Materials and Design 67 (2015) 95106

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Materials and Design

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Review

Chemical composition, microstructure and sintering temperature

modications on mechanical properties of TiC-based cermet A review
A. Rajabi a, M.J. Ghazali b,, A.R. Daud a
a
b

School of Applied Physics, Faculty of Science and Technology, National University of Malaysia (UKM), 43600 UKM, Bangi, Selangor, Malaysia
Dept. of Mechanical & Materials Engineering, Faculty of Engineering & Built Environment, National University of Malaysia (UKM), 43600 UKM, Bangi, Selangor, Malaysia

a r t i c l e

i n f o

Article history:
Received 12 June 2014
Accepted 28 October 2014
Available online 11 November 2014
Keywords:
Cermets
TiC
TiN
Sintering
Mechanical properties

a b s t r a c t
Cermets, particularly those based on TiC, are receiving considerable attention because of their unique
properties, including high hardness and resistance to thermal deformation. However, TiC-based cermets
lack sufcient toughness. To improve the performance of these cermets, numerous studies have been
conducted to determine the factors that can be manipulated to improve their toughness. However, the
results of these studies vary. This paper summarizes the studies to improve cermet design via chemical
compositions and microstructures. Critical issues including the effects of grain size and sintering temperature on the mechanical properties (i.e., toughness, hardness, and wear resistance) of TiC-based cermets
are also discussed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Since 1927, various materials have been investigated to
improve tool life and mechanical properties of cermets and cutting
tools that are extensively utilized; roughly two billion-dollar allotment in semi-nishing and nishing works have been allotted for
polymers, ferrous alloys, nonferrous alloys, and advanced materials
such as intermetallics and composites [13]. Cermets present benecial resistance to oxidation throughout metal machining and
build up edge formation towing to their good chemical stability
and high-temperature hardness [46]. In general, cermets include
two different phases (i.e., ceramic and metal binder). The ceramic
parts retain the high hardness and cutting ability, but the softer
phase (binder) can deform and absorb energy [79]. The ceramics
are compounds of carbon, nitrogen, oxide, boron, and silicon with
metals such as tungsten, titanium, tantalum, niobium, aluminum,
and molybdenum [4,1012]. Among those, carbides are very stiff
and have high melting temperature, ranging from 2000 C to
4000 C, and their hardness is second to that of diamond, which
is the hardest known material [1315].
Thus, titanium carbide (TiC), with a cubic structure similar to
that of NaCl, has been considered as one of the most signicant
metal carbides for manufacturing a new generation of cermets.
Such cermets may be endowed with intrinsic properties of TiC,
namely, low density (4.93 g/cm3), low friction coefcient, thermal
Tel.: +60 3 89216418; fax: +60 3 89259659.
E-mail
addresses:
(M.J. Ghazali).

mariyam@eng.ukm.my,

http://dx.doi.org/10.1016/j.matdes.2014.10.081
0261-3069/ 2014 Elsevier Ltd. All rights reserved.

mariyam.j.ghazali@gmail.com

stability, high solvency with other carbides, high melting point

(3067 C), high elastic modulus (410450 GPa), high thermal
conductivity (30  106 S/cm), as well as higher thermodynamic
stability and hardness than WC (33% more than WC) [1620].
Conventional cermets (WCCo) are tough and hard; however,
these materials possess poor oxidation resistance and plastic
deformation at high temperature, which prohibit their application
at elevated temperatures [2124]. As a result, a growing interest
has been given to the use of TiC-based cermets because of their several advantages [4,25]. However, using TiC-based cermets in its
early stage is not advisable because of their inherent brittleness at
low temperature [26,27]. Thus, scholars have attempted to improve
the mechanical properties of TiC-based cermets [24,28,29]. In
general, the mechanical properties of cermets depend on chemical
composition and sintering temperature [3032]. Thus, the present
study aimed to summarize the current state of knowledge concerning the effects of chemical composition, microstructure, and sintering temperature on the mechanical properties of TiC-based cermets.
2. Chemical composition
2.1. TiN
The use of TiN is constantly developing because of its prominent
physical and chemical properties, such as high melting
temperature (2927 C), relatively low oxidation, and low friction
coefcient. TiN can be utilized as hard coating and an essential
material for cermet and cutting tools owing to its high wear
resistance [3335].

