Journal of Alloys and Compounds 639 (2015) 617625

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Journal of Alloys and Compounds

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

Taguchi design and hardness optimization of ZrB2-based composites

reinforced with chopped carbon ber and different additives and
prepared by SPS
Z. Balak , Mohammad Zakeri, Mohammadreza Rahimipour, Esmael Salahi
Materials and Energy Research Center (MERC), Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 30 September 2014
Received in revised form 13 March 2015
Accepted 17 March 2015
Available online 3 April 2015
Keywords:
ZrB2-based composites
Spark plasma sintering
Hardness
Taguchi design

a b s t r a c t
ZrB2SiC composites with different additives were prepared by spark plasma sintering (SPS). Taguchi
design was applied to explore effective parameters for achieving the highest hardness. Nine factors
including contents of SiC, Cf, MoSi2, HfB2 and ZrC, milling time of Cf (M.t) and SPS parameters such as temperature, time and pressure in four levels were considered through the Taguchi technique. It has been
concluded that the most signicant effects on the hardness are related to temperature, MoSi2, ZrC, SiC
and HfB2 by 54.7%, 12.3%, 9.1%, 8.2% and 6.7%, relative importance respectively. Pressure by 0.13% and
Cf by 0.43%, M.t by 0.94 and time by 2% have the least effect on the hardness.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Zirconium diboride (ZrB2) is an ultra high temperature ceramic
(UHTC) that has strong covalent bonding, which gives it a melting
temperature above 3000 C (3250 C for ZrB2), high hardness
(23 GPa), and high elastic modulus (>500 GPa experimentally,
546 GPa by calculation). The bonding also has metallic character,
which results in high thermal conductivity (60 W/m K or higher)
and electrical conductivity (107 S/m). With this unusual
combination of properties, ZrB2 shows promise for diverse applications such as cutting tools, molten metal crucibles, and thermal
protection systems for hypersonic aerospace vehicles [14].
Typically, three routes are used to improve the densication
and microstructure of ZrB2-based ceramics. The rst route is to
use sintering aids such as WC, Si3N4, VC and Y2O3 [57]. The second
route is to explore innovative sintering techniques for densication, including spark plasma sintering (SPS), reactive SPS, and
combined SPS and self-propagating high-temperature synthesis.
Compared to conventional hot pressing, SPS allows higher heating
rates and usually involves only a very short holding time. The third
route is to adjust the sintering parameters [8].

Corresponding author. Tel.: +98 0611 4452040.

E-mail address: Zbalak1983@gmail.com (Z. Balak).
http://dx.doi.org/10.1016/j.jallcom.2015.03.131
0925-8388/ 2015 Elsevier B.V. All rights reserved.

In this article, all of these three routes were used to optimize

microstructure and hardness. For the rst route, Cf with different
contents and milling times and different contents of MoSi2, HfB2,
SiC and ZrC in different content were chosen as additives. In the
second route, different temperature (16001900 C), pressures
(1040 MPa) and times (416 min) were selected as sintering conditions. Finally, for the third route, SPS was applied as sintering
method. Of course it is clear that the investigation of all these
parameters in a single work may not be possible and accompanies
very high cost. So, an optimization strategy is necessary to evaluate
all of these parameters and the effect of each of them on the hardness. The Taguchi method is the best opportunity to eliminate
variations during the design of experiment.
This method uses a special set of arrays called orthogonal
arrays. These standard arrays stipulate the way of conducting the
minimal number of experiments which could give the full information of all the factors that affect the performance parameter. Also, it
allows independent evaluation of each factor through a small number of runs.
In this paper, we focus on the effect of different additives and
SPS conditions on the hardness of ZrB2-based ceramics. By applying the Taguchi method, the effect of nine parameters such as
SiC, Cf, MoSi2, HfB2 and ZrC content, milling time of Cf and SPS
parameters such as temperature, time and pressure at four levels
was investigated. Effect of each parameter on hardness were evaluated and discussed.

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Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

Table 2
Orthogonal array (L32) determined by Taguchi method based on the nine factors in
four levels.

