Author’s Accepted Manuscript

Effect of Ni and graphene on microstructure and

toughness of titanium boride ceramic tool material
prepared by spark plasma sintering

Zengbin Yin, Juntang Yuan, Weiwei Xu, Mingdan

Chen, Shiyu Yan, Zhenhua Wang
www.elsevier.com/locate/ceri

PII: S0272-8842(18)32064-9
DOI: https://doi.org/10.1016/j.ceramint.2018.08.017
Reference: CERI19052
To appear in: Ceramics International
Received date: 27 June 2018
Revised date: 20 July 2018
Accepted date: 1 August 2018
Cite this article as: Zengbin Yin, Juntang Yuan, Weiwei Xu, Mingdan Chen,
Shiyu Yan and Zhenhua Wang, Effect of Ni and graphene on microstructure and
toughness of titanium boride ceramic tool material prepared by spark plasma
sintering, Ceramics International, https://doi.org/10.1016/j.ceramint.2018.08.017
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 Effect of Ni and graphene on microstructure and toughness of titanium boride

ceramic tool material prepared by spark plasma sintering

Zengbin Yin, Juntang Yuan*, Weiwei Xu, Mingdan Chen, Shiyu Yan, Zhenhua Wang
School of Mechanical Engineering, Nanjing University of Science and Technology, Nanjing 210094,
PR China
Collaborative Innovation Center of High-End Equipment Manufacturing Technology (Nanjing
University of Science and Technology), Ministry of Industry and Information Technology,
PR China

Abstract: TiB2/TiC ceramic tool material toughened by Ni and graphene nanoplatelets was
prepared by spark plasma sintering. Effect of Ni and graphene nanoplatelets on densification,
microstructure and mechanical properties were studied. The composite containing 2wt.% Ni and
0.5wt.% graphene nanoplatelets can be fully densified at 1750℃ with the holding time of 5min.
Both Ni and graphene can improve densification of TiB2 ceramic. Ni also promotes more content of
graphene nanoplatelets to toughening. Excess Ni leads to cracks at grain-boundaries owing to the
large thermal expansion mismatch between Ni and graphene. The optimal fracture toughness is
8.3±0.43MPa·m1/2. Crack bridging is the most effective toughening mechanism. Except the particle
bridging, some blocky materials act as the bridging unit due to the anchoring effect of graphene.
Bridging process by graphene failed by debonding of graphene from the matrix.

Keywords: TiB2; Graphene; Metallic additive; Mechanical property; Spark plasma sintering

