 °C.
Both the worn surfaces of TSC and TCASc at 600 °C (Fig. 7g and
h) were covered by relatively smooth and continuous tribolayers.
A typical character of “crimping” of the plastic flowing tribolayers
on the edge of wear track can be distinguished in the Fig. 6a and b.
The part of the tribolayers on the worn surfaces presented clea-
vage and flaking off, which results in the abrasive wear. The ad-
hesive wear resulting from the serious plastic flow may be one of
the reasons of the higher WR of TCASc than that of TSC.
Additionally, tribo-oxidation is an important element that in-
fluences, even controls the wear mechanism, consequently results
in the variation of friction and wear behaviors [38]. In the present
study, the chemical states of Ti, Si, Cu, and Al elements on the
worn surface of TCASc at 600 °C were analyzed compared with RT
by XPS and the results are shown in Fig. 8. It can be seen that the Ti
and Si elements are partly oxidized to form TiO2 and SiO2 at RT,
while they are absolutely oxidized at 600 °C (Fig. 8a and b). The Cu
is not be oxidized at RT but is oxidized to form CuO at 600 °C. The
element Al exists mainly in the form of Al2O3 on the worn surface
of TCASc at RT. At 600 °C, the Al exists in the form of Al2O42-. So it
can be concluded that tribo-oxide layers formed on the worn
surface of TCASc. The previous studies of our group show that
when the testing temperature is higher than 400 °C, the tribo-
oxide layers consisting of oxides of Ti and Si can form on the worn
surfaces of TSC [14,17]. As reported the direct friction contact of
surfaces of TSC or TCASc will lead to the pull out and fracture and
then detaching off of TSC grains, which results to the high friction
and wear [10,14,17]. The tribo-oxides film can reduce friction and
wear of TSC and TCASc, which is derived from the barrier property
of the oxide film that can prevent the direct contact of the friction
surfaces of TSC or TCASc and Si3N4. Furthermore, with the tem-
perature increasing, the generation and consumption of these
tribo-oxides will gradually reach a dynamic equilibrium. On the
one hand, tribo-oxide layers can act as lubricant and wear-re-
duction agent, which makes the friction and wear of TSC generally
exhibit obvious decrease; On the other hand, tribo-oxidation wear
may be another wear mechanism during the dynamic removal of
the tribo-oxide layers. In the present study, the variation tenden-
cies of friction and wear of TSC and TCASc agree with previous
studies. The tribo-oxide layers, on the one hand, decrease friction
and wear when the temperature increases to 400 °C and the
higher, and on the other hand, result in tribo-oxidation wear. In
addition, the wear-reduction effect of these tribo-oxides layers on
the worn surface of TSC is better than that of TCASc. We speculate
that the distributed AlCu and SiC hard phases, on the one hand,
obstruct the formation of the continuous smooth tribo-oxides
layers, on the other hand, the hard asperities of AlCu and SiC on
the worn surfaces plough the tribo-oxides layers, which results in
the higher removal of material, e.g. WR. At 800 °C, the rate of the
generation is higher than that of the consumption of the tribo-
oxides layers. So the tribo-oxides layers covered on the worn
surface of TSC formed the loose mechanically mixed layers under
the circulatory friction stress, which results in the negative WR.
In conclusion, at RT and 200 °C, the abrasive wear derived from
the spalling and decoherence of the fractured and/or pulled-out
TSC grains dominates the wear mechanism of TSC, which leads to
the high friction and wear. While for TCASc, on the one hand, the
incorporated phase of AlCu plays an important role in reinforcing
the bonding of TSC grains, then consequently restraining the
spalling and decoherence of TSC matrix. On the other hand, the
300 W. Dang et al. / Tribology International 104 (2016) 294–302

Fig. 7. SEM micrographs of worn surfaces of TSC at (a) RT, (c) 200, (e) 400, (g) 600, and (i) 800 °C and of TCASc at (b) RT, (d) 200, (f) 400, (h) 600, and (j) 800 °C.
 W. Dang et al. / Tribology International 104 (2016) 294–302
Fig. 8. X-ray photoelectron spectroscopy for (a) Ti2p (a), (b) Si2p, (c) Cu2p, and (d) Al on the worn surface of TCASc at RT and 600 °C.
reinforcing phases of SiC and Al2O3 can nail the surrounding soft
TSC matrix and decentralize the shear stresses under sliding ball,
which results in the lower WR of TCASc than that of TSC at RT and
200 °C. As for the reason why the friction and wear for both TSC
and TCASc are the highest among all the testing temperatures, we
proposed that: at this temperature, the consumption of tribo-
oxides layers and the generation reach an extremely unbalanced
state, which means the rate of consumption is much higher than
the rate of generation. So the fast removal of the tribo-oxides
layers results in the highest WR. With the temperature increasing,
the lubricating and wear-reduction effects of the tribo-oxides
layers favor the decreasing friction and wear for both TSC and
TCASc. Whereas, the character of plastic adhesive wear for TCASc
make its WR higher than that of TSC.