2. Experimental
2.1. Materials
Six basic raw materials including ZrB2 (20 lm), SiC (25 lm), MoSi2 (25 lm),
HfB2 (30 lm), ZrC (20 lm) and Cf (T800, diameter 5 lm) were used to produce
the composites.
2.2. Experimental design
Selection of control factors is an important stage of Taguchi applications and
design of the factors is generally set by experimenters experience. It is known that
SiC, Cf, MoSi2, HfB2 and ZrC content, milling time of Cf and SPS parameters such as
temperature, time and pressure are among the most important factors in hardness
[918]. Of course it is necessary to explain it, these factors were selected not only in
order to reach best densication and hardness but to reach optimize conditions for
preparing one composite with best relative density, hardness, exural strength,
toughness, oxidation and thermal shock resistance. On the other hand, not all nine
selected factors have a positive effect on hardness and they were chosen for another
goal. For example, Cf has inuence on hardness but its effect is negative and it was
chosen due to its good inuence on toughness according to unpublished data. In
this study, all of these factors were chosen as input variables and their impacts
on the response variable (Hv) were investigated. Four combinations of variables
(levels) were selected for each of the studied factors. The used factors and levels
are presented in Table 1. The level of each factor and the values of the tested factors
were chosen based on previous researches.
In this study, L32 orthogonal array was chosen to determine the optimum conditions. With respect to the L32 orthogonal array (Table 2), conditions for preparation of each sample are shown in Table 3.
2.3. Manufacturing and characterization
The powders corresponding to 32 different compositions, according to Table 3,
were mixed by wet ball-milling at 200 rpm for 3 h in a zirconia bottle, using zirconia balls and ethanol as media. The mixtures were then dried. The powder mixture
was put into graphite die lines with graphite foil which has an inner diameter of
50 mm and sintered using SPS apparatus (SPS-20T-10, China). The sintering was
performed at Different temperatures (between 1600 C and 1900 C), different pressures (between 10 MPa and 40 MPa) and different holding times (between 4 min
and 16 min) based on Taguchi design (Table 2) in vacuum. Sintered 50 mm diameter pellets were produced with different thicknesses of 2.8 mm and 6.5 mm related
to their compositions and SPS conditions. After removing the surface layer from the
obtained disks by grinding, the bulk density was measured according to ASTM C
373-88. Then the phase composition was determined by X-ray diffraction (XRD,
Siemens, D500) using Cu Ka radiation on polished cross-sectioned composite.
Scanning electron microscopy (Sigma/VP, Zeiss) on an instrument equipped with
backscattered electron imaging (BSE) was performed to observe the microstructures of the composites. Macro-hardness (Hv30.0) was measured by a Vickers
indenter with 30 kg as applied load for 20 s on polished sections.

3. Results and discussion

In this study, to measure the density, open porosity percent was
used instead of relative density due to phase transformations. For
hardness evaluation, a Vickers indenter with 1 kg as applied load
for 20 s was used, at rst. Since the most of composites had six
constituents, micro-hardness data, was variable. Thus the indenter
with 1 kg as applied could not cover all of phases. So, the data
obtained could not indicate the real hardness of samples and therefore were not reliable. Therefore, the Macro-hardness (Hv30.0) was
applied to measure hardness.

Table 1
Process factors and their levels used in the experiments.
Factors

Unit

Symbol

Level 1

Level 2

Level 3

Level 4

SiC
Cf
Milling Time
MoSi2
HfB2
ZrC
Temperature
Pressure
Time

Vol%
Vol%
Hr
Vol%
Vol%
Vol%
C
MPa
min

SiC
Cf
M.t
MoSi2
HfB2
ZrC
T
P
t

5
0
0
0
0
0
1600
10
4

10
2.5
2.5
2
5
5
1700
20
8

15
5
5
4
10
10
1800
30
12

20
7.5
7.5
6
15
15
1900
40
16

Sample

Fac.
1

Fac.
2

Fac.
3

Fac.
4

Fac.
5

Fac.
6

Fac.
7

Fac.
8

Fac.
9

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32

1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
4
1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
4

