Journal of Non-Crystalline Solids 409 (2015) 120125

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Journal of Non-Crystalline Solids

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

Lithium ion-conducting glass-ceramics in the system

Li2OTiO2P2O5Cr2O3SiO2
P. Goharian a,, B. Eftekhari Yekta b, A.R. Aghaei a, S. Banijamali a
a
b

Ceramic Division, Materials and Energy Research Center, P.O. Box: 31787-316, Alborz, Iran
Ceramic Division, Materials Engineering Department, Iran University of Science & Technology, P.O. Box: 16846-13114, Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 5 August 2014
Received in revised form 27 October 2014
Accepted 7 November 2014
Available online 20 November 2014
Keywords:
Glass-ceramics;
Phosphate glasses;
Ionic conductivity;
Impedance spectroscopy;
Crystallization

a b s t r a c t
Conductive glass-ceramics based on Li2OTiO2P2O5Cr2O3SiO2 system were fabricated by heat-treatment at
the crystallization peak temperature for 2 h. The crystallization behavior of glass-ceramics was identied by differential thermal analysis (DTA), X-ray diffraction (XRD) and eld emission scanning electron microscopy
(FESEM) methods and their conductivity behavior was investigated by complex impedance techniques. The
glass-ceramics were mainly composed of LiTi2(PO4)3 in which Ti4+ ions were partially replaced by Cr3+ ions.
A considerable enhancement in conductivity was observed by partial substitution of Ti4+ by Cr3+ ions. 100
part [Li1.5Cr0.5Ti1.5(PO4)3] and 5 part SiO2 glass-ceramics in the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part
SiO2 system, where x = 00.8, exhibited the highest ambient conductivity value of 2.14 102 S/cm with an activation energy as low as 15.1 kJ/mol.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Lithium-ion batteries are now extensively used as electrolytes in energy storage devices due to their unmatchable properties of very light
weight and very high energy-density storage. The NASICON-type ceramics with the chemical formula LiTi2(PO4)3 are promising candidates
as solid electrolytes applied in such batteries [1].
The structure of these compounds is rhombohedral (space group
R3c). This framework is built of PO4 tetrahedra and TiO6 octahedra
linked by their corners to form the [Ti2(PO4)3] rigid three-dimensional
skeleton. This structure results in cavities whereby the lithium ions can
reside, and in channels through which they can pass. The interstitial cavities generated within the network are of two types known as A1 and A2
sites (1:3 multiplicity). (i) A1 sites surrounded by six oxygen atoms and
located at inversion centers, and (ii) A2 sites, with an irregular ten-fold oxygen co-ordination and disposed symmetrically around ternary axes.
Both sites are arranged in an alternating way along the conducting channels. The A1 sites are full of Li1+ ions but the A2 sites are vacant [27].
It is said that the ionic conductivity of NASICON-based ceramics
(106 S/cm1 at RT) may be enhanced, at least 2 orders of magnitude,
by partial substitution of Ti4+ by trivalent cations such as Al3+, Ga3+,
In3 +, Ti3 +, Sc3 +, Y3 +, La3 +, Cr3 +, and Fe3 +. An increase of overall
ionic conductivities is due to a higher charge carrier number and to a
lower porosity of the pellets [3,8].
Corresponding author.
E-mail address: parisagoharian@yahoo.com (P. Goharian).

http://dx.doi.org/10.1016/j.jnoncrysol.2014.11.016
0022-3093/ 2014 Elsevier B.V. All rights reserved.

