Accepted Manuscript

Influence of nickel boride addition on sintering behaviour and mechanical properties

of TiC–Ni based cermets

Suvalaxmi Acharya, M. Debata, T.S. Acharya, P.P. Acharya, S.K. Singh

PII: S0925-8388(16)31845-X
DOI: 10.1016/j.jallcom.2016.06.122
Reference: JALCOM 37991

To appear in: Journal of Alloys and Compounds

Received Date: 15 October 2015

Revised Date: 10 June 2016
Accepted Date: 13 June 2016

Please cite this article as: S. Acharya, M. Debata, T.S. Acharya, P.P. Acharya, S.K. Singh, Influence
of nickel boride addition on sintering behaviour and mechanical properties of TiC–Ni based cermets,
Journal of Alloys and Compounds (2016), doi: 10.1016/j.jallcom.2016.06.122.

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Influence of nickel boride addition on sintering behaviour and

mechanical properties of TiC-Ni based cermets

Suvalaxmi Acharya+, M. Debata*, T.S. Acharya, P.P. Acharya, S.K Singh

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Advanced Materials Technology Department, CSIR-Institute of Minerals and Materials
Technology, Bhubaneswar-751013, Odisha, India

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Abstract

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TiC-Ni based cermets were prepared by vacuum sintering at 1200°C, 1300°C and 1400°C.

NiB (0, 10, 20 wt %) was added to improve sintering activity by creating a liquid phase and

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enhance the densification. The effects of NiB content on density, microstructure, hardness,
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elastic modulus, fracture toughness, and thermal expansion were studied. Density, micro

hardness, elastic modulus, and fracture toughness, of the composite were increased by the
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addition of 10 wt% NiB. The 1400°C sintered sample with 10wt% NiB resulted in maximum
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densification with 97% of theoretical density. The 1400°C sintered TiC-10Ni-10NiB showed
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better mechanical properties with elastic modulus of 470GPa , hardness of 2759 HV and fracture

toughness 8.98MPa.m1/2, all better than that of TiC-20Ni sintered at same condition.
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Keywords: TiC-Ni-NiB cermet; Powder metallurgy; CTE; FESEM; Elastic Modulus; Hardness.
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+ Deceased
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* Corresponding author. Tel.: +91-674-2379489.

E-mail address: mayadhar.debata@gmail.com (M. Debata)

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1. Introduction

TiC-based cermets are commonly used as cutting tool material, especially in finishing

operations, due to their high hardness, strength, wear resistance and phase stability, which are

essential for high temperature applications [1-3]. Binders such as Fe, Cr, Co, Ni are added in

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TiC-based cermets to increase ductility and toughness. For the preparation of TiC-based cermets

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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

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to machine, it is preferred to use powder metallurgy route to obtain near net shaped final

products. The two main operations of the powder metallurgy process are compacting and

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sintering. Sintering can take place with a transient (temporary) or with a permanent liquid phase.
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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
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(wetting angle is 30° in vacuum and 17° in a hydrogen atmosphere [4], it is difficult to sinter
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TiC-Ni compared to WC-Co [2, 5-7]. During vacuum sintering, the metal binder which has
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lower melting temperature, melts and dissolution and mass transport takes place in the liquid. To

improve the wettability of Ni with TiC/ TiCN composite, Mo2C was added [8, 9]. WC has been
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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
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between grains, but also improve the densification and mechanical properties [11,12].
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Sinterability and thermal shock resistance were improved by addition of secondary carbides such

as Mo2C, WC, NbC, ZrC in TiC/TiCN composite [13-17].

Worauaychai et al. [18] have reported that P addition increases mechanical properties in

terms of hardness and toughness in TiC-Ni composites. Cardinal et al. [19] found that TiN
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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 densification 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

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a lower temperature and for good mechanical properties, especially high-temperature strength.

