Journal of Alloys and Compounds 685 (2016) 905e912

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Inuence of nickel boride addition on sintering behaviour and

mechanical properties of TiCeNi based cermets
Suvalaxmi Acharya y, M. Debata*, T.S. Acharya, P.P. Acharya, S.K. Singh
Advanced Materials Technology Department, CSIR-Institute of Minerals and Materials Technology, Bhubaneswar 751013, Odisha, India

a r t i c l e i n f o a b s t r a c t

Article history: TiCeNi based cermets were prepared by vacuum sintering at 1200  C, 1300  C and 1400  C. NiB (0, 10,
Received 15 October 2015 20 wt%) was added to improve sintering activity by creating a liquid phase and enhance the densication.
Received in revised form The effects of NiB content on density, microstructure, hardness, elastic modulus, fracture toughness, and
10 June 2016
thermal expansion were studied. Density, micro hardness, elastic modulus, and fracture toughness, of the
Accepted 13 June 2016
composite were increased by the addition of 10 wt% NiB. The 1400  C sintered sample with 10 wt% NiB
Available online 18 June 2016
resulted in maximum densication with 97% of theoretical density. The 1400  C sintered TiCe10Ni
e10NiB showed better mechanical properties with elastic modulus of 470 GPa, hardness of 2759 H V and
Keywords:
TiC-Ni-NiB cermet
fracture toughness 8.98 MPa m1/2, all better than that of TiCe20Ni sintered at same condition.
Powder metallurgy 2016 Elsevier B.V. All rights reserved.
CTE
FESEM
Elastic modulus
Hardness

1. Introduction
TiC-based cermets are commonly used as cutting tool material,
especially in nishing operations, due to their high hardness,
strength, wear resistance and phase stability, which are essential
for high temperature applications [1e3]. Binders such as Fe, Cr, Co,
Ni are added in TiC-based cermets to increase ductility and
toughness. For the preparation of TiC-based cermets the solid state
methods employed are: powder metallurgy, self-propagation high
temperature synthesis, mechanical alloying and carbon thermal
reduction etc. As these cermets are very hard to machine, it is
preferred to use powder metallurgy route to obtain near net shaped
nal products. The two main operations of the powder metallurgy
process are compacting and sintering. Sintering can take place with
a transient (temporary) or with a permanent liquid phase. In liquid
phase sintering, wetting angle plays an important role. For a
smaller value of wetting angle, the driving force will be higher.
However, due to the poor wettability between TiC and Ni (wetting
angle is 30 in vacuum and 17 in a hydrogen atmosphere [4], it is
difcult to sinter TiCeNi compared to WC-Co [2,5e7]. During vac-
uum sintering, the metal binder which has lower melting
* Corresponding author.
E-mail address: mayadhar.debata@gmail.com (M. Debata).
y
Deceased.
temperature, melts and dissolution and mass transport takes place
in the liquid. To improve the wettability of Ni with TiC/TiCN com-
posite, Mo2C was added [8,9]. WC has been added to TiC/TiCN
composite for enhancing the TRS (Transverse Rupture Strength)
and fracture toughness [10]. Mo is also added in TiC/TiCN, not only
to enhance the wettability between grains, but also improve the
densication and mechanical properties [11,12]. Sinterability and
thermal shock resistance were improved by addition of secondary
carbides such as Mo2C, WC, NbC, ZrC in TiC/TiCN composite
[13e17].
Worauaychai et al. [18] have reported that P addition increases
mechanical properties in terms of hardness and toughness in
TiCeNi composites. Cardinal et al. [19] found that TiN additions
improved both hardness and toughness. Addition of low melting
point boride in the form of nickel boride (NiB) having melting point
of 1018  C [20] leads to densication of the cermets by liquid phase
sintering because the pseudo-binary eutectic reaction occurs at
relatively low temperature. Nickel boride is generally used as a
sintering additive to increase the density at a lower temperature
and for good mechanical properties, especially high-temperature
strength. Gulsoy [21] conducted a set of sintering experiments on
17e4 PH stainless steel samples at 1280  C for 45 min to study the
effect of 0.25, 5, 0.75 and 1 wt % NiB additions on the nal sintered
density. An increase in relative density, as well as mechanical
properties was observed in the NiB containing samples. Near full