1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4

1
2
3
4
1
2
3
4
2
1
4
3
2
1
4
3
4
3
2
1
4
3
2
1
3
4
1
2
3
4
1
2

1
2
3
4
2
1
4
3
3
4
1
2
4
3
2
1
1
2
3
4
2
1
4
3
3
4
1
2
4
3
2
1

1
2
3
4
2
1
4
3
4
3
2
1
3
4
1
2
4
3
2
1
3
4
1
2
1
2
3
4
2
1
4
3

1
2
3
4
3
4
1
2
1
2
3
4
3
4
1
2
2
1
4
3
4
3
2
1
2
1
4
3
4
3
2
1

1
2
3
4
3
4
1
2
2
1
4
3
4
3
2
1
3
4
1
2
1
2
3
4
4
3
2
1
2
1
4
3

1
2
3
4
4
3
2
1
3
4
1
2
2
1
4
3
2
1
4
3
3
4
1
2
4
3
2
1
1
2
3
4

1
2
3
4
4
3
2
1
4
3
2
1
1
2
3
4
3
4
1
2
2
1
4
3
2
1
4
3
3
4
1
2

Table 3
Conditions for preparation of each sample.
Sample

SiC

Cf

M.t

MoSi2

HfB2

ZrC

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32

5
5
5
5
10
10
10
10
15
15
15
15
20
20
20
20
5
5
5
5
10
10
10
10
15
15
15
15
20
20
20
20

0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5
0
2.5
5
7.5

0
2.5
5
7.5
0
2.5
5
7.5
2.5
0
7.5
5
2.5
0
7.5
5
7.5
5
2.5
0
7.5
5
2.5
0
5
7.5
0
2.5
5
7.5
0
2.5

0
2
4
6
2
0
6
4
4
6
0
2
6
4
2
0
0
2
4
6
2
0
6
4
4
6
0
2
6
4
2
0

0
5
10
15
5
0
15
10
15
10
5
0
10
15
0
5
15
10
5
0
10
15
0
5
0
5
10
15
5
0
15
10

0
5
10
15
10
15
0
5
0
5
10
15
10
15
0
5
5
0
15
10
15
10
5
0
5
0
15
10
15
10
5
0

1600
1700
1800
1900
1800
1900
1600
1700
1700
1600
1900
1800
1900
1800
1700
1600
1800
1900
1600
1700
1600
1700
1800
1900
1900
1800
1700
1600
1700
1600
1900
1800

10
20
30
40
40
30
20
10
30
40
10
20
20
10
40
30
20
10
40
30
30
40
10
20
40
30
20
10
10
20
30
40

4
8
12
16
16
12
8
4
16
12
8
4
4
8
12
16
12
16
4
8
8
4
16
12
8
4
16
12
12
16
4
8

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Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

Table 4
Results of open porosity percent and hardness of all samples.
Sample

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32

Open porosity percent, %

Hardness, Hv

Trial 1

Trial 2

Trial 3

Trial 4

Trial 1

Trial 2

Trial 3

Trial 4

Trial 5

29.84
0
1.32
0.68
1.96
0
12.8
10.94
1.1
9.1
3.94
1.63
1.15
0.03
3.31
13.52
14.15
0
16.98
1.40
15.07
10.74
0.55
0.18
0.48
7.6
15.6
12.52
0.081
6.8
3.13
6.55

28.11
0
1.74
1.4
1.98
0
12.9
11.95
0
9.23
3.95
3.23
0.98
1.66
3.44
14.12
13.03
0
17.67
1.5
15.78
10.33
0
0
0
6.05
16.22
12.5
0
6.60
3.44
8.3

31.4
0
1.21
1.97
1.86
0
11.9
10.6
1.3
9.6
3.67
4.74
0.85
1.34
2.94
14.6
14.1
0
16.9
1.45
16.4
10.3
0.27
0.58
0.61
5.6
15.8
11.6
0.09
6.22
3.69
9.44

29.68
0
1.93
0.7
1.84
0
11.83
10.5
0
9.32
3.28
0.44
1.18
0.37
3.8
13.24
13.14
0
17.62
1.34
15.36
10.27
0.51
0.48
0.42
6.34
15.15
12.46
0.082
6.26
3.68
9.2

34.2
310.7
314.5
372
364.3
341
155.6
188.2
319
130
353.8
382.7
397.4
383.6
320.7
135.9
169.2
266.6
115
320.5
113
230.9
350.6
312.9
340.6
207.3
189
158.5
415.2
278.8
392.4
185.5

37
309
315.2
375
360.4
342.4
144.8
175.9
317.7
149.5
350.6
381.4
391
395.9
327.2
136.5
168.7
266.9
115.6
320.7
110.4
230.2
350.2
296.5
338.4
206.5
185
155.9
417.4
279.9
396.8
194

34.3
309
319
365.7
360.6
339.8
148.3
176.8
319.2
148.4
351.6
382.3
399.3
387.2
323.4
135.4
172.2
262.3
113
320
113.8
235.2
348.8
299
339.6
211
198.1
154.4
415
285.8
394.3
188.6

