Materials and Design 79 (2015) 9498

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Materials and Design

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

Characterization and application of porous Ti3SiC2 ceramic prepared

through reactive synthesis
Xinli Liu, Huibin Zhang, Yao Jiang , Yuehui He
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China

a r t i c l e

i n f o

Article history:
Received 15 January 2015
Revised 24 March 2015
Accepted 28 March 2015
Available online 24 April 2015
Keywords:
Ti3SiC2
Porous
Reactive synthesis
Corrosion
Filter

a b s t r a c t
Porous ternary compound Ti3SiC2 with purity of higher than 99.0 wt.% was fabricated through a reactive
synthesis method using titanium hydride, silicon and graphite elemental powders. The parameters of
pore structure including the maximum pore size, open porosity and air permeability, obey the Hagen
Poiseuille formula with the constant G = 0.226 m1 Pa1 s1 for the reactively synthesized porous
Ti3SiC2. The porous Ti3SiC2 shows excellent corrosion resistance in concentrated acids. Further, a typical
lter application in zinc metallurgy has been reported. The excellent overall performance predicts the
porous Ti3SiC2 material has a broad application in industry.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
The environment pollution [1] and high energy consumption [2]
are closely related to the modern metallurgical industry, where
fabric lters that were used for ltration often have insufcient
corrosion resistance, low ltering accuracy, and poor endurance
to elevated temperature. So far, the existing porous materials have
been considered to replace the fabric in the hydro- and pyro-metallurgy industry. The traditional inorganic porous materials
selected as the candidates can be classied into two types: porous
metal and porous ceramic, which have played crucial roles in the
elds of energy [3,4], environment [5], chemical [6] and medical
industries [7,8], etc. However, the utilization of porous metals in
harsh environments has not been realized due to their poor resistance to oxidation, sulfuration and corrosion in acid, alkali and salt
solutions, and low strength at high temperature. Moreover, the
application of porous ceramics which possess a good corrosion
resistance, high microstructure stability and strength at elevated
temperature, is also restricted due to their intrinsic brittleness,
poor machinability, and low thermal shock resistance [9,10]. The
question among the inorganic porous materials cannot be well
answered until recent years, a family of layered ternary ceramics
called MAX phase were intensively investigated, where M is a transition metal, A is an A-group (mostly IIIA and IVA) element, and X is
either C or N. The MAX phases combine the advantages of both
Corresponding author.
E-mail address: jiangyao@csu.edu.cn (Y. Jiang).
http://dx.doi.org/10.1016/j.matdes.2015.03.061
0261-3069/ 2015 Elsevier Ltd. All rights reserved.

metal and ceramic, making the layered ternary compounds erosion-resisting, machinable and not brittle [11], for instance Ti3SiC2.
Ti3SiC2 crystallizes in a hexagonal structure with lattice parameters a = 0.3068 nm and c = 1.7669 nm [12]. The crystalline structure shows a typical laminate characteristic [13], in which each
layer of Si atoms alternates with each of the three close-packed
Ti atoms with all the octahedral pores between Ti layers occupied
by carbon atoms. The nanolaminate structure has two typical kinds
of atom bonds [14]: covalent bond of TiC and metallic bond of Ti
Si. The special crystal lattice and bond structures make the material like a exible ceramic. As common ceramic, Ti3SiC2 has excellent corrosion resistance [15] and good performance at high
temperature (melting point > 2000 C [16] and decomposed
2300 C [17]). Moreover, Ti3SiC2 has merits such as pseudo plasticity [18], good thermal shock resistance, easy machinability [14],
electrical conductivity (4.5  106 X1 m1) and good thermal conductivity (40 W/mK) [13].
Sun et al. [13] fabricated porous Ti3SiC2 compounds (43 vol.%)
by the reactive sintering of elemental powders. Firstov et al. [17]
synthesized porous Ti3SiC2 (porosity h = 0.030.41) in volume of
0.90.95 with impurities of TiC, TiSi2 and SiC by solid-phase sintering of mixes of powders TiH2TiCSiC. The features of its short and
long-term hardness behavior were investigated and a deformation
scheme was proposed. Radhakrishnan et al. [16] synthesized
Ti3SiC2 with 50% of theoretical density and a purity of better than
98 vol.% by reactive sintering of elemental reactants. Ti3SiC2 ternary compound with good pore structure and permeability will be
anticipated as ltration material. However, few investigations on