http://dx.doi.org/10.1016/j.jallcom.2016.06.122
0925-8388/ 2016 Elsevier B.V. All rights reserved.
906 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912
density (7.8 g/cm3) was obtained with a 1 wt % NiB addition. Debata
and Upadhyaya [22] added NiB in tungsten-based alloys and ach-
ieved higher density, with increased hardness. Little experimental
work on the effect of NiB on cermets has been reported to date, and
hence there is good potential for extensive investigation.
The objective of this work was to study the inuence of NiB
additions on sintered density, microstructure, and mechanical
properties of TiCeNi cermets at different temperatures. NiB is used
as a sintering additive to achieve higher sintered density in TiCeNi
based composites at lower sintering temperatures. Milling time,
milling speed, and ball-to-powder ratio were kept constant. Sin-
tering time of 1 h was kept constant. Sintered density, hardness,
elastic modulus, fracture toughness and thermal expansion of the
sintered samples were evaluated. Detailed characterization, such as
XRD, TG-DTA, SEM and FESEM of the sintered samples were carried
out.
2. Experimental investigations
Titanium carbide powder (Alfa Aesar, 2 mm, and purity 99.9%)
and nickel powder (Alfa Aesar, 3e7 mm, purity 99.7%) were used in
the preparation of the cermets. Nickel boride (NiB, Alfa Aesar, pu-
rity 99%) was added to the TiCeNi mixed powders. Three different
compositions were prepared as listed in Table 1. The powder mix-
tures were milled in a Pulverisette 7 vial using WC-Co balls
(dia. 1.6 mm) for 1 h in isopropyl alcohol medium. The ball-to-
powder ratio was maintained at 20:1 and a speed of 300 rpm
was kept constant. The milled powders were compacted under a
uniaxial load of 1.6 T to produce cylindrical shape samples of 10 mm
diameter and 4 mm height. Sintering was performed in a high
temperature vacuum furnace (Vicco, VF-2000 series) for 1 h at
1200 , 1300 and 1400  C respectively.
Phase analysis of the as-milled powders, as well as sintered
samples, was done by XRD (X-ray diffraction) using a PAN analytical
XPert PRO X-ray diffractometer (Cu Ka radiation and Ni lter for 2q
from 10 to 80 with a scanning rate of 2 per minute). The liquid
formation temperature of each sample was measured by simulta-
neous thermal analysis (METTELER TOLEDO TGA/SDTA 851e)
technique. The differential thermal analysis (DTA) was performed
from 30  C to 1400  C at the rate of 10  C/min. The as-milled
powders for DTA tests were loaded in to the crucible under nitro-
gen. Microstructures of the as-milled powders were observed un-
der a scanning electron microscope (SEM, JEOL Model JSM-6510).
Microstructures and chemical compositions of the as-sintered
samples were studied by a Field Emission Scanning Electron Mi-
croscope (FESEM, SUPRA GEMINI55, CARL ZEISS, and GERMANY)
with an energy dispersive X-ray spectrometer (EDS). The samples
were coated with gold for the FESEM and EDS analysis, and ve
analyses in different places were taken on the dark and light re-
gions. The bulk density of the sintered samples was determined by
Archimedes principle and compared with the theoretical density,
which was calculated using the rule of mixtures. The linear co-
efcient of thermal expansion (CTE) was measured by using a
horizontal dilatometer (Linseis, L75HS 1600) under the following