1. Introduction
Titanium diboride (TiB2) possesses several excellent performances, e.g. high melting point
(~3000℃), high elasticity modulus (529GPa), extreme hardness (~32GPa) and excellent wear
resistance [1, 2]. These attractive properties give it great potential to be used as high-speed cutting
tool materials. But the application of TiB2 as cutting tools is severely limited due to its low fracture
toughness and poor sintering capability [3, 4]. So it is crucial to improve the fracture toughness for
the use of TiB2 ceramic as cutting tools.
The sintering additives introduced to TiB2 to improve its mechanical properties and sintering
capability can be classified two categories: metallic and non-metallic additives. The most
commonly used metallic additives are Ni, Mo, Ti, Ta, etc. Ni distributes in the phase interface or the
triple junctions among grains, and forms a continuous boundary phase around the matrix particles.
These promote the densification of TiB2 and enhance the interfacial bounding strength [3, 5-8]. The
densification of TiB2 ceramic with metallic additive can be finished at lower temperature with
shorter time. The relative density of TiB2 ceramic sintered at 1450℃ through spark plasma
sintering reached full theoretical density when 5wt.% Ti was added into TiB2 ceramic [9]. Ta has
well ability to inhibit grain growth and can combine with B and other metal to form stable phases
[10-13], moreover, the fracture mode of TiB2 was changed from inergranular to transgranular when
Ta and Ni were added [14]. A variety of non-metallic additives such as SiC, TiC, WC, TaC, MoSi2,
CrB2 and AlN are used for the mechanical properties improvement of TiB2-based ceramics [15-25].
The additives improve the sintering capability by removing the oxide impurity, promote the
densification of TiB2, as well as, contribute multiple toughening mechanisms like grain pining,
*
Corresponding author. Tel.: +86 25 84315421. Fax: +86 25 84315831. E-mail address: mc106@njust.edu.cn (J. Yuan).
crack bridging, branching and deflection, thus the TiB2-based ceramics could have a high density
and good toughness.
Graphene has attracted a great interest as effective additive for the toughening of ceramics
owing to its unique two-dimensional structure, high tensile strength and Young’s modulus [26-32].
The toughness of ceramic can be significantly improved even at relatively low content of graphene.
Graphene platelets or multi-layer graphene have been used as toughening additives to enhance the
mechanical properties of Al2O3-based ceramic tool materials [33-35]. With the addition of 0.2wt.%
graphene platelets or multi-layer graphene, the fracture toughness of Al2O3/TiC ceramic tool
material was increased by 67.3% and 23.3%, respectively [34-36]. However, study of TiB2-based
ceramic tool material toughened by graphene is quite a few.
In our previous study, microstructure and mechanical properties of TiB2/TiC ceramic tool
material toughened by graphene nanoplatelets (GPLs) were investigated. The average fracture
toughness (7.9MPa·m1/2) was increased by 31.7%, when 0.1wt.% graphene nanoplatelets was added
[37]. But the randomness of fracture toughness was very large (±1.2MPa·m1/2) due to the uneven
distribution of bits of GPLs. And, the increased content of GPLs leaded to more pores in the
sintered ceramic, thus much higher sintering temperature was required to get full densification. This
resulted in coarse microstructure and inferior mechanical properties. In the study, Ni was introduced
to the graphene toughened TiB2/TiC ceramic tool material in order to improve its densification and
mechanical properties. Effects of Ni on sintering behavior, microstructure and mechanical
properties of TiB2/TiC/graphene composite ceramic were studied. The toughening mechanisms of
graphene nanoplatelets were also investigated.

2. Experimental procedures
2.1 Materials fabrication
TiB2-based composite ceramic tool materials were prepared using commercial powders TiB2
(700nm, purity ＞99.5%, CW-nano Co. Ltd. Shanghai), TiC (600nm, purity ＞99.8%, Shanghai
CW-nano Co. Ltd.), graphene nanoplatelets (diameter of 1~3μm and thickness of 1~5nm, purity:
99.9%, Nanjing XFNANO Co. Ltd) and Ni (50nm, purity ＞99.9%, Shanghai CW-nano Co. Ltd.).
Composites with different contents of GPLs and Ni (Table 1) were investigated.
Table 1 Compositions and mechanical properties of TiB2/TiC/graphene composites
TiB2 TiC GPLs Ni Relative density Fracture toughness Vickers hardness
Symbol
(wt.%) (wt.%) (wt.%) (wt.%) (%) (MPa m1/2) (GPa)
TG1N0 69.9 30 0.1 0 96.5±0.28 7.3±0.95 18.6±1.20
TG1N2 67.9 30 0.1 2 99.4±0.34 7.3±0.90 18.9±0.18
TG1N4 65.9 30 0.1 4 98.9±0.15 6.8±0.53 17.3±1.42
TG1N6 63.9 30 0.1 6 98.7±0.57 7.3±0.59 17.8±0.40
TG3N0 69.7 30 0.3 0 98.5±0.46 6.3±0.66 17.3±0.21
TG3N2 67.7 30 0.3 2 101.1±0.34 8.0±0.42 17.8±0.53
TG3N4 65.7 30 0.3 4 100.2±0.49 7.7±0.55 18.0±0.53
TG3N6 63.7 30 0.3 6 99.2±0.61 7.3±0.48 18.0±0.42
TG5N0 69.5 30 0.5 0 96.9±0.32 7.6±0.73 17.2±0.36
TG5N2 67.5 30 0.5 2 101.5±0.42 8.3±0.43 19.3±0.52
TG5N4 65.5 30 0.5 4 100.2±0.58 6.8±0.45 17.9±1.09
TG5N6 63.5 30 0.5 6 99.4±0.49 6.7±0.69 16.1±0.45
The graphene nanoplatelets and Ni powders were dispersed by ultrasonic vibration and
mechanical stirring for 60min, and then mixed with TiB2 and TiC powders. The mixed powders
were ball-milled for 24 h and then dried. Next, the dried powders were sieved with a 100-mech
sieve. After that the powders were pressed-in a graphite mould with the inner diameter of 20mm.
Finally, the green compacts were sintered in a spark plasma sintering furnace (LABOX-650,
SINTERLAND, Japan) with the heating rate of 100℃/min under a pressure of 30MPa in vacuum.
Finally the compacts were naturally cooled to room temperature.
2.2 Characterization
Density of the sintered compacts was acquired according to the Archimedes’ method with
deionized water as the medium. Vickers hardness was measured by a Vickers diamond pyramid
indenter (HV50, China) with a load of 196 N for 15s. Fracture toughness was calculated based on
the Vickers indentation method [38]. Microstructure and crack propagation path were investigated
by scanning electron microscopy (SEM, SU3500, Hitachi, Japan).

