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Ceramics International
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Influence of sintering temperature on microstructure and mechanical

properties of WC-8Ni cemented carbide produced by vacuum sintering
Doan Dinh Phuong a,b,n, Pham Van Trinh b, Luong Van Duong b, Le Danh Chung b
a
Center for High Technology Development, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet Street, Cau Giay District, Hanoi, Vietnam
b
Institute of Materials Science, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet Street, Cau Giay District, Hanoi, Vietnam

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

Article history: The WC-8Ni powder was prepared by the ball milling method, then consolidated via a vacuum sintering
Received 13 June 2016 technique. The influence of sintering temperature varying from 1375 °C up to 1500 °C on microstructure
Received in revised form and mechanical properties of WC-8Ni cemented carbide was investigated. The best mechanical prop-
21 June 2016
erties of the samples have been achieved at sintering temperature of 1450 °C. At which the relative
Accepted 21 June 2016
density, hardness and fracture toughness (KIC) of the samples are 99.81%, 13.23 GPa and 24.22 MPa m1/2,
respectively. The effect of η-phase identified by Murakami etching method and XRD technique on the
Keywords: mechanical properties was also discussed.
WC-Ni cemented carbide & 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Vacuum sintering
Hardness
Facture toughness
η-Phase

1. Introduction nickel has the similarity in structure and properties in comparison

with Co. Furthermore, its more ductile FCC structure also leads to
Cemented carbides with remarkable mechanical properties and the improvement of cemented carbide fracture toughness. The
widely potential applications are one of the most attractive pow- principal difference between them is the higher stacking fault
der metallurgy materials [1]. Basically, cemented carbide consists energy of Ni that results in lower hardening rates [6–15].
of carbide particles cemented into a composite by a ductile binder Many studies on the properties of WC-Ni cemented carbide
material. Cemented carbides commonly use tungsten carbide (WC) such as hardness, fracture toughness and tribology have been re-
as the aggregate and cobalt as the matrix [2]. Increased interest in ported. Numerous studies on the effect of composition, powder
the field of alternative binders in cemented carbides has been size on the properties of cemented carbide have been done and
observed in Europe in the recent years driven by the new Eur- reported [16–18]. In contrary, a very limited number of studies
opean Community Regulation on chemicals and their safe use, investigating the effect of manufacturing parameters on the
known as the REACH program [3]. The potential health risk of properties and microstructure of this material have been
inhalation of hard metal raw powders and dust in the cemented performed.
carbide industry production lines has been reported by number of Thus, the aim of this study is to investigate the influence of
works. The toxicity of WC and Co-doped WC nanoparticles in sintering temperature on the microstructure and properties of
mammalian cells has been investigated and reported by Bastian vacuum sintered WC-8Ni cemented carbide.
et al. recently [4]. On the other hand, cobalt is unsuitable as a
binder phase in wet corrosion conditions due to its surface de-
pletion, which permits the carbide grains to become detached 2. Experimental procedure
relatively easily by the wear process. In most corrosion-wear si-
tuations, an optimum choice is the WC-Ni grades, which are re- 2.1. Preparation of WC-8Ni cemented carbide
sistant down to pH 2–3 [5]. Besides its good corrosion resistance,
Commercial WC powder with average particle size of 3.02 mm
n
(shown in Fig. 1a) supplied by TaeguTec Co. and Ni powder with
Corresponding author at: Center for High Technology Development, Vietnam
particle size distribution from 2 to 3 mm and having a spiky needle
Academy of Science and Technology, 18 Hoang Quoc Viet Street, Cau Giay District,
Hanoi, Vietnam. like morphology (shown in Fig. 1b) produced by carbonyl method,
E-mail address: [email protected] (D.D. Phuong). were used as raw materials for this study.

http://dx.doi.org/10.1016/j.ceramint.2016.06.134
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
2 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 1. SEM images of (a) WC powder and (b) Ni powder.

In order to prepare WC-8Ni cemented carbide, WC and Ni

powders were weighed and calculated to create a powder mixture
containing 92 wt% of WC and 8 wt% of Ni. The powder mixture
Fig. 3. SEM images of ball-milled WC-8Ni mixture: (a) low magnification and
was milled in an n-hexane medium for 72 h in a tungsten carbide
(b) higher magnification.
ball mill. The ball-to-powder ratio was 6:1. After milling, the as-

Fig. 2. (a) Schematic of the sintering process and (b) schematic of cutting process for the test specimens.