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

Since 1970, several studies have been conducted to improve the

toughness of TiC-based cermets by modifying their microstructure
and grain size [36,37]. Changing the chemical composition of TiN is
a crucial strategy, and TiN has been considered more than other
elements. The hardness of TiN is much less than that of TiC
(TiC = 32 GPa; TiN = 20 GPa); thus, TiN can effectively improve
the toughness of TiC. However, the hardness and Youngs modulus
of TiC are reduced, as shown in Table 1 [38,39].
Another important issue to be noted is the quantity of TiN added
in the TiC-based cermets. Moskowitz et al. [40] demonstrated that
the maximum tool life value (TiCTiN22.5Ni10Mo10VC) is
achieved when the R = TiN/(TiN + TiC) ratio is approximately 45,
as illustrated in Fig. 1, because of grain renement and dissolution
of Mo in binder phase, which leads to solid solution hardening. In
this case, the fracture toughness (KIC) is decreased when R > 5,
resulting in a decreased tool life because of the formation of ner
grains. Although the effect of R ratio [TiN/(TiN + TiC)] on mechanical
properties of the cermets was investigated [40], the main reason of
the decrease in grain size is not signicantly considered. As
described in several studies [4143], typical microstructures of
TiC-based cermets involve a rim that encompassed the whole core,
as shown in Fig. 2. In general, dissolution and re-precipitation of the
metallic carbide (Ti, W, Mo, Ta) on the cores in the binder phase
results in rim formation [41]. Due to the complexity of the core
rim formation of the cermets, a fair assessment of the formation
mechanisms remain a difcult task [38]. Recently, many studies
have been conducted to understand the mechanisms of corerim
formation in cermets. Solid solution of rim, such as that in Ti(CN),
can be made through partial replacement of C atoms with N because
TiN decomposes at elevated temperature [42,43]. In this case, a dissolutionreprecipitation process is limited due to the declining
amount of TiC that is dissolving in the liquid phase, which results
in decrease in grains and moderate rims. As Ling et al. [42] observed
that the average grain size of the cermets decreases from 1.44 lm to
0.78 lm with increasing TiN addition from 0 to 37 wt.%, as shown in
Fig. 3; however, this nding is controversial. How rim thickness can
be hindered by existence of TiN particles in the cermets at during
sintering has not been elucidated. Liang et al. [42] found that N in
the cermets can act as an obstacle that is capable of preventing
the diffusion of Mo into rim at temperatures above 900 C; hence,
this process can be effectively employed to decrease rim thickness.
If these conditions are met, then the toughness of the cermets can be
improved, probably because of tensile stress reduction at the core
rim interface [43]. Tensile stress promotes crack propagation within
a corerim interface, leading to a decline in toughness [44].

Fig. 1. Tool life of AISI 4140 steel at 158 m/min as a function of TiN-to-(TiC + TiN)
ratio at sintering temperature of 1400 (s), 1475 (d), and 1550 C (N) [40].

Fig. 2. FE-SEM image of sintered cermet by SPS at 1718 K [32].

Previous studies [36,45,46] observed that microstructures with

coarse grains provide higher KIC than ner grains, in which the
transcrystalline fracture of the coarse grains offer a higher bonding
force than the intergranular fracture of ne grains. In general, the
ner grains of alloys assist in the increase in hardness, resulting
in a decline in KIC, as described by the following equation [47,48].