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X. Liu et al. / Materials and Design 79 (2015) 9498

the pore structure and ltration property were carried out in the
literatures.
In this paper, we demonstrate that porous Ti3SiC2 can be fabricated through a reactive synthesis of titanium hydride, silicon and
graphite elemental powders. The pore structure and corrosion
resistance of this novel porous material were investigated in detail.
The application of porous Ti3SiC2 in the rened purication of zinc
sulfate (ZnSO4) solution in a zinc hydrometallurgy process was also
showed in this paper.
2. Experimental section
2.1. Preparation of porous Ti3SiC2
The reactive synthesis of porous Ti3SiC2 compound was started
with elemental powders of TiH2 (median diameter, 36.5 lm,
99.5%, Chengdu Guoheng technology co., LTD), Si (median diameter,
14.6 lm, 99.5%, Beijing Xingrongyuan technology co., LTD) and graphite (median diameter, 5.5 lm, 99.0%, Qingdao Furongda graphite
co., LTD). The particle sizes of the powders were cross-checked by
laser particle size analyzer (Micro-Plus, Malvern, England) before
the experiment. The addition of TiH2 is benecial to the fabrication
of compounds because the elemental titanium has higher chemical
activity and cleaner reaction interface after dehydrogenation than
common titanium powder. The nominal composition of the powders
is 72.1 wt.% TiH2-16.3 wt.% Si-11.6 wt.% C with the element mol
ratio of Ti:Si:C = 3:1.2:2. Excessive silicon addition can make up
for the evaporation loss of Si at high temperature, which is benecial
to obtain single phase Ti3SiC2 [16]. The reactant powders were wetmixed in a tumbler ball mill for 12 h with ethanol as milling medium. The rolling rate was 60 rpm. The ratio of grinding media to
material was set to be 2:1. High-purity nitrogen was selected as
the protective atmosphere. After mixing, the mixture was dried at
60 C in vacuum oven to remove ethanol. The mixture was then
cold-pressed into green compacts with a dimension of
30 mm  3 mm under pressing pressure of 200 MPa. The relative
density of the compacts was determined to be 81% by comparing
the theoretical material volume and the measured apparent volume.
The green compacts were sintered in a vacuum furnace with a digital
temperature control system and Mo heating element under a pressure of 1.0  103 Pa. A stepped heating method was used in the sintering procedure to obtain the near-net-shaping synthesis of the
reactants [19]. The nal sintering condition was 1350 C for 3 h with
furnace cooling.
2.2. Characterization of porous Ti3SiC2
The open porosity of Ti3SiC2 was measured using the
Archimedes method. The maximum pore size and permeability
were determined based on the bubble point method [20] using
pure N2 as the uid medium on a porous material test instrument
(Pore structure performance tester, FBP-IV, Northwest institute for
non-ferrous metal research, China). The phase of porous samples
were grinded into powders and analyzed by X-ray diffraction
(XRD Rigaku D Max 2500 VB) using a Cu Ka source. The
microstructures were characterized using a eld-emission scanning microscopy (SEM FEI NovaNano 230). The relative volume
percentage of TiC in the synthesized products was calculated by
the calibrated standard addition method [21] according to the following formula:

W TC

ITC =ITSC
1:80 ITC =ITSC

WTC is the weight percentage of TiC phase. ITC/ITSC is the integrated

diffraction intensity ration of TiC to Ti3SiC2 main peaks.