In comparison to LiTi2(PO4)3-based ceramic electrolytes, glassceramics based on NASICON crystalline phase can be made more easily
into the desired shapes and sizes, with dense microstructure and negligible grain boundary effects. The glass-ceramic process provides also a
homogeneous microstructure with controlled grain size and grain
boundaries [9,10].
However, the glass formation in the Li2OTiO2P2O5 system is extremely difcult as the glass transition temperature (Tg) and crystallization temperatures (Tc) of the related glasses are relatively close together
[11,12].
Fu [13] studied the effect of Al and Ga dopants on the ionic conductivity of Li2OTiO2P2O5 glass-ceramics and Abrahams also [11] studied the
effect of Al dopant on the ionic conductivity of this system, they prepared
a nonstoichiometric glass composition with excess of AlPO4 and GaPO4,
2[Li1 + xAlxTi2 x(PO4)3]AlPO4 and 2[Li1 + xGaxTi2 x(PO4)3]GaPO4,
probably to enhance the glass-forming ability of the initial glass.
In another work, Fu [12] also used 10 mol% SiO2 in a stoichiometric
NASICON glass composition. The present authors have used 5 mol%
SiO2 to improve the glass forming ability of the Li2OTiO2P2O5 system.
In this way they had been able to prepare a dopant-free glass-ceramic
with high ionic conductivity, which makes the authors able to investigate the role of dopant addition on the electrical properties of the
derived glass-ceramic. Therefore, the present authors have chosen Cr
dopant and synthesized new NASICON type Li1+ ion conductor glassceramic via partial substitution of Ti4+ by trivalent Cr3+ cation. This cation was chosen as its ionic radius is very close to that of Ti4+ ion, which
may yield the most substitution and so increasing the charge carrier

P. Goharian et al. / Journal of Non-Crystalline Solids 409 (2015) 120125

121

number and ionic conductivity. In the present paper, composition dependence of conductivity will be reported.
2. Experimental procedure
Analytical reagent-grade chemicals of Cr2O3, Li2CO3, TiO2, P2O5 and
SiO2 were used as starting materials to prepare the batch compositions
of the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 glass system,
where x = 00.8. After being sufciently mixed, the glass batches
were melted in alumina crucibles at 1450 C in an electric furnace for
1.5 h. The melts were cast in a stainless steel mold. The resultant glasses
were then annealed at 450 C for 2 h and allowed to be naturally cooled
to room temperature.
The crystallization peak temperatures (Tp) of the resultant glasses
were determined using differential thermal analysis (Polymer Laboratories, STA-1640) at a heating rate of 5 C/min. The glass-ceramics were
prepared by heating the glasses at their crystallization peak temperatures (Tp) for 2 h. Crystalline phases precipitated during heat treatment
were identied by an X-ray diffractometer (Siemens D500) with Cu-K
radiation. According to the XRD data, the lattice constants were determined by the Rietveld method by using MAUD (material analysis
using diffraction) software. In the Rietveld renement, the relevant accuracy is 0.5% [14].
The microstructure of polished and fractured surfaces of the glassceramics was investigated by means of eld emission scanning electron
microscopy (Sigma/VP, Zeiss).
Polished specimens were used to measure the ionic conductivity.
Gold electrodes were sputtered on both parallel surfaces of the specimens. Before sputtering, glass specimens were cut and polished into
disc with diameter of about 10 mm and a thickness of 1 mm.
Each gold-coated glass-ceramic electrolyte was gently assembled
into stainless steel (SS) blocking electrodes in a cell xture. The xture
containing the SS/electrolyte/SS cell was subsequently placed in a stable
xture holder and attached to the impedance spectrometer. Electrical
conductivity was measured by impedance spectroscopy, using a Solartron
instrument (Model 1260) in the 0.1107 Hz frequency range. The AC impedance of the glass-ceramic electrolyte was measured in the 0 to 100 C
temperature interval. At each temperature, the specimen was equilibrated for 1 h before the impedance measurement.
3. Results and discussion
3.1. Phase and structure analysis
DSC curves of 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2
glasses containing various Cr2O3 amounts at the heating rate of 5 K/min
are shown in Fig. 1.
By increasing the amount of x, the system became more complicated
and the opportunity for the formation of eutectic between constituents
was increased according to the Mixing Rule. Furthermore, the Li2O content, which is a strong ux, was enhanced. These both events lower the
glass viscosity.
It is well known that [15] two factors were involved in the crystallization behavior. One factor is the favorable thermodynamic condition
and the other one is the favorable kinetic condition.
The decrease in glass viscosity leads to the increase of the diffusion
rate of the crystal's constituents, kinetically. As a result, increasing the
amount of x has led to a decrease in the crystallization peak temperature (Tp), suggesting that crystallization of the glasses becomes much
easier by probable decrease of viscosity.
Fig. 2 shows the XRD patterns of the glasses after heat-treatment at
their crystallization peak temperatures (Tp) for 2 h.
As can be seen from Fig. 2, a slight shift of diffraction peak position
towards low angle indicated that the replacement indeed took place because of the larger ionic radius of Cr+3 (0.615 ) compared with that of
Ti+4 (0.605 ).