K IC 2:15  106

 0:6 
0:6
E
1 0:012E
 H1:5
H
H

where H, E, and KIC are the hardness, Youngs modulus, and fracture
toughness, respectively.
By contrast, Sun et al. [49] observed an increase in toughness in
WC11Co cermets with the formation of ne grains, which may be
induced by increasing the density. The formation of ner grains
results in a decline in pore size and an increase in fracture toughness. Such changes can be explained by the existence of cracks that
can be easily propagated from pores during fracture process
[50,51]. A brief comparison demonstrates that poor densication
can be derived from large particles, whereas high densication is
obtained by nano-grains to create large surface areagrain boundary [5254]. Consistent to this, the physicalmechanical properties
of materials with the same chemical composition can be improved
using nano-grains [5558]. This hypothesis can be approved by the
HallPatch relationship [59,60]. Previous studies [32,61] showed
that the presence of nano-TiN (10 wt.%) in TiC cermets provides
higher fracture toughness and transverse rupture strength (TRS)
than that of WCCo cermets (Table 2). Such improvement is
believed to be due to the existence of nano-TiN in grain boundary
that acts as an obstacle for grain growth; nano-TiN do not dissolve
in the sintering process completely and do not diffuse into the
ceramic hard phase. Moreover, nano-TiN sharply hinders the coalescence of TiC grains when distributed between TiC particles
(Fig. 4), resulting in disrupted motion of dislocations. Thus, grain
size reduction (renement) in the cermets can improve mechanical
properties such as TRS, based on HallPetch formula [62]. A previous study [32] indicated that intergranular fracture (along the
grain boundaries) is usually the dominant failure mode. Thus, crack
propagation can be limited by nanoparticles of TiN that are distributed in grain boundaries of TiC [63]. The main reason for the occurrence of such phenomenon is that cracks growing along the TiC/
TiNnano need more energy to propagate, resulting in improved
mechanical properties. Therefore, the distribution of TiN nanoparticles between TiC particles or inlayed between particles can be a
signicant factor [32,61]. In addition, Han et al. [32,61] indicated

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

Fig. 3. SEM micrographs of polished specimens: (a) 0 wt.%TiN, (b) 7.5 wt.%TiN, (c) 22.5 wt.%TiN, and (d) 37.5 wt.%TiN [42].

Table 1
Physical and mechanical properties for the two compositions [39].

Youngs modulus (GPa)

Microhardness (Hv)
p
Toughness (MPa m)

Cermet A

Cermet B

370 10
1510 120
61

290 10
1270 70
10 1

Cermet A: 65TiC10Mo2C25Ni. Cermet B: 55TiC10TiN10Mo2C25Ni.

that some added TiN nanoparticles (<80 nm) might be entrapped

within TiC grains, whereas nanoparticles with sizes ranging from
50 nm to100 nm are distributed at the ceramic grain boundaries,
forming an intra/inter-type microstructure, as shown in Fig. 5.
Micropits are also found because of breakage of TiN nanoparticles
during milling.
2.1.1. Effects on wear resistance
Fig. 6 displays the chipping and ank edge occurring at the tip
of the cermets. The crater wear zone between these two features
is wider in WCCo cermet than that in the TiCTiN cermet. The formation of the thermal cracks is not destructive in TiCTiN cermets
[61], which may be induced by higher thermal conductivity of TiN,
leading to an increase in thermal shock resistance of the cermets
[67,68]. This improvement is also due to the fact that low thermal
conductivity in cutting tools favors local overheating and results in
formation of microcracks and failure [66,69]. Consequently, an

increase in heat conductivity is considered an important factor in

controlling microcracks [7072].
The effect of chemical composition of TiC-based cermets on
ank wear is illustrated in Fig. 7 and Table 3. The tests were conducted under the same conditions: cutting speed (VC = 200 m/
min), feed rate (f = 0.5 mm/r), and depth of cutting (ap = 0.5 mm).
As shown in Fig. 7, an increase in the wear resistance for TiC-based
cermets is accompanied by existence of nano-TiN. These results are
in accordance with those reported by Han et al. [61], in which they
found an increase of tool life by approximately 15 times than that
of WCCo cermets by incorporating 10 wt.% nano TiN in TiC-based
cermets at 294 mm/min cutting speed. However, tool life of the
cermets depends on cutting speed, and its value can be decreased
as cutting speed is increased.
Despite the unique features of nanomaterials, some scholars
[73,74] reported that the development trend of nanoparticles is
sometimes inadequate. This phenomenon can be related to pores
existence in the cermets, resulting in decrease of density and fracture toughness of the cermets as shown in the Fig. 8. However, the
main reason of pore formation is not sufciently dealt with [63].
Moreover, nanoparticles can be contaminated by oxygen
[23,75,76], mainly because of the increase in surface area and surface energy of nanoparticles, which can be a result of oxygen
absorption [77,78]. Table 4 shows that the oxygen quantity in
nanoparticles is higher than the micropowders. Thus, when the
amount of added nanopowders is too high, the surface energy of
the solids decreases, thereby enhancing the wetting angle, as
described by Eq. (2) [73,79].