conditions: temperature range 25  Ce600  C, heating rate 5  C/min,
Table 1
Composition of cermet samples.
Weight [%] Volume [%]
Cermet no. TiC Ni NiB TiC Ni
C1 80 20 0 88 12
C2 80 0 20 88 0 12
C3 80 10 10 88 06
and Ar atmosphere. The micro-hardness of the sintered samples
was measured by Vickers hardness tester (Zwick/Roell ZHV), under
a load of 5000 g for a dwell time of 10 s. The nanoindentation
technique was used to determine elastic modulus. Fracture
toughness (KIC) was calculated using the indentation method under
the load of 5000 g using the equation derived by Shetty et al. [23]:
KIC 0:0889Hv P=4l1=2 (1)
where Hv is the Vickers hardness, l is the crack length in (mm), and
P is the indentation load in (MPa).
3. Results and discussion
3.1. Thermal analysis
Fig. 1 shows the DTA of TiCeNi/NiB phase transformations with
different Ni/NiB contents up to 1400  C. These DTA curves show
that not much change occurred from 200  C to 1000  C, showing no
phase transition or chemical reaction took place in nitrogen during
heating. Thus, thermal stability of composite powders, as well as
the stability of their phases, at 200e1000  C was conrmed.
The onset points of DTA heating curves were used as a beginning
of melting. Three peaks were observed at 1155  C, 1213  C and
1369  C from DTA for the TiCe20Ni cermet. The peak at 1369  C
corresponds to the appearance of liquid phase of the Ni binder
(liquid phase formation has an endothermic peak). Substituting Ni
by NiB, the temperature at which liquid phase appeared decreased
to 1356  C. In TiCe10Nie10NiB sample, peaks were at 1155  C,
1214  C, and 1359  C, which were lower than for TiCe20Ni. Thus,
the addition of NiB lowered the melting point about 10  C.
3.2. Phase constitution
Fig. 2 (a) shows XRD patterns of the as-milled TiCe20Ni,
TiCe20NiB and TiCe10Nie10NiB powders, milled for 1 h, and Fig. 2
(b), (c) and (d) show the patterns of TiCe20Ni, TiCe20NiB and
TiCe10Nie10NiB sintered at 1200  C, 1300  C and 1400  C.
The XRD patterns had peak of the major phases TiC, Ni, and NiB.
The patterns of TiC and Ni were of the space group Fm-3m, 225, and
the lattice parameters of TiC and Ni were 0.4311 nm and 0.3555 nm
respectively, calculated by Cohens method [24].
3.3. Powder morphology
Fig. 3 (a) shows the SEM image of un-milled pure TiC powder,
and Fig. 3 (bed) show the images of 1 h milled sample of TiCe20Ni,
TiCe20NiB and TiCe10Nie10NiB. In the as-milled powder, much
ner particles were observed with some agglomerates. The milled
powder became agglomerated because of very ne size and also
due to pick up of moisture from atmosphere.
3.4. Density
Fig. 4 shows the sintered density of all three cermets sintered at
1200 Ce1400  C. The green density was measured and found to be
approximately 60e65% theoretical density. TiCeNi with 10 wt% NiB
additions produced a maximum sintered density of 97% theoretical
density when sintered at 1400  C.
It can be seen from Fig. 4 that among the three cermets sintered
at three different temperatures, maximum densication was
NiB
observed in the case of cermet C3 sintered at 1400  C. Taking the
0 effect of errors into account, the sintered density values of C1 and
C2 for temperatures 1300  C and 1400  C can be considered similar
06
(~93e96% of theoretical). The densication mostly depends upon
 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912 907