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Gulsoy [21] conducted a set of sintering experiments on 17-4 PH stainless steel samples at

1280°C for 45min to study the effect of 0.25, 5, 0.75 and 1 wt % NiB additions on the final

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sintered density. An increase in relative density, as well as mechanical properties was observed

in the NiB containing samples. Near full density (7.8 g/cm3) was obtained with a 1 wt % NiB

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addition. Debata and Upadhyaya [22] added NiB in tungsten-based alloys and achieved higher
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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.
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The objective of this work was to study the influence of NiB additions on sintered density,
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microstructure, and mechanical properties of TiC-Ni cermets at different temperatures. NiB is

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used as a sintering additive to achieve higher sintered density in TiC-Ni based composites at

lower sintering temperatures. Milling time, milling speed, and ball-to-powder ratio were kept
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constant. Sintering time of 1h was kept constant. Sintered density, hardness, elastic modulus,
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fracture toughness and thermal expansion of the sintered samples were evaluated. Detailed
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characterization, such as XRD, TG-DTA, SEM and FESEM of the sintered samples were carried

out.
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2. Experimental investigations

Titanium carbide powder (Alfa Aesar, 2 µm, and purity 99.9%) and nickel powder (Alfa

Aesar, 3-7µm, purity 99.7%) were used in the preparation of the cermets. Nickel boride (NiB,

Alfa Aesar, purity 99%) was added to the TiC-Ni mixed powders. Three different compositions

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were prepared as listed in Table 1. The powder mixtures were milled in a Pulverisette 7 vial

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using WC-Co balls (dia. =1.6mm) for 1h in isopropyl alcohol medium. The ball-to-powder ratio

was maintained at 20:1 and a speed of 300rpm was kept constant. The milled powders were

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compacted under a uniaxial load of 1.6 T to produce cylindrical shape samples of 10mm

diameter and 4mm height. Sintering was performed in a high temperature vacuum furnace

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(Vicco, VF-2000 series) for 1h at 1200°, 1300° and 1400°C respectively.
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Phase analysis of the as-milled powders, as well as sintered samples, was done by XRD (X-
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ray diffraction) using a PAN analytical X’Pert PRO X-ray diffractometer (Cu Kα radiation and

Ni filter for 2θ from 10° to 80° with a scanning rate of 2° per minute). The liquid formation
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temperature of each sample was measured by simultaneous thermal analysis (METTELER

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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
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in to the crucible under nitrogen. Microstructures of the as-milled powders were observed under
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a scanning electron microscope (SEM, JEOL Model JSM-6510). Microstructures and chemical
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compositions of the as-sintered samples were studied by a Field Emission Scanning Electron

Microscope (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 five analyses in different places were taken on the dark and light regions. The

bulk density of the sintered samples was determined by Archimedes principle and compared with
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the theoretical density, which was calculated using the “rule of mixtures”. The linear coefficient

of thermal expansion (CTE) was measured by using a horizontal dilatometer (Linseis, L75HS

1600) under the following conditions: temperature range 25°C to 600°C, heating rate 5°C/min,

and Ar atmosphere. The micro-hardness of the sintered samples was measured by Vickers

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hardness tester (Zwick/Roell ZHV), under a load of 5000g for a dwell time of 10s. The

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nanoindentation technique was used to determine elastic modulus. Fracture toughness (KIC) was

calculated using the indentation method under the load of 5000g using the equation derived by

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Shetty et al. [23]:

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KIC=0.0889(Hv P/4l) 1/2 (1)

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where Hv is the Vicker’s hardness, l is the crack length in (mm), and P is the indentation load in

(MPa).
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Table 1
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Composition of cermet samples.

Weight [%] Volume [%]
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Cermet no. TiC Ni NiB TiC Ni NiB

C1 80 20 0 88 12 0
C2 80 0 20 88 0 12
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C3 80 10 10 88 06 06
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3. Results and discussion

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3.1 Thermal analysis

Fig. 1 shows the DTA of TiC-Ni/NiB phase transformations with different Ni/NiB contents

up to 1400°C. These DTA curves show that not much change occurred from 200ºC to 1000ºC,

showing no phase transition or chemical reaction took place in nitrogen during heating. Thus,
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thermal stability of composite powders, as well as the stability of their phases, at 200-1000°C

was confirmed.