Table 2
Mechanical properties for TiC-based ceremts and WCCo.
Composition (wt.%)

Hardness

T.R.S. (MPa)

p
KIC (MP m)

References

TiC9.3TiNnm14WC9.3Ni7.5Mo2C
TiC10TiNnm8Ni
TiC10TiN20Ni15WC16Mo2C
WC6.5Co
WC6Co
WC8Co

89.7 0.2 (HRA)  1295 22 (HV)

1580 (HV)
1660 (HV)
89 (HRA)  1222 (HV)

1895
1898 50
1192

1470

12
12.0 0.3
11.85
10
10.9

[32]
[61]
[63]
[39]
[64]
[65]

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

Fig. 4. TEM micrographs showing TiN nano particles distributed at the interface of TiC/TiC grains (a [66]), (b [32]) and (c [47]).

Fig. 9 shows the variation in bending strength of TiC-based

cermets and FeTiC composite with the nano-TiN content. The gure also shows that bending strength decreases when the added
nano-TiN exceeds 6 wt.%, which corresponds to increase of oxygen
contamination of nano-TiN; studies are being conducted to solve
this problem. Using a vacuum heat treatment at 1200 C for 1 h,
the quantity of oxygen can be considerably decreased from
6.64 wt.% to 1.18 wt.% (i.e. about 82%) in the nano-TiN powder [82].
2.2. Ti(CN)

Fig. 5. FE-SEM image of cermet etched by nitric acid solution (0.1 mol/l) at 298 K
(a) [32] and (b) [61].

Cos h

csv  csl
clv

where csv, csl, and clv are the surface energy of the solid, solidliquid
interfacial energy, and surface energy of the liquid, respectively
[79]. Eq. (2) also shows that the wetting of ceramic particles with
binder decreases as the wetting angle increases because of the
oxidation of nanoparticles, thereby resulting in low density for sintered cermets. Under this condition, lack of wettability in the two
phases (ceramic and binder) creates a clear trend toward decreasing
the mechanical properties [7981].

Ti(CN) can be far better than TiN because of its high microhardness as well as the presence of carbon that serves as a lubricant
may enhance the cutting tool speed and service life [83]. Nitrogen
assists in increasing the coefcient of thermal expansion (CTE),
which is directly related to the inherent properties of TiN
(Fig. 10) [84]. In fact, Ti(CN) includes privileged characteristics to
both TiC and TiN, as shown in Table 5. These unique properties make Ti(CN) one of the advanced ceramic-based composites
employed in several applications such as electrical and electronics,
automotive, composites, refractory industries, and cutting tools
with much lower friction coefcient [39,85,86]. In addition, lack
of built-up edges, scaling, crescent depression, and formation of
oxidation layers during machining are another benets of Ti(CN)based in comparison to the TiC cermets [87,88]. Other advantages
include high microhardness, TRS, and thermal conductivity
(Table 6), resulting in better machining of high hardness/strength
of materials [39,67,68]. Thus, Ti(CN)-based cermets are good candidate for milling and rough machining of steelworks and hard materials, as supported by the following two reasons. First, surface
nishing, dimensional accuracy in work pieces, and resistance to
chipping are more desirable in Ti(CN)-based cermets than in
WCCo cermets [40,89]. Second, the mechanicalphysical properties, such as microhardness and density of Ti(CN) cermets are
higher than TiC/TiN cermets [90,91].
Ti(CN) has a common structure, that is, sodium chloride structure, wherein carbon atoms on the TiC superlattice can be replaced
by nitrogen atoms in any proportions that means C for TiC or N for
TiN-led edges of face-centered cubic, while Ti atoms occupied
(0.5, 0, 0) position of the superlattice, as shown schematically in
Fig. 11 [67,92]. Thus, a continuous series of solid solutions Ti(C1x,
Nx) (0 6 x 6 1) can be achieved, in which the physicalmechanical
properties would change with an increasing amount of nitrogen
and carbon, as listed in Table 7.