3. Results and discussion

3.1 Densification, microstructure and mechanical properties
The curves of temperature-displacement of composite with different content of Ni are shown in
Fig. 1(a). Densification of the composites containing 2wt.% and 4wt.% Ni started at about 850℃
and basically finished at 1450℃. But the composite without Ni began to densify at about 900℃ and
the densification finished at 1550℃. Specifically, the composite with 2wt.% Ni had the fastest
densification rate. It indicated that Ni could decrease sintering temperature and accelerate
densification of the TiB2 ceramic. Compared to the composite without Ni [37], the sintering
temperature of the composite with 2wt.% Ni was decreased from 1800℃ to 1750℃ and the
temperature for final stage of densification decreased about 100℃ as illustrated in Fig. 1(a). The
curves of temperature-displacement of the composites containing different contents of GPLs are
shown in Fig. 1(b). GPLs could also promote the densification of TiB2 ceramic. More content of
GPLs resulted in faster densification rate. But, the effect of GPLs on densification was less than that
of Ni.

(a) (b)

Fig. 1 Curves of temperature-displacement of the composites with different content of (a) Ni and (b) GPLs
Relative density and mechanical properties of TiB2/TiC composites with different content of
Ni and GPLs sintered at 1750℃ for 5min are listed in Table 1. The composites containing different
content of GPLs reached the highest density when the content of Ni was 2wt.%. The relative density
of TG1N0 was 96.5%, and higher sintering temperature (1800℃) was needed for the full
densification based on our previous study [37]. But, when adding 2wt.% Ni, the composite was
almost fully densified (99.4%) at 1750℃. Previous studies showed that cavities were easily formed
with the increase of graphene content [27, 30, 37], which leaded to inferior properties. However, in
the present study, the composites containing high content of graphene could reach full densification
at 1750℃ with the addition of 2wt.% Ni. The maximal toughness and hardness were achieved when
the content of Ni was 2wt.%. It was worth noting that the variation of toughness decreased with the
increase of the GPLs content. The average toughness (8.3±0.43MPa·m1/2) of the TG5N2 was
increased a little but had a much smaller variation than that of TG1N0 (7.9±1.2MPa·m1/2) sintered
at 1800℃ [37].
Toughness of the composite containing graphene nanoplatelets was higher than that of the
other TiB2-based ceramic tool materials (Table 2). Moreover, the present composite contained much
lower content of metallic phase. It means that better high-temperature performance is to be
expected.
Table 2 Comparison of TiB2-based ceramic tool materials
Sintering Relative density Fracture toughness Vickers hardness
Composite
method (%) (MPa m1/2) (GPa)
TiB2/TiC/GPLs/2wt.% Spark plasma
101.5±0.42 8.3±0.43 19.3±0.52
Ni, the present study sintering
Spark plasma
TiB2/TiC/GPLs [37] 101.4±0.51 7.9±1.2 20.0±0.7
sintering
TiB2/TiN/17.8wt.% (Ni,
Hot-pressing 99.12 7.54 21.53
Mo) [3]
TiB2/TiC/WC/8wt.% (Ni,
Hot-pressing 99.3±0.3 7.4±0.2 24.8±0.3
Mo) [8]
TiB2/TiC/10wt.% Ni [22] Hot-pressing 99.4 7.80 22.54
The SEM morphologies of fractured surfaces of composites with 2wt.% Ni and different
content of GPLs sintered at 1750℃ for 5min are shown in Fig. 2. Pores were distributed not only at
(a) (b)