Fig. 1. Differential thermal analysis of mixed powders: (a) as-milled TiCe20Ni (b) as-milled TiCe20NiB and (c) as-milled TiCe10Nie10NiB (all milled for 1 h each).

Fig. 2. XRD patterns of (a) TiCeNi/NiB composite powders as-milled, (b) sintered at 1200  C, (c) sintered at 1300  C, and (d) sintered at 1400  C.

the amount of liquid phase formed [25]. As the melting point of the the density increased as the porosity decreased. However, the
binders was in the range of 1356e1369  C from the DTA curves reason for higher density for cermet C3 at 1400  C may be attrib-
(Fig. 1), sufcient liquid formed at 1400  C which lled the pores uted to the presence of NiB with Ni.
around the TiC particles, and due to the rearrangement of grains,
908 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912
Fig. 3. Scanning electron micrographs of powder; (a) un-milled TiC, (b) milled TiCe20Ni, (c) TiCe20NiB and (d) TiCe10Nie10NiB.
Fig. 4. Inuence of NiB on sintered density of the cermets sintered at 1200 , 1300 ,
and 1400  C.
3.5. Microstructure analysis of sintered cermets
Figs. 5e7 show the microstructures of cermets sintered at
1200  C, 1300  C and 1400  C with different binder contents. The
microstructure shows that TiC particles were homogeneously
distributed in Ni/NiB matrix and also shows the core-rim structure
embedded with Ni/NiB matrix, which is common in TiC-based
cermets produced by conventional technology [3,18,19,26,27]. The
dark-gray cores of un-dissolved TiC were precipitation sites for the
Ni and (Ti,Ni)C solid solutions. The gray rims were solid solutions of
(Ti,Ni)C, and the bright regions were rich in Ni with some dissolved
TiC. This is in good agreement with literature [3,26,27] and was also
shown by EDS. The core/rim structure observed in this work is
similar to the structure reported by Monteverde et al. [28]. The
decrease of specic surface energy (Yr) of the system is the driving
force, and is given by Equation (2) [25]:
gr gS gL  gSL (2)
where YS, YL are the specic surface energies for solid and liquid
respectively, and YSL is the specic phase boundary energy for
solid/liquid. Energy decreases when YSL YS, YL.
If the specic phase boundary energy is low, LPS (liquid phase
sintering) will be more successful. So, spherical and smaller particle
sizes are desirable for LPS. The as-milled powders used in this work
were very ne, which possessed more surface area and high surface
energy, resulting in increased driving force.
3.5.1. Effect of sintering temperatures on the microstructures
Cermets sintered at 1200  C (Fig. 5) had pores indicating that
sintering was limited and incomplete. At lower temperatures,
imperfect penetration of Ni/NiB binder phase, as well as non-
uniform distribution of TiC in the matrix occurred. Cermets sin-
tered at 1300  C (Fig. 6) showed that some Ni/NiB binder particles
started melting and wetted the TiC particles. At 1400  C, the sin-
tered cermet had TiC grains well-surrounded by the NieNiB matrix
as the solubility was higher. DTA analyses showed endothermic
peaks at 1356e1369  C (Fig. 1) which is the melting point of the
binder. At 1400  C, complete melting occurred, which helped to
remove pores, and produced dense microstructures. The primary
purpose of liquid phase sintering is to achieve highest possible
densication, combined with high strength and high toughness.
The liquid lls the gaps between the TiC particles and reduces
pores. Steps in LPS include liquid formation, solution re-
precipitation and nally solid state sintering. Important concepts
are grain shape accommodation and stable microstructure based
on the liquid content and dihedral angle between solid-solid grain
boundary and liquid [25]. Since these processes are typically
involved in liquid phase sintering for producing dense micro-
structures, the melting of the binder phase affects the microstruc-
ture greatly.
 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912 909

Fig. 5. Effect of NiB content on microstructure of: (a) TiCe20Ni, (b) TiCe20NiB, and (c) TiCe10Nie10NiB cermets sintered at 1200  C. The dark-gray phase/gray phases show the
typical core/rim structure and the bright phase is the binder. Some pores are also indicated.

Fig. 6. Effect of NiB content on microstructure of: (a) TiCe20Ni, (b) TiCe20NiB, and (c) TiCe10Nie10NiB cermets sintered at 1300  C. The dark-gray phase/gray phases show the
typical core/rim structure and the bright phase is the binder.