A. Rajabi et al. / Materials and Design 67 (2015) 95106

99

Fig. 6. SEM micrographs of the frontal view of the ank wear from (a) (TiC10% nano TiN) and (b) (WC8%Co), after 30 min milling [61].

Fig. 7. Cutting performance of different cutting tools [6] (13 details are in Table 3).

Table 3
Chemical composition of the tested cutter and cutting parameters [6].
No.

1
2
3

Chemical composition (wt.%)

TiC

WC

TiN

Mo2C

Co

0
15
39

92
79
15

0
0
10

0
0
16

8
6
0

The desired mechanical properties (fracture toughness and TRS)

are related to Ti(C0.5N0.5) composition. This phenomenon can be
explained from the fracture surfaces, as depicted in Fig. 12, indicating that Ti(C0.5N0.5) microstructure is ner than other
compositions.
Furthermore, the effect of stoichiometry on wear behavior and
coefcient friction of the TiCN is shown in Fig. 13. For different
stoichiometries of the TiCxN1x a moderate decrease in wear rate
and coefcient friction is accompanied by an increase in amount
of carbon [93,94]. Therefore, increasing the stoichiometry of the
carbide increases hardness values, as shown in Table 7. For this
similar result, Zhan et al. [95] explained that the decrease of C/N
ratio results in decreasing mechanical properties of the cermets
because of TiN decomposition at high temperature. An example
of this nding is illustrated in ank-worn SEM images in Fig. 14,
which shows an improvement in wear resistance achieved by
increasing C/N. Weight loss of the cermets can be inversely proportional to the bulk hardness based on Archards law [9698].
The variation of TRS of Ti(CN) cermets with different nano-TiC
and TiN additions is illustrated in Fig. 15. Table 4 shows chemical
compositions of sintered Ti(CN) cermets (33 wt.% TiC10 wt.%

Fig. 8. Effect of TiN nanoparticles on (a) density and (b) fracture toughness KIC [63].

TiN32 wt.% Ni16 wt.% Mo6.9 wt.% WC1.5 wt.% C0.6 wt.% Cr3
C2) using two different methods; vacuum furnace and spark
plasma sintering (SPS). Weight ratios of nano-TiC to micro-TiC
and that of nano TiN to TiN micro-TiN are 0%:100%, 20%:80%,
60%:40%, and 100%:0%, respectively. As can be seen from Fig. 15,
a signicant increase in TRS is observed in sintered samples in
vacuum furnace, when the weight ratio of nanopowder to micropowder reaches 0.2. However, the cermet with greater content of
nanoceramic powders shows a different trend; indicating that
the contaminated nano-particles are still stable [79]. By contrast,
Zheng et al. [23] indicated that the change in TRS of cermets is
relatively small and, there is a peak when the quantity of the ratio
is 1. This trend may indicate that oxygen contamination could be
declined during SPS method because of detached oxide layers on
the particle surface, resulting in improved TRS.

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

Table 4
Mean particles and oxygen content of raw materials.
Powders

TiC (nm)

TiC (lm)

TiN (nm)

TiN (lm)

Ni

Mo

WC

Cr3C2

References

Particle size (lm)

O2 content (mass%)
Particle size (lm)
O2 content (mass%)

<0.1
2.47
<0.1
2.47

2.58
0.77
2.88
0.37

<0.1
7.51
<0.1
7.51

14.89
0.36
1.18
0.33

2.3
0.22
1.7
0.30

2.80
0.10
2.80
0.10

0.72
0.56
0.85
0.21

1.80
0.14
2.77
0.16

5.5

5.5

[79]
[79]
[23]
[23]

Fig. 11. Illustration of lattice structure of TiC or TiN crystal [67].

Fig. 9. The inuence of nano TiN addition on bending strength (a) TiC-based cermet
[60] and (b) FeTiC [73].