34.6
311
315.4
376.3
362
340
155.1
187.8
316.7
140.3
348
380
400.2
398.4
320.1
138.16
171.4
260.6
118.4
318
110
231
350
292.5
338
209
186.2
154
410.8
295
392
182.6

35.2
310
315.3
369.6
360.4
341.3
147
190
317.4
143.6
349.5
380
398.2
389
326.2
136.3
166.5
263.5
113.6
320
112.4
232.3
352
298
345.6
210
186
155
410
290
385
185

Fig. 1. SEM images of 5, 9, 11 and 18 composites.

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Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

error of DOE (design of experiment), is 5.48% which is acceptable.

This error originates from some factors which have negligible
effect on these properties (hardness and open porosity) such as
Cf, M.t and pressure. In the other hand, selecting un-effective factors cause makes an error. So, factor selecting, is a very important
step in DOE. If the step is not done carefully, DOE error will be high
(more than 15%) and so, it will not be acceptable. Standard analysis
method was used to investigate the effect of each parameter on
hardness.
3.1. Effect of SiC, Cf and M.t on hardness

Fig. 2. SEM image of composite 1.

Table 5
Hardness ANOVA analysis results for all parameters.
Fac.

DOF
(f)

Sum of Sqrs
(s)

Variance
(V)

F-ratio
(F)

Pure sum
(s0 )

Percent P
(%)

SiC
Cf
M.t
MoSi2
HfB2
ZrC
Temp.
Press.
Time
Error
Total

3
3
3
3
3
3
3
3
3

138493.4
8927
17494.4
207941.2
114177.3
153864.3
917843.3
3864.2
35,927

46164.5
2975.7
5831.5
69313.7
38,059
51288.1
305947.7
1288
1197.7

80
5.2
10.1
120.2
66
88.9
530.5
2.2
20.7

136763.1
7196.7
15764.1
206210.9
112,447
152,134
916,113
2133.9
34196.7

8.168
0.428
0.94
12.309
6.712
9.08
54.709
0.128
2.044
5.48
100

Table 4 shows the results of the open porosity percent and

hardness conducted on the 32 mixtures prepared as suggested by
the Taguchi method. Open porosity percent measurement was
repeated four times for each mixture are shown as Trial 14 in
Table 4. The hardness was obtained by ve correct indents for each
mixture. Results of each indent are shown as Trial 15 in Table 4. It
is apparent that the average hardness in samples 26, 9, 1115, 20,
2325, 29 and 31 which their open porosity percent is less than 3%,
is more than 300 Hv except 18. The hardness of 18 is 264 Hv
because its microstructure is much larger than other sample such
as 5, 9 and 11. Fig. 1 shows the SEM images of 5, 9, 11 and 18 composites. These images conrm the hardness results.
Also, according to Table 3, sample 1 with most open porosity
percent, 29.8%, has least hardness, 35 Hv. SEM image of sample 1
is shown in Fig. 2. With respect to the open porosity percent and
hardness data (Table 4), it can be found that they change adversely
together. On the other hand, by increasing open porosity percent,
hardness decreases.
In our next work, it will be discussed in detail and nine parameters will be optimized to reach maximum hardness and less open
porosity percent.
The data were entered to Qualitek-4 software (version 14.5).
The results of ANOVA (analysis of variance) analysis are given in
Table 5. It is clear that Temperature with 54.7%, MoSi2 with
12.3%, ZrC with 9.08%, SiC with 8.16% and HfB2 with 6.7% and have
the most portions on the open porosity, respectively. These results
indicated that the temperature of SPS and MoSi2 are very important parameters on hardness.
Time with 2.04%, M.t with 0.94%, Cf with 0.42% and pressure
with 0.12% have the least impact on hardness. Also, it is clear that