2.3. Immersion test

The samples with average pore size of 3 lm immersed in the
following solutions at room temperature: concentrated hydrochloric acid (HCl, 36.5%, 11.9 M), sulfuric acid (H2SO4, 60.0%, 7.9 M),
concentrated phosphoric acid (H3PO4, 85.1%, 14.6 M). All the acid
solutions were made by the Sinopharm Chemical Reagent Co.,
Ltd. Shanghai, China. The samples were periodically removed from
the acid solutions, rinsed in ultrasonic cleaner with deionized
water and acetone for 5 times, respectively, and then dried in vacuum oven. The samples then were weighed, measured for pore size
changes and re-immersed in solution. Weight and pore size
changes were measured over a whole period of 180 days.
2.4. Filtration of zinc sulfate solution
The ltration of ZnSO4 solution is processed in a factory with a
homemade porous Ti3SiC2 lter system. The contents of metal
impurities before and after ltering were detected by inductively
coupled plasma emission spectrometer (ICP, IRISAdvantage1000,
Thermo Electron Corporation, America).Ten original mineral leaching ZnSO4 solutions come from the factory (Zhuzhou Smelter,
Zhuzhou, China), and the contents of the metal impurities were
shown in Table 1.
3. Results and discussion
3.1. Characterization of the synthesized porous Ti3SiC2
Fig. 1a and b are the different magnication SEM images of the
compacts after sintering at 1350 C for 3 h. It can be seen that a
large number of pores were generated among the compacts as
shown in Fig. 1a. The open porosity of this material is measured
to be 4855% according to the Archimedes method. The pore size
is in the range of 310 lm (Fig. 1b). The resultant skeleton has a
smooth surface, indicating small resistance against passed gas or
liquid and good uid permeability for this potential ltration
material. The phase of the synthesized material was shown in
Fig. 1c, and it is obvious that nearly single Ti3SiC2 phase was synthesized with the strongest peak of Ti3SiC2 (1 0 4) at 2h = 39.52
(JCPDS: 74-0310), and only a very weak TiC (2 0 0) peak was found
at 2h = 41.68 (JCPDS: 89-3828). That means TiH2, Si and C powders
react with each other and generate Ti3SiC2 [22]. In the XRD pattern,
the peak of Ti3SiC2 (1 0 4) has the highest intensity of 13866.7 at
2h = 39.54, but the strongest peak of TiC (2 0 0) with intensity of
135.9 at 2h = 41.68 is much weaker. The weight content of TiC calculated according to Eq. (1) is 0.6 wt.%. The content of TiC impurity
was also determined by the standard Rietveld renement method,
revealing the weight percentage of TiC is 0.8 0.2, so the purity of
the Ti3SiC2 is higher than 99.0 wt.%. The inset of Fig. 1c is the
microstructure of porous Ti3SiC2 skeleton, displaying a

Table 1
The metal contents in the mineral leaching ZnSO4 solutions.
Number Zn (g/L) Cu (mg/L) Cd (mg/L) Co (mg/L) As (mg/L) Sb (mg/L)
1
2
3
4
5
6
7
8
9
10

149.81
155.13
154.37
149.81
152.85
147.53
152.09
146.01
154.25
143.79

714.28
285.71
257.14
785.81
428.57
714.29
857.14
300.00
228.57
523.81

450.98
552.94
637.25
529.41
470.58
517.65
735.29
511.76
568.63
705.88

2.23
1.82
1.99
1.36
2.07
1.90
2.06
1.62
2.01
1.38

1.00
0.80
0.80
0.80
0.80
0.80
0.80
1.00
1.10
0.10

0.40
0.40
0.50
0.40
0.50
0.40
0.40
0.50
0.50
0.05

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X. Liu et al. / Materials and Design 79 (2015) 9498

(a)

100 m

(b)

Fig. 2. Relation of pore structure parameters in porous Ti3SiC2 compounds.

5 m

(104)

(c)
Intensity (a.u.)

Ti3 SiC 2

40

50

60

(201)

70

(1,0,12)
(205) (0,0,14)
(1,0,13)

(008)

(109)
(110)

(0,0,12)

30

(107)
(108)

20

(102)
(103)

(006)

10

(004)

(101)

(105)

1m

80

(d)

nanolaminate characteristic with the spacing interval of about 80

120 nm, which is the typical feature of this ternary compound. The
surface of outward laminate acts as the pore inwall, contributing to
the connectivity of pores. Fig. 1d is the open pore size distribution
of this porous compound measured by bubble point method. The
pore size distribution curve of porous Ti3SiC2 exhibits a characteristic of double peaks. The intensive peak is at the pore size of 3
4 lm, and the weak peak is at the pore size of 910 lm. The initial
porosity of green compact is 20% and the nal porosity is 50%,
so the majority of pores formed in the reaction procedure. There
are 2 kinds of normal sites in compacts for pores to nucleate and
grow: the initial interstitial pores and the interfaces between
grains. Thus 2 kinds of pores generated in the reactively synthesized porous Ti3SiC2: I. The expansion pores based on initial clearance, and II. The main pores formed in the matrix. The expansion
pores have relatively larger pore size and lower porosity considering the size and amount of initial clearance. By varying the size of
powders, the pressing presser and the sintering conditions (sintering temperature, holding time, heating rate, and the sintering pressure), porous Ti3SiC2 with different pore size and porosity can be
fabricated.
In order to investigate the quantitative relation of pore structure parameters including pore size, porosity and permeability, a
series of porous Ti3SiC2 compounds with different pore structure
parameters were fabricated through varying the size of the raw
powders and pressing pressure.
According to the HagenPoiseuille formula [23], there is a relationship between the air permeability, maximum pore size and
open porosity:
2