(c) (d)

Fig. 2 SEM morphologies of composites with 2 wt.% Ni and different content of GPLs, (a) 0.1wt.%, (b) 0.3wt.%,
(c) and (d) 0.5wt.%
grain-boundaries but also in grains as shown in Fig. 2(a) when the content of GPLs was 0.1wt.%.
Pores were hardly observed with increasing the GPLs content, the composites were fully densified.
When adding 0.5wt.% GPLs, the GPLs were uniformly located at grain-boundaries and wrapped the
matrix grains as indicated by arrows in Fig. 2 (c). It is well known that graphene’s wrapping effects
can lead to finer microstructure. That benefits from the pining effect of graphene on movement of
grain-boundary, which inhibits grain growth [16, 36, 39], but there were still some coarse grains
with a diameter of 5~10μm in the present composites.
Fracture mode was the combination of intergranular fracture and transgranular fracture. It can
be seen that transgranular fracture predominantly took place in the coarse grains as marked by
dotted box in Fig. 2 (c). The GPLs distributing at grain-boundaries prevented the cracks propagating
intergranularly, so the cracks might enter into the coarse grains with low strength, leading to the
transcrystalline fracture. Agglomerated GPLs were also observed, especially for the composite with
high content of GPLs as marked by arrows in Fig. 2(d).
The SEM morphologies of fractured surfaces of composites with 0.5wt.% GPLs and different
content of Ni sintered at 1750℃ for 5min are shown in Fig. 3. The microstructure of composite
(a) (b)

(c) (d)

Fig. 3 SEM morphologies of composites with 0.5 wt.% GPLs and different content of Ni, (a) 0wt.%, (b) 2wt.%, (c)
4wt.% and (d) 6wt.%
without Ni was inhomogeneous, with plenty of irregular grains and unclean grain-boundaries. Some
large cavities existed in the composite as indicated by arrows in Fig. 3(a). This was responsible for
the low relative density (96.9±0.32%) of TG5N0. When the content of Ni was 2 and 4wt.%, no
large cavities were observed, the grain became regular, and grain-boundaries was clear. However,
with furtherly increasing the content of Ni, the cracks along the interface was clearly seen as shown
in Fig. 3(d). As mentioned above, Ni and graphene were distributed along grain-boundaries. The
coefficient of thermal expansion of Ni and graphene are 8.6×10-6/℃ and ~1×10-6/℃, respectively
[40]. Large mismatch of coefficient of thermal expansion will induce large thermal stress, which
can cause the interface separation after sintering.
3.2 Effect of sintering temperature on microstructure and mechanical properties
Fig.4 shows the displacement versus temperature of TG5N2 sintered at different temperatures.
Sharp shrinkage of the composites was from 1050℃ to 1500℃. Full densification was achieved at
1700℃ (Fig. 5a). With the increase of sintering temperature, the hardness decreased first and then
increased, but the fracture toughness kept rising (Fig. 5b). The optimal mechanical properties were
obtained at 1750℃.