Table 7
Mechanical properties of TiC + TiN powders hot pressed 1 h at 1850 C [90].
Composition

p
KIC (MP m)

rf (MPa)

Hv 0.3 (kg/mm2)

E (GPa)

Ti(C0.3N0.7)
Ti(C0.5N0.5)
Ti(C0.7N0.3)

5.4 0.62
6.3 0.03
5.7 0.1

360 30
435 10
330 40

1740 150
2100 165
2120 84

467
473
510

2.3. Carbon

Fig. 10. Temperature-dependent molar linear thermal expansion coefcients for

the various Ti(C1xNx) [84].

Table 5
The properties of TiC and TiN [68].
Properties

TiC

TiN

Molecular weight
Unit cell parameter (nm)
Melt point (K)
Density (g/cm3)
Thermal conductivity (W m1 K1)
Modulus of elasticity (GPa)

59.9
0.43180.4328
33403530
4.904.93
1724
315450

61.9
0.42400.4249
3223
5.395.44
29
251

A large number of potential applications of carbon that motivated researchers to study its effect on the properties of cermets.
According to earlier studies, carbon can change the mechanical
properties of cermets [100102]. Therefore, the importance of carbon has attracted interest to obtain desired qualications caused
by oxygen reduction. The reaction rate between carbon and oxygen
increased moderately with the increase in temperature during sintering. Ettmayer et al. [103] illustrated that the maximum value of
CO released is achieved at 1100 C, but decreased slowly because of
oxygen depletion, as shown in Fig. 16. The exact reaction sequence
is still under debate. Chen et al. [104] observed that the rst pick of
CO related to reaction of the surface of the binder phase particles
around 600700 C. Oxygen reaction in ceramic particles is
accompanied with the formation of main CO peak at around
11001250 C. The small CO peak located at around 1250
1300 C is attributed to the action of liquid phase and reduction
of particles ceramic, which is consistent with the observation of
Zhu et al. [105]. They reported that the reduction reaction is significantly performed at 11001300 C is due to the rapid decrease in
oxygen content of Ti(CN) cermets. Considering all of the mentioned
facts, carbon may have some different effects (positive or negative)
on the mechanical properties of cermets. Fig. 17 shows the variation of TRS with carbon content for different TiC-based cermets

Table 6
Comparison of high-temperature properties of a TiC-cermet and a Ti(C, N)-cermet [67].
Cermets

Microhardness (1000 C Kgf/mm2)

TRS (900 C, MPa)

Thermal conductivity (1000 C, W m1 k1)

TiC-based cermets
TiCN-based cermets

500
600

1050
1360

24.7
42.3

A. Rajabi et al. / Materials and Design 67 (2015) 95106

Fig. 12. Fracture surfaces of Ti(C, N) based materials observed by SEM. (a) Ti(C0.3N0.7) (b) Ti(C0.5N0.5) and (c) Ti(C0.7N0.3) [90].

Fig. 13. Dependence of friction and wear coefcients versus the stoichiometry of
the TiCx N1x hard phase [93].

and Ti(CN). However, the absolute value cannot be compared

because of different chemical composition and particles sizes.
The investigators found that an increase in TRS can be noticed
when the carbon content of the cermet is increased. This effect
can be attributed to improve of wettability in binder with ceramic
phase because of the carbon reaction with oxygen-contaminated
nanoparticles, and lower solid solubility of alloy elements in the
binder phase, as a result of the formation of carbides through reaction alloy element with carbon addition [106108]. However,
increasing the carbon content in cermets possesses limitation
when dealing with the mechanical properties. For example, the
TRS for TiC10%TiN15%WC20%Co is considered minimum when
the added carbon exceeds 1.5 wt.% because of the presence of
pores, which may be explained by the following criteria: (I) The
main source of pores maybe related to the release of trapped gas
because of a reduction reaction during sintering temperature
[101,109,110]. (II) At the nal stage of solidication, a part of the
binder phase has the lowest melting point because of segregation
phenomenon, leading to a rich carbon. Therefore, no existing supplier supports the shrinkage at this condition [111,112]. (III) In
addition, high carbon content (more than 2.5%, 1.5%, and 2.0% for

Fig. 15. The inuence of different nano TiC and TiN additions on TRS.