J G  dm  hP

Fig. 1. (a) and (b) different magnication SEM image of the sintered compact; (c)
XRD pattern of the compact after sintering at 1350 C for 3 h (inset is the layered
structure); (d) the pore size distribution of the synthesized porous Ti3SiC2.

where J is the air permeability; G is a constant related to the properties of permeation uid, macroscopic dimension and pore size
distribution characteristic of the given porous material; dm and hp
are the maximum pore size and open porosity, respectively. The
relationship between the experimental data J and is shown in
Fig. 2. The experimental data follows the rule disclosed by Eq. (2)
well. The constant G is then determined to be 0.226 m1 Pa1 s1
according to the slope coefcient of the tted regression line shown
in Fig. 2.
So the quantitative expression of pore structure parameters
including the maximum pore size dm, open porosity hp and air permeability J of the reactively synthesized porous Ti3SiC2 can be
described by:
2

J 0:226  dm  hP

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X. Liu et al. / Materials and Design 79 (2015) 9498

3.2. Corrosion resistance of porous Ti3SiC2

Many hydrometallurgy processes, in which metallic and ceramic porous materials are not able to bear the rigorous atmosphere
of strong acids, must use the traditional cloth lters with low ltration accuracy and poor backwash effect. Therefore, the advanced
porous material is urgently needed. First of all, the corrosion resistance of porous Ti3SiC2 is characterized by immersing porous
Ti3SiC2 samples in concentrated hydrochloric acid (36.5 wt.%), sulfuric acid (60.0 wt.%), and phosphoric acid (85.1 wt.%) for a whole
period of 180 days, respectively. The mass variations of the porous
Ti3SiC2 immersing in the above three acids are exhibited in
Fig. 3(ac). It is seen that the mass losses of the porous Ti3SiC2 in
these acids after 180 days immersion are less than 0.01 g per
square meter, demonstrating excellent corrosion resistance. The
weight loss of the porous Ti3SiC2 is less than the bulk Ti3SiC2
reported in the literature [15], which may be due to the high purity
of the synthesized porous Ti3SiC2.
The reason that the porous Ti3SiC2 has the outstanding resistance to strong acids corrosion is mainly due to the passivated
dense SiO2-based layer formed on the surface of Ti3SiC2, which prevents the Ti3SiC2 from being corroded by the acid solutions [15].
The maximum pore size variations of the porous Ti3SiC2 vs. immersion time in the acids are also shown in Fig. 3(df). It can be seen
that the porous Ti3SiC2 exhibits excellent corrosion resistance and
pore structural stability in the strong acids. This ensures the longevity in service life and high accuracy in ltration of this material
under rigorous environments.
3.3. Application of porous Ti3SiC2
An application of the porous Ti3SiC2 as lter material in industrial is carried out for the purication of ZnSO4 solution preparing
for the electrolytic zinc. Usually, the ZnSO4 mineral leaching solution contains lots of ne mineral particles, colloids and metallic
ions of Cu, Cd, Co, As, etc. (Table 1). Before the ZnSO4 solution
was used for electrolytic zinc, the ne acid insoluble particles
and metal impurities must be thoroughly removed, because they
can directly inuence the power consumption and zinc product
quality. In the conventional separation process, plate-frame pressure ltrations with fabrics are utilized to purify the mineral
leaching solution and the metallic powders of Cu, Cd, Co