Fig.3 shows effect of SiC, Cf content and M.t hardness. It can be

observed that hardness increases by increasing SiC content
(Fig. 3a). SiC increases the hardness by 3 mechanisms; rstly, SiC
improves the sinterability of ZrB2-based ceramics by formation of
intergranular liquid phases [9] which decreases the porosity.
Since, the pores in ceramics have no resistance to applied stress,
materials with more porosity have lower apparent microhardness
values than the dense counterparts [10]. In this study, it is clearly
indicated that porosity decreases by SiC increasing (Fig. 3a).
Secondly, it is well-known that SiC acts as inhibitor and restrains
grain growth [11]. Chamberlain et al. [12] prepared ZrB2 ceramics
at different temperatures (19002150 C) and 180 min holding
time by the pressureless method and compared the data with
hot-pressed ZrB2. They concluded that hardness decreases in pressureless method relative to hot-pressing due to larger grain size in
the pressureless materials. The larger grain size decreases the frequency with which dislocations encounter grain boundaries, thus
reducing the amount of stress required for deformation to occur.
Thirdly, SiC particles have more hardness than ZrB2 particles.
So, dispersion hardening of ZrB2 with the harder SiC phase
increases ZrB2-base ceramics with higher SiC content. Hwang
et al. [13] prepared ZrB2SiC composites with different SiC content
(0 vol%, 5 vol%, 11 vol% and 22 vol%) by hot pressing at 1650 C.
They found that relative density and hardness increase by increasing SiC content.
It can be seen that the hardness does not change more by
increasing Cf at rst (until 5 vol%) and then decreases slightly
(Fig. 3b). Firstly, hardness reduction due to Cf addition is reected
from the Cf effect on densication. Secondly, according to Guo
foundings [14], Cf increases the SiC grain and so, decreases the
hardness. Fig. 4 shows the SEM images of composites 6 and 12.
Although, composite 12 has a lower temperature (18001900 C)
and time (412 min) SPS than composite 6, it is clearly observed
that SiC grains in composite 12 are larger than composite 6 due
to more Cf. The addition of ber hindered from breaking apart
the agglomeration of SiC particles during the mixing process. As
a result, clusters of SiC particles were fused together during hot
pressing to form larger SiC particles. Furthermore, the hindering
effect is enhanced with increasing ber volume fraction [14].
Totally, we can conclude that for Cf as low as 5 vol%, the hardness
is not changed.
Fig. 3c shows that M.t improves hardness until 5 h and then
decreases it.
3.2. Effect of MoSi2, HfB2 and ZrC on hardness
Effect of MoSi2, HfB2 and ZrC on hardness is shown in Fig. 5. It is
clearly observed that MoSi2 increases hardness strongly at rst
(2 vol%) and then the curve is nearly smooth (Fig. 5a). MoSi2 is very
effective sintering aid and improves sinterability of ZrB2-based
ceramics by liquid phase formation [15], as shown in Fig. 3a. So,
due to open porosity reduction by increasing MoSi2, and respect
to the fact that the porosities have no resistance to applied stress,
hardness increases.

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Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

(b) Cf

300

300

12

250
9

200
150

Hardness, Hv

12

Porosity %

Hardness, Hv

15

350

(a) SiC

250
9

200
150

Porosity %

15

350

100

100

50

50
0

0
1

0
1

Level

Level

15

350

(c) M.t
12

250
9

200
150

Porosity %

Hardness, Hv

300

100
3
50
0

0
1

Level
Fig. 3. Effect f (a) SiC, (b) Cf and (c) M.t on hardness for combinations of variables (levels) as dened in Table 1.

SiC

SiC

Fig. 4. SEM images of composites 6 and 12.

It is observed that HfB2 decreases hardness initially and then

increases it (Fig. 5b). HfB2 has two-sided behavior. Open porosity
percent increases by increasing HfB2 due to its higher melting
point and so has negative effect on hardness. But, on the other
hand, HfB2 has more hardness than ZrB2, and due to dispersing
harder particles in matrix, is expected to increase hardness and
have a positive effect on hardness. At the result, there is challenge
between two factors: (1) the amount of open porosity percent
caused by HfB2, and (2) hardness was obtained by HfB2 particles.
It can be seen, the former factor is dominate up to 10 vol% HfB2
and hardness decreases by increasing HfB2. For 15 vol% HfB2

second factor is dominated. Finally, we can conclude, for the same

open porosity percents, increasing HfB2 improves the hardness.
The effect of ZrC on hardness is shown in Fig. 5c. It can be
observed that ZrC improves the hardness. It can be reected from
three mechanisms: (1) ZrC improves densication up to 10 vol%,
according to Fig. 5c which is accordance with other researches
founding [11,16]. (2) According to other studies [11,16] ZrC is very
good grain growth inhibitor which is completely in accordance
with our results. SEM images of composites 4, 18, 5, 32, 29 and
15 are shown in Fig. 6. By comparing composites 4 and 18, 5 and
32, 29 and 15 together, it is clearly observed that grains size of

Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

15

350

200
150

Hardness, Hv

250
9

(b) HfB2

300

12

Porosity %

Hardness, Hv

300

15

350

(a) MoSi2

100

12

250
9

200
150

Porosity %

622

100
3

3
50

50
0

0
2

0
1

Level

Level
15

350

(c) ZrC

300

Hardness, Hv

12

250
9

200
150

Porosity %

100
3
50
0

0
1

Level
Fig. 5. Effect of (a) MoSi2, (b) HfB2 and (c) ZrC at different levels (Table 1) on hardness.

ZrB2 (gray grain) and SiC (black grain) decrease by increasing ZrC
content at same sintering temperatures. In addition by comparing
the reduction amount of grain size in each temperature, we can
conclude that ZrC is more effective at higher temperatures due to
more grain growth which occurs. So, by using ZrC, it is possible
to have nearly same grain size at higher temperature rather than
lower sintering without ZrC addition. For example, composite 5
have nearly same grain size in comparison by composite 15 while
it is sintering temperature and time is higher (Fig. 6). The addition
of the second phase leads to a signicant decrease in the grain size
of the main material. This is due to the fact that the second phase
constitutes an additional obstacle (together with pores and impurities) to grain-boundary migration. According to Zener [16], inclusions in a material are capable of strongly affecting boundary and
surface-diffusion parameters, which ultimately govern collective
recrystallization.
3.3. Effect of SPS condition hardness
Fig. 7 shows the effect of SPS conditions on hardness. It is
observed that increasing temperature, obviously improves the
hardness. Also, according to Table 4 data and Fig. 5a, it can be seen,
that temperature has the highest inuence on hardness and open
porosity percent rather than other parameters. In fact, it is
reected from two factors: (1) the signicant effect of temperature
on open porosity percent and (2) grain size. It is well-known that
by increasing temperature, grain size increases and depending on
its amount may affect hardness. If this amount be noticeable, there

will be challenge between porosity percent reduction and grain

size as result of increasing temperature.
Hardness signicantly increases from 1600 C to 1700 C at rst,
and then the curve is nearly smooth and nally increases noticeably in the range of 18001900 C, as shown in Fig. 7. By comparing
open porosity curve with hardness (Fig. 7a), it is clearly observed
this hardness behavior is related to its densication manner. To
explain it, two composites series were chosen: rst, 16, 27, 17
and 11 (without MoSi2); second, 28, 15, 3, 24. In each series, effect
of temperature (16001900 C) is investigated.
In rst series, it can be found that open porosity percent is
approximately constant (14%) by increasing temperature from
1600 C to 1800 C, and then decreases to 3.5% (Table 3). So, we
can conclude critical temperature for densication is 1900 C. In
second series, open porosities percent in 28, 15, 3, 24 composites
are 12%, 3%, 1.7% and 0.3% respectively (Table 3) and so reduction
in open porosity percent occurs in 1700 C which is different to
rst series. This is related to MoSi2 content in each series. In rst
series, there is no MoSi2 and so the only parameter which affects
open porosity percent is temperature while in second series, there
is MoSi2 in all composites. Therefore, in this series, in addition of
temperature, MoSi2 causes open porosity percent reduction.
Since, MoSi2 is very effectiveness sintering aid which acts in temperatures more than 1700 C [17], the critical densication temperature is 1700 C, in this series. So, two noticeable arises in
hardness (1700 C, 1900 C) are related to the two reductions in
open porosity percent (1700 C, 1900 C). Also, it is concluded that
grain size changing range in this article has little effect on the

Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

623

Fig. 6. SEM images of composites 4 (15 vol% ZrC), 18 (0 vol% ZrC) sintered at 1900 C, 16 min; 5 (10 vol% ZrC, 16 min), 32 (0 vol% ZrC, 8 min) sintered at 1800 C; 29 (15 vol%
ZrC) and 15 (0 vol% ZrC) sintered at 1700 C, 12 min.