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

Fig. 4. BSE-SEM images of WC-8Ni cemented carbide sintered at (a-b) 1375 °C, (c-d) 1400 °C and (e-f) 1425 °C.

received powder mixture was dried at 50 °C and then reduced in 2.2. Characterization
hydrogen to eliminate the major part of nickel oxide, which was
generated during the ball milling. The reduction process was done To evaluate accurately, a centered part of sintered specimens
in a tube furnace at 450 °C under hydrogen gas flow for 4 h. Then was selected to investigate and determine the material properties.
reduced WC-Ni powder was mixed with 2 wt% paraffin wax and The schematic of the preparation process for test specimens was
shown in Fig. 2b. The centered part with 6 mm in thickness and
dried again in vacuum. The dried powder was compacted in a
9 mm in diameter was prepared by cutting 3 mm at top and bot-
cylindrical mould to obtain pellets with thickness of 12 mm and
tom parts, and then removing a 2 mm outside surrounded mate-
13 mm in diameter. The pellets were subsequently pre-sintered at
rial layer of the specimens. The ready-cut specimens were grinded,
850 °C in Ar. Finally, the sintering was carried out on a vacuum then polished in diamond slurry for phase investigation, micro-
furnace at the different sintering temperatures. The regime of the structure observation, density measurement and hardness test.
sintering process is shown in Fig. 2a. The specimens were heated The morphology of the starting powders and microstructure of the
up to desired sintering temperatures (1375, 1400, 1425, 1450, 1475 sintered specimens were examined using a Hitachi S-4800 field
and 1500 °C) and kept at that temperature for 2 h in vacuum be- emission scanning electron microscope (FESEM) and an Axiovert
fore cooling down to ambient atmosphere in the furnace. 40 MAT optical microscope (OM). The phase compositions were
investigated by the X-rays diffraction technique using a XRD

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
4 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 5. BSE-SEM images of WC-8Ni cemented carbide sintered at (a-b) 1450 °C, (c-d) 1475 °C and (e-f) 1500 °C.

Bruker D8 Endeavor equipped with CuKα radiation. To identify the different sizes were observed where larger particles are de-
η-phase (eta phase) on optical microscope, the specimens were termined as WC and the finer particles as Ni.
etched by Murakami's etchant for 2 s (100 ml water þ10 g KOH Back-scattered electron (BSE) SEM images of specimens sin-
þ10 g K3Fe(CN)6). The bulk density of the samples was measured tered at different temperature are shown in Figs. 4 and 5, where
by Archimedes principle (AND GR-202, Japan). The mechanical white-colored, gray-colored, and dark-colored areas are WC par-
properties were investigated in terms of Vickers hardness (HV30) ticles, binder phase and pores respectively. Higher porosity was
by the Vickers hardness tester AVK-CO (Mitutoyo, Japan) and the observable in the specimens sintered at 1375 °C (Fig. 4a,b) and
fracture toughness (KIC) was calculated based on the Palmqvist 1400 °C (Fig. 4c–d). From these figures, pores and defect regions
crack method [19]. The value of material density, hardness and can be observed. The formation of defect regions could be attrib-
fracture toughness for each sintering temperature reported in this uted to the sintering temperatures applied significantly lower than
study is the average of three specimens sintered in the same batch. melting point of binder. This assumption is strengthened when
higher sintering temperatures were applied. No defect regions
3. Results and discussion were observed except the pores. Elimination of pores and defect
regions leads to improve the densification of specimens during
FESEM images of WC-8Ni mixture after 72 h of milling were sintering process. However, besides of the pores, some cracks are
shown in Fig. 3. From the figure, two kinds of particles with observed inside specimen sintered at 1500 °C. It could be a result