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Fig. 1. Differential thermal analysis of mixed powders: (a) as-milled TiC-20Ni (b) as-milled
TiC-20NiB and (c) as-milled TiC-10Ni-10NiB (all milled for 1 h each).
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The onset points of DTA heating curves were used as a beginning of melting. Three peaks
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were observed at 1155°C, 1213°C and 1369°C from DTA for the TiC-20Ni 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 TiC-10Ni-10NiB sample, peaks were at 1155°C,

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1214°C, and 1359°C, which were lower than for TiC-20Ni. Thus, the addition of NiB

lowered the melting point about 10°C.

3.2. Phase constitution

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Fig. 2 (a) shows XRD patterns of the as-milled TiC-20Ni, TiC-20NiB and TiC-10Ni-10NiB

powders, milled for 1 h, and Figs. 2 (b), (c) and (d) show the patterns of TiC-20Ni, TiC-20NiB

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and TiC-10Ni-10NiB sintered at 1200°C, 1300°C and 1400°C.

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Fig. 2. XRD patterns of (a) TiC-Ni/NiB composite powders as-milled, (b) sintered at 1200°C, (c)
sintered at 1300°C, and (d) sintered at 1400°C.
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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 0.4311nm

and 0.3555nm respectively, calculated by Cohen’s method [24].

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3.3. Powder morphology

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Fig. 3 (a) shows the SEM image of un-milled pure TiC powder, and Fig. 3 (b-d) show the

images of 1h milled sample of TiC-20Ni, TiC-20NiB and TiC-10Ni-10NiB. In the as-milled

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powder, much finer particles were observed with some agglomerates. The milled powder became

agglomerated because of very fine size and also due to pick up of moisture from atmosphere.

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a b
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c d
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Fig. 3. Scanning electron micrographs of powder; (a) un-milled TiC, (b) milled TiC-20Ni, (c)
TiC-20NiB and (d) TiC-10Ni-10NiB.
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3.4. Density

Fig. 4 shows the sintered density of all three cermets sintered at 1200°C-1400°C. The green

density was measured and found to be approximately 60-65% theoretical density. TiC-Ni with 10

wt% NiB additions produced a maximum sintered density of 97% theoretical density when

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sintered at 1400°C.

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C1: TiC-20Ni; C2: TiC-20NiB; C3: TiC-10Ni-10NiB

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Fig. 4. Influence of NiB on sintered density of the cermets sintered at 1200°, 1300°, and
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1400°C.

It can be seen from Fig. 4 that among the three cermets sintered at three different
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temperatures, maximum densification was observed in the case of cermet C3 sintered at 1400°C.
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Taking the effect of errors into account, the sintered density values of C1 and C2 for

temperatures 1300°C and 1400°C can be considered similar (~93 to 96 % of theoretical). The

densification mostly depends upon the amount of liquid phase formed [25]. As the melting point

of the binders was in the range of 1356-1369°C from the DTA curves (Fig. 1), sufficient liquid

formed at 1400°C which filled the pores around the TiC particles, and due to the rearrangement
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of grains, the density increased as the porosity decreased. However, the reason for higher density

for cermet C3 at 1400°C may be attributed to the presence of NiB with Ni.

3.5. Microstructure analysis of sintered cermets

Figs. 5-7 show the microstructures of cermets sintered at 1200°C, 1300°C and 1400°C

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with different binder contents. The microstructure shows that TiC particles were homogeneously

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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,

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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

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a AN b

Pore
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Pore
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c
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Binder
Core
Rim
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Fig. 5. Effect of NiB content on microstructure of: (a) TiC-20Ni, (b) TiC-20NiB, and (c) TiC-
10Ni-10NiB 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.
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a b

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c

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Fig. 6. Effect of NiB content on microstructure of: (a) TiC-20Ni, (b) TiC-20NiB, and (c) TiC-
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10Ni-10NiB cermets sintered at 1300°C. The dark-gray phase/gray phases show the typical
core/rim structure and the bright phase is the binder.
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a b
Core

Rim
Pore

Binder

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c

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Fig. 7. Effect of NiB content on microstructure of: (a) TiC-20Ni, (b) TiC-20NiB, and (c) TiC-
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10Ni-10NiB 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.
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rich in Ni with some dissolved TiC. This is in good agreement with literature [3, 26, 27] and was
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also shown by EDS. The core/rim structure observed in this work is similar to the structure
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reported by Monteverde et al. [28]. The decrease of specific surface energy (ϒr) of the system is
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the driving force, and is given by Equation 2 [25]:

ϒr =ϒS +ϒL-ϒSL (2)

where ϒS, ϒL are the specific surface energies for solid and liquid respectively, and ϒSL is the

specific phase boundary energy for solid /liquid. Energy decreases when ϒSL≤ ϒS, ϒL.
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If the specific 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 fine, which possessed more surface area and high surface energy,

resulting in increased driving force.