Fig. 14. Flank worn micrographs of TiCN matrix cermets: (a) TiC

Fig. 16. Schematic diagram of the released CO [103].

0.5

0.5

and (b) TiC0.4N0.6 [99].

101

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

3. Sintering

Fig. 17. The effect of carbon content on transverse rupture strength ,(a) Ti(C, N)
15%Ni15Mo%15%WC [108], (b) 33%TiC10%TiN32%Ni16%MoWC [107], (c)
TiC10%TiN15%WC20%Co [112].

cermets, Ti(C, N)15%Ni15Mo%15%WC, 33%TiC10%TiN32%Ni

16%MoWC, and TiC10%TiN15%WC20%Co, respectively) may
generate graphite formation and a decrease in the mechanical
properties, particularly along the ceramic particle boundaries
(Fig. 18a) [113]. Characterization by EDX spectroscopy conrmed
the presence of graphite phase, as observed in Fig. 18b. This phase
can promote crack propagations because of the relatively low
strength of graphites [114,115]. As indicated in Fig. 18c, cracks
are easily propagated when graphite precipitation occurs at grain
boundaries.
These results are in accordance with the investigation of Seo
et al. [101], who have studied the effect of carbon on mechanical
properties of Ti(CN) cermets. They showed that carbon excess
can assist in the formation of pores and graphite phase, resulting
in a decrease in hardness and fracture toughness (Fig. 19).

Most TiC-based cermets are synthesized via hot pressing (HP)

and vacuum furnace (VF) depending on specic requirements for
practical applications [116,117]. However, there are disadvantages
that limit the performance of cermets, hence, the application areas
for HP are particularly for maintenance costs and design exibility
[118,119].
Comprehensive knowledge has been acquired for sintering TiCbased cermets at different temperatures. Wang [120] showed that
the mechanical properties (i.e., hardness and TRS) of TiCTiN cermets depend on sintering temperature. The chemical composition
of cermets are TiC13%TiN13%NiMo2C (Mo2C/TiC:1/4), which
were milled for 24 h. The green samples were pressed at
149 MPa and sintered in vacuum (104 torr). Fig. 20a shows the
variations of the hardness of the cermets with TiN content and sintering temperature. The explanation is that the solubility of TiC in
TiN is anticipated according to phase diagram of TiCTiN [121].
Hardness can be decreased with an increase in TiN and sintering
temperature towing to the reaction of TiN with TiC during sintering, resulting in the formation of Ti(CN) solid solution; thus, the
hardness of this element is lower than that of the TiC phase
[93,122]. Fig. 20b displays the variations in TRS of the cermets in
relation to the sintering temperature during the sintering process.
The TRS value exhibits a tendency to increase as the sintering
temperature rises between 1400 and 1460 C, as shown in
Fig. 20b. This phenomenon can be attributed to the formation of
more Ti(CN) at 1460 C than at 1400 C. Ti(CN) is produced by a
substitutional mechanism, where C atoms replace N atoms.
Therefore, a higher sintering temperature is expected to produce
more Ti(CN). Thus, the cermet TRS exhibits the maximum value
when sintering temperature reaches 1460 C. Higher TRS value is
derived from higher sintering temperature, and its performance
is more inferior at 1520 C compared with that at other temperatures. This phenomenon may be due to TiN decomposition, that

Fig. 18. (a) Graphite precipitation [112], (b) EDX of graphite precipitation and (c) the rupture mode of crack through grains of high carbon content cermets (3.5 wt.%C) [108].

A. Rajabi et al. / Materials and Design 67 (2015) 95106

103

Fig. 21. SEM micrograph of TiC0.8N0.2 showing entrapped porosity in the grains
[125].
Fig. 19. Hardness and fracture toughness of various carbon after sintering for
(Ti0.7W0.3)CxNi [101].

Fig. 22. Mechanical properties of Ti(CN) based cerements. Transverse rupture

strength and hardness with different sintering temperature [123].