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 5

temperature. The effect of sintering temperatures on the formation

of η-phase was clarified by microstructure studies. Specimens
were etched by Murakami's reagent to reveal the position of η-
phase. Except the existence of pores, there was no η-phase de-
tected with the specimens sintered at 1425 °C and 1450 °C as
shown in Fig. 7a and b. It was quite different with the results
observed with specimens sintered at 1475 °C and 1500 °C where
some η-phase regions were detected and higher amount of η-
phase was observed in the specimen sintered at 1500 °C than the
specimen sintered at 1475 °C. The morphology of η-phase regions
are shown in Fig. 8. It can be seen from the images that the
morphology of the holes formed by Murakami's etching is differ-
ent between specimens sintered at 1475 °C and 1500 °C. The
etching rate of η-phase in the specimen sintered at 1475 °C was
much higher than in the specimen sintered at 1500 °C. The de-
ference in etching rate may be caused by different types of η-
phase formed at different sintering temperature. However, this
behaviour should be studied in more details by using TEM and
other powerful techniques in the future. In summary, both XRD
Fig. 6. XRD patterns of sintered specimens at the various sintering temperatures.
and microstructure studies demonstrated that η-phase was
formed in the specimens sintered at temperature above 1450 °C,
of a large amount of η-phase formed during sintering, that made
which could effect on the mechanical properties of specimens.
the material extremely brittle and leads to cracks during the The relative density of the carbide is calculated as a ratio (in
cooling process. percentage) of the measured density of carbide to its theoretical
XRD patterns of WC–Ni cemented carbide specimens sintered density, which is 14.74 g/cm  3 for the WC-8Ni carbide. Fig. 9
at 1425 °C, 1450 °C, 1475 °C and 1500 °C are presented in Fig. 6. As shows the effect of sintering temperatures on the density and
can be seen, the main phases of WC and Ni were recorded with all relative density of the specimens. All specimens showed an in-
specimens. There was no carbon phase and no η-phase (N2W4C) creased relative density with increasing sintering temperature.
detected with the specimens sintered at 1425 °C and 1450 °C. With Specimen sintered at 1375 °C has the lowest relative density
specimens sintered at temperatures above 1450 °C, some re- (96.2%) and then there are 97.1%, 99.6%, 99.81%, 99.82% and 100%
presentative peaks of η-phase (N2W4C) have been detected and for the specimens sintered at 1400 °C, 1425 °C, 1450 °C, 1475 °C
higher intensity was recorded with specimen sintered at higher and 1500 °C, respectively. The increase of the relative density

Fig. 7. Optical images of specimens sintered at (a) 1425 °C, (b) 1450 °C, (c) 1475 °C and (d)1500 °C (Etched in Murakami's reagent for 2 s).

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
6 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 8. SEM images of etched surface of specimens sintered at (a-b) 1475 °C and (c-d) 1500 °C.

Fig. 9. Density and relative density of specimens sintered at the various sintering Fig. 10. Vikers hardness and fracture toughness of specimens sintered at the var-
temperatures. ious sintering temperatures.

seems to be related to the viscosity of the liquid binder. Liquid increases with the increase in the sintering temperature, where
binder with low viscosity at higher temperature will fill out the the values of 11.24, 12.65, 13.15, 13.23, 13.43, and 13.43 GPa cor-
pores during the sintering, thus leads to the denser carbides. The respond to hardness of specimens sintered at 1375 °C, 1400 °C,
relative density of specimens is in good agreement with the results 1425 °C, 1450 °C, 1475 °C and 1500 °C, respectively. However, two
of microstructure studies, where larger pores were observed at hardness stages can be seen in Fig. 10; first stage begins with
specimens sintered at temperature lower than 1425 °C and smaller specimens sintered at temperature from 1375 °C to 1425 °C and
ones observed at specimens sintered at higher temperature. second stage with specimens sintered at higher temperatures. The
Fig. 10 presents the dependence of Vickers hardness (HV30) hardness is significantly increases with the increase in the sin-
and fracture toughness (KIC) of specimens sintered at different tering temperature in first stage and nearly the same in second
temperatures. It can be seen clearly from figures that the hardness stage.

Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i
 D.D. Phuong et al. / Ceramics International ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 7

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Please cite this article as: D.D. Phuong, et al., Influence of sintering temperature on microstructure and mechanical properties of WC-
8Ni cemented carbide produced by vacuum sintering, Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.06.134i