Fig. 4 Curves of temperature-displacement of TG5N2 sintered at different sintering temperatures

(a) (b)

Fig. 5 (a) Relative density, (b) fracture toughness and Vickers hardness of the composites sintered
at different temperatures

(a) (b)
 (c) (d)

Fig. 6 SEM morphologies of TG5N2 sintered at (a) 1600℃, (b) 1650℃, (c) 1700℃ and (d) 1750℃
When the composite was sintered below 1700℃, cavities were clearly observed as indicated
by the dotted box in Fig. 6(a) and (b). Especially, for the sample sintered at 1600℃, large gaps
existed around the graphene as indicated by arrows. When the sintering temperature exceeded
1700℃, the microstructure became much denser. Graphene nanoplatelets were uniformly located at
the grain-boundaries.
3.3 Toughening mechanisms
The SEM morphologies of crack propagation of TG5N2 prepared at 1750℃ with the holding
time of 5min are shown in Fig. 7. Crack bridging frequently occurred, and was the most effective
toughening mechanism for the present ceramic. Some cracks were bridged by particles as denoted
by the circular dotted box, and some cracks were bridged by blocky material as denoted by the
rectangular dotted box. As mentioned above, graphene was commonly distributed at
grain-boundaries (Fig.2c). Due to the unique two-dimensional structure of graphene, it acts like an
anchor and can wrap the matrix grains (Fig. 8a). This made the matrix grains combine firmly into a
whole. Therefore, some bridging units were lager size. When crack was bridged by the large unit,
the crack would pass through a long bridging region, about 2~4 times longer than the particle
bridging, until the bridging unit was destroyed. Thus, more fracture energy was consumed, resulting
in larger contribution to toughness.
(a) (b)

Fig. 7 SEM morphologies of crack propagation of TG5N2 sintered at 1750℃ for 5min
The toughening effect of bridging will lose efficacy when the bridging units are reptured or
debonded from the matrix. In the present TiB2/TiC/graphene composite, the bridging process by
particles ended by the repture of particle and debonding with the matrix (Fig. 7). But for the
bridging by graphene, no repture of graphene was observed. That was attributed to the high strength
of graphene, higher than particles and even higher than interfacial bonding strength. So, the
bridging process ended by debonding as shown in Fig. 7 and Fig. 8(b). Moreover, pulling-out of
graphene from matrix (Fig. 8a), crack deflection and crack branching (Fig.7) also contribute to the
toughness improvement.
(a) (b)

Fig. 8 Characteristic toughening mechanisms of graphene on fractured surface

4. Conclusions
TiB2-based ceramic tool materials with Ni and graphene nanoplatelets were prepared by spark
plasma sintering. Several conclusions drawn from the study are as below:
(1) TiB2/TiC/Ni/graphene composite ceramic tool material containing 2wt.% Ni when sintered
at 1750℃ for 5min with the pressure of 30MPa can be fully densified, and the best fracture
toughness and Vickers hardness are 8.3±0.43MPa·m1/2 and 19.3±0.52GPa, respectively. Compared
to the composite without Ni, the fracture toughness is increased with much smaller randomness due
to the uniform distribution of large content of graphene in the composite.
(2) Ni benefits densification of the composite containing more graphene. Ni also refines
microstructure and strengthens interfacial bonding. The content of Ni required for densification of
TiB2 is much lower than the traditional TiB2-based ceramics, but more content of Ni induces cracks
at grain-boundaries owing to the large thermal expansion mismatch between Ni and graphene.
(3) Crack bridging is the main toughening mechanism for the TiB2/TiC/Ni/graphene composite.
Bridging by particles fails in the form of the repture of particle and debonding from the matrix.
Bridging process by graphene ends by the debonding of graphene from the matrix.

5. Acknowledgements
The work is supported by National Natural Science Foundation of China (51505227,
51675285), Natural Science Foundation of Jiangsu Province of China (BK20150783), National
Science and Technology Major Project (2013ZX04002-011), and Fundamental Research Funds for
the Central Universities (309171A8805, 30917014101, 30918011304).

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