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3.5.1. Effect of sintering temperatures on the microstructures

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Cermets sintered at 1200°C (Fig. 5) had pores indicating that sintering was limited and

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incomplete. At lower temperatures, imperfect penetration of Ni/NiB binder phase, as well as

non-uniform distribution of TiC in the matrix occurred. Cermets sintered at 1300°C (Fig. 6)

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showed that some Ni/NiB binder particles started melting and wetted the TiC particles. At

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1400°C, the sintered cermet had TiC grains well-surrounded by the Ni-NiB matrix as the

solubility was higher. DTA analyses showed endothermic peaks at 1356-1369°C (Fig. 1) which
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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
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sintering is to achieve highest possible densification, combined with high strength and high
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toughness. The liquid fills the gaps between the TiC particles and reduces pores. Steps in LPS

include liquid formation, solution re-precipitation and finally solid state sintering. Important
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concepts are grain shape accommodation and stable microstructure based on the liquid content
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and dihedral angle between solid-solid grain boundary and liquid [25]. Since these processes are
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typically involved in liquid phase sintering for producing dense microstructures, the melting of

the binder phase affects the microstructure greatly.

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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

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(i) diffusion of atoms along grain contacts and rapid mass transfer through the liquid and (ii)

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grain shape accommodation, leading to pore elimination.

Boron activates the sintering process by forming the liquid phase. Ni/NiB forms a liquid

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phase and this liquid remained almost continuous between the TiC grains, thus favoring liquid

phase sintering. When the amount of NiB was increased (20wt%), boron tended to segregate to

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the surfaces and grain boundaries, and did not improve the density and microstructure. It may
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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 densification.
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The correct amount of liquid phase has significant impact on interfaces between the solid
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grains, and improves wetting, accelerates diffusion according to interfacial energy and phase
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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
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enhanced mechanical properties could be achieved.

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Fig. 8. SEM-BSE micrograph of TiC-10Ni-10NiB cermet sintered at 1400°C, (a) Dark region
(TiC), and (b) bright region (binder).

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In order to clarify the composition of the dark as well as bright regions, EDS analysis was
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conducted on the TiC-10Ni-10NiB cermet sintered at 1400°C, Fig. 8. As expected, the dark
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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, five different
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locations in dark phase, as well as bright phase, were selected and average values are reported in
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Table 2. For TiC, though one would expect the C content to be in the range of ~31 to 49 atomic

% [20], but ~59 to 67 atomic % C was observed. This could have arisen primarily due to the
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limitation of EDS for reporting carbon. The TiC phase was also confirmed by XRD (Fig. 2).
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Table 2
Chemical composition obtained from EDS analysis.
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Weight [%] Atomic [%]

Spectrum 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
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.
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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

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of 2759±43 Hv was achieved with 10wt % NiB addition, while the maximum hardness of C1

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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 densification during liquid phase sintering. The high hardness of

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the cermet C3 was due to enhanced densification during sintering. Apart from higher density, the

high hardness obtained may be attributed to the strong interfacial bonding between TiC-TiC

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grains due to presence of both Ni and NiB as binder [29], but this needs to be confirmed. Further
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detailed studies are required to confirm the finding, which is beyond the scope of current work.
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C1: TiC-20Ni
C2: TiC-20NiB
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C3: TiC-10Ni-10NiB
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Fig. 9. Vicker’s micro-hardness of TiC-Ni cermets with 0, 20 and 10 wt % NiB additions

sintered at 1200°C, 1300°C and 1400°C.
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Fig. 10 shows the variation in elastic modulus with composition of the cermets sintered at

1200°C, 1300°C, and 1400°C for 1h. The sintered TiC-10Ni-10NiB cermet had significantly

higher elastic modulus compared to TiC-20NiB. An elastic modulus of 460±6 GPa was achieved

for TiC-Ni without NiB after sintering at 1400°C. The maximum elastic modulus of 470±4 GPa

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was attained with samples containing 10Ni-10NiB after sintering at 1400°C, whereas TiC-20NiB

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showed a maximum elastic modulus of 444±7 GPa.