Fig. 1. DTA curves of the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 (x = 00.8)
glasses.

The major crystallized phase and the minor one are LiTi2(PO4)3
(JCPDS card 35-0754) and TiO2 (JCPDS card 71-1168) at x = 0, respectively. Based on the utilized TiO2 reference card, the relevant modication was Anatase.
However, partial substitution of Ti 4 + by Cr + 3 led to precipitation of only conductive phase LiTi 2 (PO 4 ) 3 in the 100 part
[Li 1 + x Crx Ti2 x (PO 4 ) 3 ] and 5 part SiO2 (x = 0.2, 0.4 and 0.5) glassceramics, which seems to be reasonable when one considers the reduction of the concentration of TiO2 in the glass.
No new peak appears as Cr+3 ions replace Ti4+ ions, inferring that
the added Cr+ 3 ions were accommodated into the LiTi2(PO4)3-type
structure by replacing Ti4+ ions.
When the x value increased from 0 to 0.5, the XRD intensity was
rst gradually increased, due to the growth of the LiTi2(PO4)3-type
phase, so that a maximum intensity was obtained for x = 0.5, and decreased after further increasing of x and ultimately led to formation
of unknown phase or phases at x = 0.6 and 0.8. The crystallization of
Cr2Ti5O13 phase (JCPDS card 35-0099) was also observed at x = 0.8.
As a matter of fact, the crystallinity of the specimen was increased
due to enhancement of both Li+ and Cr+3 ions. The farmer is a known
ux which can reduce the viscosity as well as the crystallization temperature of the glass [15]. It seems that crystallization of NASICON has been

Fig. 2. X-ray diffraction patterns of the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2
(x = 00.8) glass-ceramics.

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P. Goharian et al. / Journal of Non-Crystalline Solids 409 (2015) 120125

improved by Cr+3 substitution up to x = 0.5. After that, the Cr2O3 solubility into the NASICON structure becomes lower and precipitates as
Cr2Ti5O13 phase and an unknown crystalline phase and/or remains
within the glass structure as an ionic element.
Also it should be noted that with the increase of x from 0 to 0.8, the
TiO2 amount decreases. Therefore, all these events decline the constituents' concentration of the LiTi2(PO4)3, which lead to reduction of
NASICON amounts.
The observed, calculated and difference patterns obtained from the
Rietveld renement of the data of the 100 part [Li1 + xCrxTi2 x(PO4)3]
and 5 part SiO2 (x = 0 and 0.4) are shown in Fig. 3. The Rietveld renement for the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 (x = 0,
0.2, 0.4, 0.5, 0.6 and 0.8) glass-ceramics was performed based on the
Li1.12In0.12Ti1.88(PO4)3 and TiO2 phases and their Crystallographic Information File (CIF). Based on the utilized CIF for TiO2, the relevant modication was anatase.
The rening agreement factor of Rw and cell parameters of the
chromium-doped compounds determined by Rietveld calculations
were plotted in Table 1.
The structural renement data are acceptable, when a) for a medium
complex phase, Rw b 10%, b) for a highly complex phase (monoclinic to

Table 1
The agreement factor (Rw) and lattice parameters for the glass-ceramics in the system 100
part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 (x = 00.8).
100 part [Li1 + xCrxTi2 x(PO4)3]
and 5 part SiO2
x
x
x
x
x
x

=
=
=
=
=
=

0
0.2
0.4
0.5
0.6
0.8

Lattice parameters
a/nm

b/nm

0.8497
0.8499
0.8501
0.8502
0.8505
0.8508

2.0964
2.098
2.103
2.1054
2.1088
2.1123

Rw (%)

8.3
9.4
8.5
8.4
9.7
9.5

triclinic), the value of Rw b 15% and c) for a highly symmetric material or

compound (cubic) with few peaks, the value of Rw b 8% [14].
According to Table 1, a slight increase in a-parameter and a considerable increase in c-parameter are visible with increasing x. The substitution of Ti4+ by Cr3+ inuences mainly the size of the TiO6 octahedra.
The slightly larger ionic radius of Cr+3 (0.615 ) than that of Ti+4
(0.605 ) and incorporation of excess lithium ions into vacant A2 sites
lead to the gradual increase of the cell constant c of the solid solution.