hardness except composite 18. In order to investigate the effect of

grain size on hardness, composites with most and least grain size
were measured by Optika Vision Pro-Video and it was found composite 18 have the most (8 lm) grain size (Fig. 6) between all
composites and although its porosity is zero, has hardness below
300 Hv which originates from its high SPS temperature and time
(Table 2).
After composite 18, composite 4 have the most grain size,
6 lm, (Fig. 6). The smallest grain size belongs to composite 29,
2 lm. Therefore, by ignoring composite 18, the maximum difference grain size in not more than 4 lm and which cannot overcome open porosity reduction.
However, additives such as SiC, ZrC and HfB2 have inuence on
hardness, as mentioned in Section 3.2. It means, it is possible that

composites with more open porosity percent have more hardness

effects related to composition. For example, composite 22
(332 Hv) with 10.5% porosity is harder than composite 32
(190 Hv) with 8% porosity due to its more ZrC and HfB2.
Pressure does not have any signicant effect on hardness and
open porosity, as shown in Fig. 7b which is in accordance by other
researches [18].
Effect of time on hardness is shown in Fig. 7c. It is clear that
hardness increases strongly by increasing time until 8 min and
then curve is approximately smooth. It is related to the open porosity reduction due to time increasing as shown in Fig. 7c. Also, it can
be found that increasing grain size due to time has less inuence
on hardness rather than open porosity percent reduction except
composite 18 as mentioned above.

Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

15

350

150

100

Hardness, Hv

250
200

(b) Press.

300

12

Porosity %

Hardness, Hv

300

15

350

(a) Temp.

12

250
9

200
150

Porosity %

624

100
3

3
50

50

0
3

Level

Level
15

350

(c) Time

Hardness, Hv

300

12

250
9

200
150

Porosity %

0
1

100
3
50
0

0
1

Level
Fig. 7. Effect of (a) temperature, (b) pressure and (c) time at various levels (Table 1) on hardness.

Table 6
Hardness, open porosity percent and porosity & hardness optimum levels as dened in Table 1.
Factor

SiC

Cf

M.t

MoSi2

HfB2

ZrC

Optimum level, open porosity

Optimum level, hardness
Optimum level, porosity & hardness

4
4
4

2
3
2

2, 3
3
3

4
4
4

1,2
1
1

3
3
3

4
4
4

3
2, 3
3

4
4
4

3.4. Optimization
Optimum conditions to reach the best densication and hardness are shown in Table 6. In order to reach best densication
and hardness together (in one composite), the multiple criteria
(OEC) of Taguchi method is used. The optimum conditions are
shown in Table 6. It is clear that the optimum level of SiC, MoSi2,
ZrC, temperature and time to reach best densication and hardness
are same. So, their optimum level to reach best densication &
hardness together will be same, too. Optimum Cf level is different
in open porosity and hardness and for best densication & hardness, optimum level of densication is obtained by OEC due to
more weights (8020%) that we gave to open porosity percent
responds rather than hardness responds. These weights are given
based on open porosity and hardness important for us. For M.t,
HfB2 and pressure, the level which both maximum densication
and hardness is available, is obtained by OEC.

4. Conclusion
4.1. It has been concluded that the most signicant effects on the
hardness are related to temperature, MoSi2, ZrC, SiC and
HfB2 by 54.7%, 12.3%, 9.1%, 8.2% and 6.7%, respectively.
4.2. Pressure by 0.13% and Cf by 0.43%, M.t by 0.94% and time by
2% have the least effect on the hardness.
4.3. By increasing the temperature, time, MoSi2 and SiC from
level 1 to 4, hardness improved continuously while by
increasing HfB2 from level 1 to 4, hardness decreased
consistently.
4.4. The optimum condition, to reach the most densication is
(levels from Table 1 are indicated in parentheses) T (4), t
(4), P (3), SiC (4), Cf (2), M.t (2 or 3), MoSi2 (4), HfB2 (1 or
2) and ZrC (3).
4.5. The optimum condition, to reach the most hardness is
(levels from Table 1 are indicated in parentheses) T (4), t

Z. Balak et al. / Journal of Alloys and Compounds 639 (2015) 617625

(4), P (2 or 3), SiC (4), Cf (3), M.t (3), MoSi2 (4), HfB2 (1) and
ZrC (3).
4.6. The optimum condition, to reach the most densication &
hardness is (levels from Table 1 are indicated in parentheses) T (4), t (4), P (3), SiC (4), Cf (2), M.t (3), MoSi2 (4), HfB2
and ZrC (3).