4. Conclusions
TCASc was successfully produced by the technology of spark
plasma sintering. The phase composition and the microstructure
of the composite were analyzed by XRD and SEM-EDS. The tri-
bological properties were investigated and the wear mechanisms
were discussed in details compared to TSC. The results are as
follows:
1. The main phases of the composite include TSC, AlCu, SiC, and
Al2O3. The incorporation of Al restrained the decomposition of
TSC. Cu reacted with Al to produce AlCu intermetallic com-
pound and Al2O3 derived from the oxidation of Al. The hardness
301
and the flexural strength of the composite are slightly lower
than those of TSC.
2. As the temperature increase, the mean COFs of TCASc and TSC
increase firstly to reach the highest value at 200 °C and then
decrease, and the mean COFs of TCASc are lower than that of
TSC at all the temperatures. The variation tendency of WRs for
both TSC and TCASc is similar to the mean COFs with the
temperature increasing: firstly increased; reached highest value
at 200 °C; and then decreased. The WRs of TCASc are lower than
those of TSC at RT and 200 °C, while at 400, 600, and 800 °C the
WRs of TCASc are higher than those of TSC. Negative WR
(  9.53
10  5 mm3/N m) was found for TSC at 800 °C.
3. Abrasive wear dominates the wear mechanism at RT and 200 °C
for both TSC and TCASc. The incorporated phases of AlCu, SiC,
and Al2O3 reinforce the bonding of TSC grains and nail the
surrounding soft TSC matrix and decentralize the shear stresses,
which results in the lower WR of TCASc than that of TSC at RT
and 200 °C. With the temperature increasing, dynamic-equili-
brium tribo-oxides layers show the lubricating and wear-re-
duction effects favoring the decreasing friction and wear for
both TSC and TCASc. The adhesive wear resulting from the
serious plastic flow is one of the reasons of the higher WR of
TCASc than that of TSC.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China, China (Grant no. 51405475 and 51475444).
302 W. Dang et al. / Tribology International 104 (2016) 294–302
References
[1] Barsoum MW. The MN þ 1AXN phases: a new class of solids; thermo-
dynamically stable nanolaminates. Prog Solid State Chem 2000;28:201–81.
[2] Jeitschk W, Nowotny H. Crystal structure of Ti3SiC2 a new type of complex
carbide. Mon Chem 1967;98:329–37.
[3] Radovic M, Barsoum MW. MAX phases: bridging the gap between metals and
ceramics. Am Ceram Soc Bull 2013;92:20–7.
[4] Hashimoto H, Sun ZM, Inoue Y, Tada S. Synthesis of Ti3SiC2 from powder blend
of Ti, Si and TiC. J Alloy Compd 2006;426:263–7.
[5] Li JF, Pan W, Sato F, Watanabe R. Mechnical properties of policrystallic Ti3SiC2
at ambient and elevated temperatures. Acta Mater 2001;49:937–45.
[6] Barsoum MW, El-Raghy T T. Synthesis and characterization of a remarkable
ceramic: Ti3SiC2. J Am Ceram Soc 1996;79:1953–6.
[7] Myhra S, Summers JWB, Kisi EH. Ti3SiC2-a layered ceramic exhibiting ultra-
low friction. Mater Lett 1999;39:6–11.
[8] Crossley A, Kisii EH, Bennett Summers JW, Myhra S. Ultra-low friction for a
layered carbide-derived ceramic, Ti3SiC2, investigated by lateral force micro-
scopy (LFM). J Phys D-Appl Phys 1999;32:632–8.
[9] Gupta S, Barsoum MW. On the tribology of the MAX phases and their com-
posites during dry sliding: a review. Wear 2011;271:1878–94.
[10] El-Raghy T, Blau P, Barsoum MW. Effect of grain size on friction and wear
behavior of Ti3SiC2. Wear 2000;238:125–30.
[11] Souchet A, Fontaine J, Belin M, Le Mogne T, Loubet JT, Barsoum MW. Tribo-
logical duality of Ti3SiC2. Tribol Lett 2005;18:341–52.
[12] Hu CF, Zhou YC, Bao YW, Wan DT. Tribological properties of polycrystalline
Ti3SiC2 and Al2O3-reinforced Ti3SiC2 composites. J Am Ceram Soc
2006;89:3456–61.
[13] Gupta S, Filimonov D, Zaitsev V, Palanisamy T, Barsoum MW. Ambient and
550 °C tribological behavior of select MAX phases against Ni-based super-
alloys. Wear 2008;264:270–8.
[14] Ren SF, Meng JH, Lu JJ, Yang SR. Tribological behavior of Ti3SiC2 sliding against
Ni-based alloys at elevated temperatures. Tribol Lett 2008;31:129–37.