Fig. 3. Observed (black dots), calculated (black line at the top) and difference (black line at the bottom) powder XRD proles of the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 glassceramics, (a: x = 0 and (b: x = 0.4.

P. Goharian et al. / Journal of Non-Crystalline Solids 409 (2015) 120125

The rening agreement factor of Rw (Table 1) is reliable when Rw b 15%

[14].
3.2. Microstructure of the glass-ceramics
The microstructures of the polished and fractured surfaces of the resultant glass-ceramics heat-treated at the crystallization peak temperature (Tp) are shown in Fig. 4.
As can be seen from the micrographs, more homogenous structures
composed of ne LiTi2(PO4)3 crystals have been obtained with increasing the amount of x up to 0.5. Furthermore, the crystallinity of the specimens has been improved when x b 0.6. These observations come from a
lower crystallization temperature of glasses as well as a high concentration of NASICON's constituents.
A narrow size distribution of crystalline particles is observed when x
reached to 0.5, contacted with each other tightly. A more direct contact
between grains can result to higher mobility of Li+1 ions at the grain
boundaries which endows the material high conductivity and low activation energy.
This favorable microstructure should be the main reason for the low
activation energy and high conductivity of the glass-ceramic with
stoichiometric of the 100 part [Li1.5Cr0.5Ti1.5 (PO4)3] and 5 part SiO2,

123

which will be reviewed in the following section. In the case of x = 0.6

and x = 0.8, the crystallinity is declined due to the decreased amount
of LiTi2(PO4)3 phase. In these glass-ceramics, the presence of the unknown phase was not evident probably due to its low content.

3.3. Electrical conductivity

The impedance plots of polycrystals show characteristics of a pure
ionic conductor composed of bulk, grain boundary and electrode
contributions [16]. It is said that [1620] the impedance spectra of the
glass-ceramics can be separated into two semi-circles, one in the midfrequency range that can be attributed to the resistance of grain boundary (Rgb), and the other small semicircle in the high frequency range due
to resistance of grain (Rg). There is also an inclined line in the lowfrequency part corresponding to the impedance of the electrode/
electrolyte interface belonging to the Warburg diffusion.
The total resistance (Rg + Rgb) and the grain resistance of the specimens are obtained from the right and left intercepts of the semicircles
with the real axis in the plots, respectively. The value of the grain
boundary resistance (Rgb) is simply calculated from the difference between (Rg + Rgb) and Rg.

Fig. 4. Microstructures for the 100 part [Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 (x = 0, 0.2, 0.4, 0.5, 0.6 and 0.8) glass-ceramics containing various Cr2O3 contents.

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P. Goharian et al. / Journal of Non-Crystalline Solids 409 (2015) 120125

Fig. 6. Complex impedance plots of different temperatures for the 100 part
[Li 1.5 Cr 0.5 Ti 1.5 (PO 4 ) 3 ] and 5 part SiO 2 glass-ceramic treated at the crystallization
peak temperature for 2 h.

at 25 C for the high-frequency range with an oblique line in the lowfrequency range, caused by an electrode contribution. At higher temperatures viz. 75 and 100 C, no semicircle was observed and only a
spike caused by the electrode contribution was observed.
The temperature dependence of conductivity for the 100 part
[Li1 + xCrxTi2 x(PO4)3] and 5 part SiO2 (x = 00.8) glass-ceramics
over the temperature range from 0 to 100 C has been presented in
Fig. 7. The conductivity, , obeys the Arrhenius equation (Eq. (2)):
A expEa = KT

Fig. 5. Complex impedance plots of room temperature for the 100 part [Li1 + xCrxTi2
and 5 part SiO2 (x = 00.8) glass-ceramics treated at the crystallization peak
temperature for 2 h.

x(PO4)3]

Fig. 5 shows the complex impedance plots of the 100 part

[Li 1 + x Cr x Ti 2 x (PO 4 ) 3 ] and 5 part SiO2 glass-ceramics, where
x = 00.8, determined at room temperature. Accordingly, there is
only one depressed semicircle, followed by an electrode spike at low
frequency, characteristic of electrode polarization and ionic conduction.
Disappearance of the small semicircle at room temperature is due to the
very low resistance of the crystalline part, which usually responds at
very high frequencies [9,21], and is outside of the testing frequency
range, i.e. higher than 107 Hz. Since it was not possible to separate
grains and grain boundary contributions in these samples, only the
total resistance was analyzed. From the plots, the total resistance (Rt)
of the samples was obtained from the right intercepts of the semicircle
with the real axis in the plots, while the total conductivity (t) of the
glass-ceramics was calculated from Eq. (1):