References
[1] M. Thompson, Densication and Thermal Properties of Zirconium Diboride
Based Ceramics, P.H.D Thesis, University of Missouri-Rolla, 2012.
[2] Ji Zoua, Guo-Jun Zhang, Hui Zhang, Zheng-Ren Huang, Jef Vleugels, Omer Van
der Biest, Improving high temperature properties of hotpressed ZrB220 vol%
SiC ceramic using high purity powders, Ceram. Int. 39 (2013) 871876.
[3] Huiping Yuan, Junguo Li, Qiang Shen, Lianmeng Zhang, Preparation and
thermal conductivity characterization of ZrB2 porous ceramics fabricated by
spark plasma sintering, Int. J. Refract. Metals Hard Mater. 36 (2013) 225231.
[4] De-Wei Ni, Ji-Xuan Liu, Guo-Jun Zhang, Pressureless sintering of HfB2SiC
ceramics doped with WC, J. Eur. Ceram. Soc. 32 (2012) 36273635.
[5] V. Zamoraa, A.L. Ortiza, F. Guiberteaua, M. Nygren, In situ formation of ZrB2
ZrO2 ultra-high-temperature ceramic composites from high-energy ball-milled
ZrB2 powders, J. Alloys Comp. 518 (2012) 3843.
[6] W.M. Guo, Z.G. Yang, G.J. Zhang, Comparison of ZrB2SiC ceramics with Yb2O3
additive prepared by hot pressing and spark plasma sintering, Int. J. Refract.
Metals Hard Mater. 29 (2011) 452455.
[7] W.M. Guo, Z.G. Yang, J. Vleugels, G.J. Zhang, Effect of pressure loading cycle on
spark plasma sintered ZrB2SiCYb2O3 ceramics, Ceram. Int. 38 (2012) 5293
5297.

625

[8] W.M. Guo, J. Vleugels, G.J. Zhang, P.L. Wang, O. Van der Biest, Effect of heating
rate on densication, microstructure and strength of spark plasma sintered
ZrB2-based ceramics, Scr. Mater. 62 (2010) 802805.
[9] M. Ikegami, S. Guo, Y. Kagawa, Densication behavior and microstructure of
spark plasma sintered ZrB2-based composites with SiC particles, Ceram. Int. 38
(2012) 769774.
[10] S. Zhu, W.G. Fahrenholtz, G.E. Hilmas, Inuence of silicon carbide particle size
on the microstructure and mechanical properties of zirconium diboride
silicon carbide ceramics, J. Eur. Ceram. Soc. 27 (2007) 20772083.
[11] A. Snyder, D. Quach, J.R. Groza, T. Fisher, S. Hodson, L.A. Stanciu, Spark plasma
sintering of ZrB2SiCZrC ultra-high temperature ceramics at 1800 C, Mater.
Sci. Eng. A 528 (2011) 60796082.
[12] Adam L. Chamberlain, William G. Fahrenholtz, Gregory E. Hilmas, Pressureless
sintering of zirconium diboride, J. Am. Ceram. Soc. 89 (2) (2006) 450456.
[13] Sung S. Hwang, Alexander L. Vasiliev, Nitin P. Padture, Improved processing
and oxidation-resistance of ZrB2 ultra-high temperature ceramics containing
SiC nanodispersoids, Mater. Sci. Eng., A 464 (2007) 216224.
[14] S. Guo, K. Naito, Y. Kagaw, Mechanical and physical behaviors of short pitchbased carbon ber-reinforced HfB2SiC matrix composites, Ceram. Int. 39
(2013) 15671574.
[15] S. Guo, Densication of ZrB2-based composites and their mechanical and
physical properties: a review, J. Eur. Ceram. Soc. 29 (2009) 9951011.
[16] V.M. Gropyanov, L.M. Beltyukova, Sintering and recrystallization of ZrCZrB2
compacts, Institute of Refractories, Leningrad. Translated from Poroshkovaya
Metallurgiya, 7(67) 2532.
[17] D. Sciti, L. Silvestroni, M. Nygren, Spark plasma sintering of Zr- and Hf-borides
with decreasing amounts of MoSi2 as sintering aid, J. Eur. Ceram. Soc. 28
(2008) 12871296.
[18] Pachanee Thapnuy, Siriporn Larpkiattaworn, Tachai Luangvaranunt, Jun
Ikeuchi, Effect of temperature and pressure on the densication of titanium
silicide compound, J. Metals, Mater. Miner. 20 (2) (2010) 710.