[15] Zhang Y, Ding GP, Zhou YC, Cai BC. Ti3SiC2-a self-lubricating ceramic. Mater
Lett 2002;55:285–9.
[16] Zhai HX, Huang ZY, Zhou Y, Zhang ZL, Wang Y, Ai M. Oxidation layer in sliding
friction surface of high-purity Ti3SiC2. J Mater Sci 2004;39:6635–7.
[17] Ren SF, Meng JH, Lu JJ, Yang SR, Wang JB. Tribo-physical and tribo-chemical
aspects of WC-based cermet/Ti3SiC2 tribo-pair at elevated temperatures. Tribol
Int 2010;43:512–7.
[18] Hibi Y, Miyake K, Murakami T, Sasaki S. Tribological behavior of SiC reinforced
Ti3SiC2-based composites under dry condition and under lubricated condition
with water and ethanol. J Am Ceram Soc 2006;89:2983–5.
[19] Yang J, Gu W, Pan LM, Song K, Chen X, Qiu T. Friction and wear properties of
in situ (TiB2 þTiC)/Ti3SiC2 composites. Wear 2011;271:2940–6.
[20] Shi XL, Wang M, Xu ZS, Zhai WZ, Zhang QX. Tribological behavior of Ti3SiC2/
(WC-10Co) composites prepared by spark plasma sintering. Mater Des
2013;45:365–76.
[21] Zhai HX, Huang ZY, Ai M. Tribological behaviors of bulk Ti3SiC2 and influences
of TiC impurities. Mater Sci Eng A 2006;435–436:360–70.
[22] Lu JR, Zhou Y, Zheng Y, Li HY, Li SB. Interface structure and wetting behaviour
of Cu/Ti3SiC2 system. Adv Appl Ceram 2015;114:39–44.
[23] Zhou YC, Gu WL. Chemical reaction and stability of Ti3SiC2 in Cu during high-
temperature processing of Cu/Ti3SiC2 composites. Z Metallkd 2004;95:50–6.
[24] Dang WT, Ren SF, Zhou JS, Yu YJ, Li Z, Wang LQ. Influence of Cu on the me-
chanical and tribological properties of Ti3SiC2. Ceram Int 2016;42:9972–80.
[25] Yang SL, Sun ZM, Yang QQ, Hashimoto H. Effect of Al addition on the synthesis
of Ti3SiC2 bulk material by pulse discharge sintering process. J Euro Ceram Soc
2007;27:4807–12.
[26] Yu R, He LL, Ye HQ. Effects of Si and Al on twin boundary energy of TiC. Acta
Mater 2003;51:2477–84.
[27] Xu ZS, Xue B, Shi XL, Zhang QX, Zhai WZ, Yao J, Wang YF. Sliding speed and
load dependence of tribological properties of Ti3SiC2/TiAl composite. Tribol
Trans 2015;58:87–96.
[28] Archard JF. Contact and rubbing of flat surfaces. J Appl Phys 1953;24:981–8.
[29] Yin XH, Li MS, Zhou YC. Microstructure and mechanical strength of diffusion-
bonded Ti3SiC2/Ni joints. J Mater Res 2006;21:2415–21.
[30] Gao NF, Miyamoto Y. Joining of Ti3SiC2 with Ti-6Al-4V. J Mater Res
2002;17:52–9.
[31] El-Raghy T, Barsoum MW, Sika M. Reaction of Al with Ti3SiC2 in the
800 1000 °C temperature range. Mater Sci Eng A 2001;298:174–8.
[32] Tzenov N, Barsoum MW, El-Raghy T. Influence of small amounts of Fe and V
on the synthesis and stability of Ti3SiC2. J Eur Ceram Soc 2000;20:801–6.
[33] 〈http://www.crct.polymtl.ca/fact/documentation/FSstel/FSstel_Figs.htm〉.
[34] Aravind M, Yu P, Yau MY, Ng DHL. Formation of Al2Cu and AlCu intermetallics
in Al(Cu) alloy matrix composites by reaction sintering. Mater Sci Eng A
2004;380:384–93.
[35] Zhang ZF, Sun ZM, Zhang H, Hashimoto H. Micron-scale deformation and
damage mechanisms of Ti3SiC2 crystals induced by indentation. Adv Eng
Mater 2004;6:980–3.
[36] E1-Raghy T, Zavaliangos A, Barsoun M, Kalidindi SR. Damage mechanisms
around hardness indentations in Ti3SiC2. J Am Ceram Soc 2007;80 513-6.
[37] Kalin M. Influence of flash temperatures on the tribological behaviour in low-
speed sliding: a review. Mater Sci Eng A 2004;374:390–7.
[38] Woydt M, Skopp A, Dörfel I, Witke K. Wear engineering oxides/anti-wear
oxides. Wear 1998;218:84–95.