where A is the pre-exponential factor, Ea is the activation energy for

conductivity, and k is the Boltzmann constant.
To determine the accuracy for activation energy of ionic conductivity, correlation coefcient (R2) was calculated and inserted to Fig. 7. The
measured correlation factors were found to be around 1, conrming the
appropriate accuracy for measurement of the activation energy of ionic
conductivity.
Table 2 presents the activation energies (Ea) calculated from the
Arrhenius plots for ionic conductivity and also the value of overall electrical conductivity at room temperature (ov 25 C) for the specimens.
As can be seen, the ionic conductivity enhanced from x = 0 to 0.5 and
then decreased with further increase in x because of appearance of
the unknown phase or phases.
The increase in conductivity is most likely due to enhancement of
the charge carrier number due to the occupancy of the A2 sites by excess
Li1+ ions by substitution of Ti4+ by Cr3+ ions, the growth of the conductive phase LiTi2(PO4)3 and the elimination of the phase TiO2. The maximum value of conductivity comes up to 2.14 102 S/cm at 25 C when
x = 0.5. The best ionic conductivity value is about three orders of
-2
-3

where H is the sample's thickness and S is the area of the samples [6,14,
22].
According to Fig. 5, the total resistance Rt obviously decreased when
x increased from 0 to 0.5, and then raised with further increase of x,
probably due to crystallization of unknown phase or phases. These
phases have an insulative effect because they block the conduction
path for lithium ions within the grain boundary and therefore reduce
the lithium ion conduction [23].
The ionic conductivities of the prepared glass-ceramics were calculated from their total resistance. Fig. 6 shows the complex impedance
plots of the 100 part [Li1.5 Cr0.5Ti1.5 (PO 4)3] and 5 part SiO 2 glassceramics tested at different temperatures. A semicircle was observed

-4

ln (Scm-1)

t H=S  Rt

-5
-6
-7
-8
-9

-10

x = 0.5
x = 0.4
x = 0.2

R = 0.9994

x = 0.6

R = 0.9995

x = 0.8

R = 0.9989

x=0
2.6

2.8

3.2

3.4

3.6

3.8

R = 0.9992
R = 0.9993

R = 1

1000/T (K-1)
Fig. 7. Arrhenius plot of overall electrical conductivity of the 100 part [Li1 + xCrxTi2 x(PO4)3]
and 5 part SiO2 (x = 00.8) glass-ceramics.

P. Goharian et al. / Journal of Non-Crystalline Solids 409 (2015) 120125

Table 2
Overall electrical conductivity at room temperature (ov 25 C) and activation energy (Ea)
for the glass-ceramics.
100 part [Li1 + xCrxTi2 x(PO4)3]
and 5 part SiO2

ov 25 C (S cm

x
x
x
x
x
x

3
1.1
1.65
2.14
0.57
0.18

=
=
=
=
=
=

0
0.2
0.4
0.5
0.6
0.8

105
102
102
102
102
102

Ea (kJ/mol)
27.9
18.7
16.3
15.1
20.2
23.3

magnitude higher than that of the glass-ceramics with x = 0. Furthermore, the value was higher than the highest room temperature conductivity of the glass-ceramics in the system of Li1 + xAlxTi2 x(PO4)3
obtained by Fu [13].
4. Conclusions
Highly Li-ion conductive glass-ceramics containing the 100 part
[Li1 + x Cr xTi2 x(PO4 ) 3 ] and 5 part SiO2 (x = 00.8) crystalline
phase have been prepared from Li2OTiO2P2O5Cr2O3SiO2-based
glasses.
The ionic conductivity of these glass-ceramics was enhanced by partial substitution of Ti4+ by Cr3+ ions. The increase of the ionic conductivity is due to a higher charge carrier number and to the lower
activation energies. The 100 part [Li1.5Cr0.5Ti1.5(PO4)3] and 5 part SiO2
glass-ceramics exhibited the highest ambient conductivity value of
2.14 102 S/cm with an activation energy as low as 15.1 kJ/mol suggesting that these glass-ceramics are promising electrolyte for practical
application in all-solid-state lithium batteries.

125

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