3.5.2. Effect of NiB addition on the microstructure
Addition of 10 wt% NiB enhanced the sintering rate, which may
be due to the presence of low melting point boride phase. The
liquid phase provided large contact areas between the TiC and
matrix phase (Ni/NiB) and facilitated the process of solution-
precipitation, which involved (i) diffusion of atoms along grain
contacts and rapid mass transfer through the liquid and (ii) grain
shape accommodation, leading to pore elimination.
Boron activates the sintering process by forming the liquid
phase. Ni/NiB forms a liquid phase and this liquid remained almost
continuous between the TiC grains, thus favoring liquid phase
sintering. When the amount of NiB was increased (20 wt%), boron
tended to segregate to the surfaces and grain boundaries, and did
not improve the density and microstructure. It may therefore be
inferred that certain amount of B is required to form a layer at the
grain boundaries, which provides the path of high diffusivity and
allows rapid densication.
The correct amount of liquid phase has signicant impact on
910 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912
Fig. 7. Effect of NiB content on microstructure of: (a) TiCe20Ni, (b) TiCe20NiB, and (c) TiCe10Nie10NiB cermets sintered at 1400  C. The dark-gray phase/gray phases show the
typical core/rim structure and the bright phase is the binder. Pores are also shown.
interfaces between the solid grains, and improves wetting, accel-
erates diffusion according to interfacial energy and phase relations,
which allows fast sintering or lower sintering temperatures [25].
Thus, it can be surmised that if the amount of NiB and sintering
temperature are optimized, full density and enhanced mechanical
properties could be achieved.
In order to clarify the composition of the dark as well as bright
regions, EDS analysis was conducted on the TiCe10Nie10NiB
cermet sintered at 1400  C, Fig. 8. As expected, the dark region was
TiC with a little Ni and NiB. The bright phase was the binder (Ni and
NiB) with some Ti and C. The Au peak was from the gold coating. In
the cermet samples, ve different locations in dark phase, as well as
bright phase, were selected and average values are reported in
Table 2. For TiC, though one would expect the C content to be in the
Fig. 8. SEM-BSE micrograph of TiCe10Nie10NiB cermet sintered at 1400  C.
Spectrum
3 corresponds to Dark region (TiC) and Spectrum 2 corresponds to Bright region
(binder).
range of ~31e49 atomic % [20], ~59 to 67 atomic % C was observed.
This could have arisen primarily due to the limitation of EDS for
reporting carbon. The TiC phase was also conrmed by XRD (Fig. 2).
The EDS results did not show B due to the limitation of the
available EDS instrument (Silicon drift detector) in not being able to
detect elements with atomic numbers below carbon.
3.6. Micro-hardness and elastic modulus
Fig. 9 shows the variation in micro-hardness with composition
of the cermets sintered at 1200  C, 1300  C, and 1400  C, and the
errors were small. For cermet C3, the maximum hardness of
2759 43 Hv was achieved with 10 wt % NiB addition, while the
maximum hardness of C1 was 1862 27 Hv and C2 was 1833 18
Hv. The addition of 20 NiB (C2) reduced the hardness which is
attributed to the lower densication during liquid phase sintering.
The high hardness of the cermet C3 was due to enhanced densi-
cation during sintering. Apart from higher density, the high hard-
ness obtained may be attributed to the strong interfacial bonding
between TiCeTiC grains due to presence of both Ni and NiB as
binder [29], but this needs to be conrmed. Further detailed studies
are required to conrm the nding, which is beyond the scope of
current work.
Fig. 10 shows the variation in elastic modulus with composition
of the cermets sintered at 1200  C, 1300  C, and 1400  C for 1 h. The
sintered TiCe10Nie10NiB cermet had signicantly higher elastic
modulus compared to TiCe20NiB. An elastic modulus of
460 6 GPa was achieved for TiCeNi without NiB after sintering at
1400  C. The maximum elastic modulus of 470 4 GPa was attained
with samples containing 10Nie10NiB after sintering at 1400  C,
whereas TiCe20NiB showed a maximum elastic modulus of
444 7 GPa.
3.7. Fracture toughness
Fig. 11 shows the variation in fracture toughness with compo-
sition of the cermets sintered at 1200  C, 1300  C, and 1400  C.
 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912 911

Table 2
Chemical composition obtained from EDS analysis.