Fig. 20. The effect of sintering temperature on (a) hardness and (b) transverse
rupture strength TiCTiN ceremts [120].

is, denitrication (2TiN = 2Ti + N2). The generated N2 gas results in

internal pores, thereby decreasing the mechanical properties of
cermets. Evidence shows the decomposition of TiN during hightemperature sintering is greater than that of 1400 C [50,123,124].
These values are in good agreement with those reported previously [125]. They indicated that porosities at the grains could be
detected by SEM due to TiN decomposition (Fig. 21).

Fig. 23. The bending strength and density of Ti(CN) based ceremts [109].

Comprehensive studies have been performed by Yan et al. [123]

to obtain additional details about TiN decomposition. They demonstrated that the mechanical properties (i.e., hardness and TRS) in
Ti(CN) cermets have a similar trend with that of the variation in
sintering temperature, as depicted in Fig. 22. TRS and hardness
increase with the increase in sintering temperature, reaching a
maximum value at 1430 C, but decrease with a further increase
in sintering temperature. Decomposition of TiN occurs when the
sintering temperature is higher than 1430 C.

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A. Rajabi et al. / Materials and Design 67 (2015) 95106

Recently, Li et al. [109] reported that the density of Ti(CN)based cermets increased sharply when the sintering temperature
reaches approximately 1450 C because of melting of metal binders, which can improve wettability for binder and ceramic particles
(Fig. 23). Furthermore, the increase in TRS can be attributed to the
dissolution of heavy elements, such as W, Mo, and Ta in the binder,
causing a solution hardening.
4. Conclusions
Recent investigations on the improvement of TiC-based cermets are summarized in this review to evaluate the different
research results. The high hardness of TiC has been well known
to increase the mechanical properties of cermets, except for
toughness. The studies in this review showed that chemical composition, grain size, microstructure, and sintering temperature are
key factors for increasing toughness in TiC-based cermets. Among
the different elements, TiN is more crucial in improving the
toughness of cermets because of low hardness and similar crystal
structure. The use of nano-TiN is believed to have an effect in
increasing the performance of cermets. The advantages of using
nano-TiN in cermets include high densication, control of grain
growth, lack of easy motion of dislocations, and control over
micro-crack propagation during wear. Using nanoparticles can
pose some negative consequences, which can be induced by contamination of nanoparticles with oxygen. Under this condition,
the mechanical properties of cermets decrease with the decline
in wettability between nanoparticles and binder. The limitation
may be improved by using vacuum heat treatment.
Previous studies have presented that microstructure of the cermets included binder and grains because most of them have a typical corerim structure, in which the rim is formed during sintering
process via dissolutionreprecipitation. The increase in rim thickness can be a result of decreasing mechanical properties of the cermets because of the existence of tensile stress at the corerim
interface. Therefore, rim thickness has been moderated with the
use of TiN. In fact, released N from decomposition TiN during sintering act as barrier of diffusion of elements, such as Mo, into rim
above 900 C.
The increase in carbide stoichiometry in the Ti(CN), such as
Ti(C0.7N0.3), decreases the wear rate because of its high hardness.
However, the best toughness is achieved at Ti(C0.5N0.5).
In general, the increase in sintering temperature can be noted
because of relatively high rate of Ti(CN) solid solution. Increasing
the sintering temperature to just above 1430 C results in the
decomposition of TiN. Moreover, the formation of porosities
because of TiN decomposition favors to the decrease in mechanical
proprieties.
In the last 10 years, a strong interest for TiC-based cermets
motivated researchers to produce cermets with higher toughness
without losing too much of their other properties. These properties
make such cermets as adequate candidate for WCCo cermets.
Therefore, the trend of developing TiC-based cermets is still motivated by its potential use as a source of a kind of tool wear and
numerous engineering applications. Further studies are necessary
to fabricate novel materials consisting of characterization TiC/TiCN
with excellent performance and ideal durability for use in more
demanding applications.
Acknowledgement
Financial support from FRGS, Govt. of Malaysia (Grant No. UKMKK-03-FRGS 0120-2010) to conduct the study is gratefully
acknowledged.

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