0.04

displaced by the added zinc powders. However, there are some

insurmountable issues in this process, such as short life cycle,
low efcient production, poor backwashing ability, and low ltering accuracy (which often requires the addition of 0.045 g/L polyacrylamide occulants to aggregate the ne particles and
colloids). Besides, the intercepted ne Cd powders are easy to
be redissolved so that another two times of substitution and ltration have to be carried out for the further removal of Cd in
the ZnSO4 solution. Therefore, four times ltrations are usually
applied when using the fabric lter. The attempts to replace the
fabrics with porous ceramic and metal lters for the purication
of ZnSO4 solution have not been successful due to the brittleness
and tight-seal difculty of the porous ceramic and the poor corrosion resistance of the porous metal.
The porous Ti3SiC2 lters used for the purication of ZnSO4
solution has excellent corrosion resistance and high ltering
accuracy. One role of the porous Ti3SiC2 lter is to purify the
ZnSO4 mineral leaching solution containing ne acid insoluble
mineral particles and colloids. The other role is ltering the
metallic powders of Cu, Cd, Co displaced by the added zinc powders. To test the porous Ti3SiC2 lters, a new process ow chart
was developed for the purication of the mineral leaching and
the zinc powder substituting ZnSO4 solutions, as shown in
Fig. 4a. With the new lters, the ltration was successfully completed to purify the mineral leaching zinc sulfate solution without any addition of occulants and the zinc powder
substituting ZnSO4 solution with no leakage of ne Cd particles
occurred. Fig. 4b is the comparison of the supernatant liquid of
mineral leaching ZnSO4 solution (left) and the puried nal solution (right) by the porous Ti3SiC2 lter. It can be seen the original
ZnSO4 mineral leaching solution (metal contents are shown in
Table 1) becomes clear. The high-quality zinc sulfate solution
with less than 3 mg/L solid content and 0.5 mg/L Cd metal ions
(see Table 2) after only two time ltrations was obtained, in
comparison with the conventional fabric purication solution of
760 mg/L solid content after four time ltrations. In the newly
developed ltration process with Ti3SiC2 porous lters, electricity
consumption was reduced by 8%, zinc powder consumption
reduced by 40% and zinc product was improved to the rst grade
(the highest grade of the electrolytic zinc). The technological and
economic signicance of this novel ltration technology is huge
in China as it has zinc production of 5 million tons annually.

(a)

0.02
0.00

Maximum pore diameter (m)

-0.02

Mass variation (g/m 2 )

-0.04
0.04

(b)

0.02
0.00
-0.02
-0.04

0.04

(d)

(c)

0.02
0.00

1
0
4

(e)

3
2
1
0
4

(f)

3
2

-0.02

-0.04
0

1000

2000

3000

Corrosion time (hours)

4000

0
0

1000

2000

3000

4000

Corrosion time (hours)

Fig. 3. Mass losses of porous Ti3SiC2 after immersing in the solutions of (a) 60.0 wt.% H2SO4, (b) 36.5 wt.% HCl, (c) 85.1 wt.% H3PO4 and the average pore size of the porous
Ti3SiC2 in the solutions of (d) 60.0 wt.% H2SO4, (e) 37.5 wt.% HCl, (f) 85.1 wt.% H3PO4 plotted as a function of immersing time.

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X. Liu et al. / Materials and Design 79 (2015) 9498

(a)
Vapor

Thickener

Pre-treatment of

Tank

Zinc powders
Leached residue

Vapor

Reaction kettle

the solution

Sb2O3-Zinc
powders

Reaction kettle

Cd residue
Terminal filter

Filtered solution
Tank

Leached residue
Terminal filter

(b)

Fig. 4. (a) The ow chart of the ltering process using porous Ti3SiC2 lters. (b) Comparison of the supernatant liquid of mineral leaching ZnSO4 solution (left) and the puried
nal solution (right) by the porous Ti3SiC2 lter.

Table 2
The metal contents in the solution puried by the porous Ti3SiC2 lter.

References

Number Zn (g/L) Cu (mg/L) Cd (mg/L) Co (mg/L) As (mg/L) Sb (mg/L)

1
2
3
4
5
6
7
8
9
10

150.27
150.57
141.17
146.4
137.91
133.98
131.37
136.93
107.18
120.91

0.10
0.10
0.18
0.10
0.10
0.10
0.10
0.10
0.36
0.10

0.20
0.29
0.19
0.31
0.33
0.43
0.40
0.08
0.33
0.50

0.54
0.61
0.45
0.45
0.49
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0.49
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0.05
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0.05
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0.05
0.08
0.05
0.08
0.08
0.08
0.05
0.04
0.05
0.05

4. Conclusions
Porous Ti3SiC2 ternary compound with the purity higher than
99.0 wt.% was successfully fabricated through a reactive synthesis
method using TiH2, Si and graphite elemental powders as raw materials. The pore structure parameters of porous Ti3SiC2 including the
maximum pore size, open porosity and air permeability obey the
Hagen-Poiseuille formula with the constant G = 0.226 m1 Pa1 s1.
The synthesized porous Ti3SiC2 has excellent corrosion resistance in
concentrated acids. Furthermore, the application of porous Ti3SiC2
for the ltration of ZnSO4 solution prepared for the electrolytic zinc
is successfully realized, suggesting their wide application prospects
in the elds of ltration and separation.
Acknowledgement
This research is supported by the State Science and Technology
support program of China (Grant No. 2012BAC02B05).

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