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C1: TiC-20Ni
C2: TiC-20NiB
C3: TiC-10Ni-10NiB

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Fig. 10. Elastic modulus of TiC-Ni cermets with 0, 20 and 10 wt % NiB additions sintered at
1200°C, 1300°C and 1400°C for 1h.
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3.7. Fracture toughness

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Fig. 10 shows the variation in fracture toughness with composition of the cermets sintered at

1200°C, 1300°C, and 1400°C.

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C1: TiC-20Ni

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C2: TiC-20NiB
C3: TiC-10Ni-10NiB

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Fig. 11. Fracture toughness of vacuum sintered TiC-Ni cermets with 0, 20 and 10 wt % NiB
additions sintered at 1200°C, 1300°C, and 1400°C.
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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

(8.98MPa.m1/2) increased, which is comparable with WC-Co (10-12 MPa.m1/2) cermet [2, 30]

and suitable for commercial use. Previously reported values of fracture toughness for TiC-Ni

cermets are 6.8-7.4 MPa.m1/2 [31]. The improved toughness may be due to the dense
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microstructure obtained in the TiC-10Ni-10NiB cermet as a result of the addition of NiB and the

homogeneous distribution of TiC particles in Ni/NiB matrix.

3.8. Coefficients of thermal expansion

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Fig. 12 shows the variation in coefficients of thermal expansion (CTE) with temperature for

the cermets sintered at 1200°C, 1300°C and 1400°C.

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Fig. 12. CTE of 1400°C vacuum sintered TiC-Ni cermets with different NiB additions.
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The CTE of the TiC-20Ni cermet (C1) calculated using the Kerner model [30] was
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8.35×10-6/°C, which was in good agreement with the experimental value of CTE of 1400°C
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sintered TiC- 20Ni measured at 300°C (9.0×10-6/°C ) in the present study. According to the

Kerner model, CTE is given by [30]:

(α r − α m )( K r − K m )
α c = α rVr + α mVm + VrVm
V r K r + V m K m + ( 3 K r K m / 4G m ) (3)
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where α is CTE, V is volume fraction, K is bulk modulus, G is shear modulus, and

subscripts c, r and m represent composite, reinforcement and matrix respectively. The low CTE

of TiC-10Ni-10NiB composite sintered at 1400°C may be due to enhanced densification due to

presence of NiB in the binder, and also due to the strong interface bonding [29,32] by the

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addition NiB, which restrains the deformation of metal matrix.

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4. Conclusions

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a) Metal matrix composites of TiC–Ni with different amounts of NiB binder were

successfully prepared. The 1400°C sintered sample with 10 wt% NiB had the maximum

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densification with 97±0.21% theoretical density, using pressureless liquid phase sintering.

b)
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In TiC-10Ni-10NiB cermet, a fine and dense microstructure was developed, which

accounted for the enhanced hardness of 2759±43 Hv sintered at 1400°C.

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c) Elastic modulus of 470±4 GPa, fracture toughness 8.98±0.28 MPa m1/2 was obtained in
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the sintered cermet containing 10wt % NiB.

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d) A reduced CTE (8.36±0.01) ×10-6/°C was found for TiC-10Ni-10NiB cermet.

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Acknowledgements
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This work was carried out in the Supra Institutional Project ESC 0401 titled “Centre for Special
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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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Highlights

• Preparation of TiC-Ni cermets with addition of nickel boride by vacuum sintering at

1200, 1300, 1400ºC is reported.

• The optimal sintering temperature and composition were found to be 1400ºC and TiC-

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10Ni-10NiB.

• There was fine and uniform distribution of TiC in Ni/NiB matrix for 1400ºC sintered

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TiC-10Ni-10NiB.

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• Bulk density, micro hardness, Elastic modulus, fracture toughness and CTE of

sintered specimens were reported.

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