Spectrum Weight [%] Atomic [%]

CK Ti K Ni K Au M CK Ti K Ni K Au M

Dark region 28.0 2.9 63.0 1.8 1.0 3.2 8.0 0.3 63.0 3.8 35.0 3.1 1.0 1.8 1.0 0.2
Bright region 29.0 1.9 28.0 2.9 34.0 2.9 9.0 0.4 66.0 0.6 16.0 1.3 17.0 0.8 1.0 0.2

Fig. 9. Vickers micro-hardness of TiCeNi cermets with 0, 20 and 10 wt % NiB additions Fig. 11. Fracture toughness of vacuum sintered TiCeNi cermets with 0, 20 and 10 wt %
sintered at 1200  C, 1300  C and 1400  C. NiB additions sintered at 1200  C, 1300  C, and 1400  C.

(CTE) with temperature for the cermets sintered at 1200  C, 1300  C

and 1400  C.
The CTE of the TiCe20Ni cermet (C1) calculated using the Kerner
model [30] was 8.35  106/ C, which was in good agreement with
the experimental value of CTE of 1400  C sintered TiCe 20Ni
measured at 300  C (9.0  106/ C) in the present study. According
to the Kerner model, CTE is given by Ref. [30]:

ar  am Kr  Km
ac ar Vr am Vm Vr Vm (3)
Vr Kr Vm Km 3Kr Km =4Gm

where a is CTE, V is volume fraction, K is bulk modulus, G is shear

modulus, and subscripts c, r and m represent composite, rein-
forcement and matrix respectively. The low CTE of

Fig. 10. Elastic modulus of TiCeNi cermets with 0, 20 and 10 wt % NiB additions
sintered at 1200  C, 1300  C and 1400  C for 1 h.

The fracture toughness was highest for C3 and the errors

showed that there were similar values for C1 and C2. The value of
fracture toughness after the addition of 10NiB (8.98 MPa m1/2)
increased, which is comparable with WC-Co (10e12 MPa m1/2)
cermet [2,30] and suitable for commercial use. Previously reported
values of fracture toughness for TiCeNi cermets are
6.8e7.4 MPa m1/2 [31]. The improved toughness may be due to the
dense microstructure obtained in the TiCe10Nie10NiB cermet as a
result of the addition of NiB and the homogeneous distribution of
TiC particles in Ni/NiB matrix.

3.8. Coefcients of thermal expansion

Fig. 12 shows the variation in coefcients of thermal expansion Fig. 12. CTE of 1400  C vacuum sintered TiCeNi cermets with different NiB additions.
912 S. Acharya et al. / Journal of Alloys and Compounds 685 (2016) 905e912
TiCe10Nie10NiB composite sintered at 1400  C may be due to
enhanced densication due to presence of NiB in the binder, and
also due to the strong interface bonding [29,32] by the addition NiB,
which restrains the deformation of metal matrix.
4. Conclusions
a) Metal matrix composites of TiCeNi with different amounts of
NiB binder were successfully prepared. The 1400  C sintered
sample with 10 wt% NiB had the maximum densication
with 97 0.21% theoretical density, using pressureless liquid
phase sintering.
b) In TiCe10Nie10NiB cermet, a ne and dense microstructure
was developed, which accounted for the enhanced hardness
of 2759 43 Hv sintered at 1400  C.
c) Elastic modulus of 470 4 GPa, fracture toughness
8.98 0.28 MPa m1/2 was obtained in the sintered cermet
containing 10 wt % NiB.
d) A reduced CTE (8.36 0.01)  106/ C was found for
TiCe10Nie10NiB cermet.
Acknowledgements
This work was carried out in the Supra Institutional Project ESC
0401 titled Centre for Special Materials supported by CSIR, New
Delhi, India. The authors would like express their deep gratitude to
the Director, CSIR-IMMT, for granting permission to publish this
paper.
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