Int. J. Appl. Ceram. Technol.

, 1–8 (2014)
DOI:10.1111/ijac.12237

Extending and Enhancing the Properties of Porous Cordierite

Ceramics by Mo6+ ion Incorporation via Facile Combined Synthesis
Technique
Moustafa M. S. Sanad,* Mohamed M. Rashad, and El-Sayed A. Abdel-Aal
Central Metallurgical R and D Institute, P.O. Box 87, Helwan, Cairo, Egypt
Particle Engineering Research Center, University of Florida, Gainesville, FL 32611

Mohamed F. El-Shahat
Faculty of Science, Ain Shams University, Cairo, Egypt

Kevin W. Powers
Particle Engineering Research Center, University of Florida, Gainesville, FL 32611

Molybdenum-doped cordierite ceramics have been fabricated through facile combined techniques, coprecipitation followed
by solid state. XRD results revealed that a-cordierite phase is predominated with increasing Mo6+ ion content. The density mea-
surements showed that the bulk density reduced to the minimum value of 0.61 g/cm3, which corresponds to the maximum
porosity of about 76.8% at 5% Mo6+ ion. The dielectric permittivity (e) of pure cordierite is decreased with increasing Mo6+
ion content. The minimum dielectric loss of Mo-doped cordierite at 1 MHz was equal 0.008 with 10% Mo6+, while at 1 GHz
was equal 0.03 with 5% Mo6+.

Introduction the hexagonal rings structure are connected through Mg

Cordierite (Mg2Al4Si5O18) is a magnesium alumino-
silicate which is widely used in high-temperature applica-
tions, such as catalytic converter substrates for exhaust gas
control of automobile engines1–5 and refractory materi-
als,1–3,5 due to its low coefficient of thermal expansion
(a = 1.5–4.0 9 10 6 per K),1–3,6–12 excellent thermal
shock resistance,1,3,6,10–13 high refractoriness,2,3,6 good
mechanical properties2,4,10, and chemical resistance.4,5,14
Recently, cordierite-based ceramics have been suggested
for use as packaging substrate materials for electronic
devices because of its low dielectric constant.2–5,8–17 Pure
cordierite exists in three polymorphic forms: a hexagonal
high-temperature form, named indialite or a-cordierite,
an orthorhombic low-temperature form designated b-cor-
dierite, and a metastable form referred to as l-cordierite,
which is a solid solution with b-quartz structure.18,19 The
hexagonal and orthorhombic structures are characterized
by their six-membered rings of tetrahedral-coordinated
cations (T2) perpendicular to the c-axis. Alternate layers of
*mustafa_sanad2002@yahoo.com
© 2014 The American Ceramic Society
octahedra and T1 tetrahedra. Silicon occupies mostly T2
tetrahedra and aluminum T1 tetrahedra. Differences
between high- and low-temperature cordierites lie in a
greater or lesser degree of disorder between the aluminum
and silicon atoms within T1 and T2 sites.20,21 Most natu-
ral cordierites are impure cordierites and contain other
cations or molecules which either substitute for Mg2+,
Al3+, or Si4+ are inserted in the channel sites of cordierite
framework.22,23 The preparation of pure cordierite con-
taining several dopants and the effect of substitution of
different elements in the high cordierite lattice on its prop-
erties have been widely reported by several authors.9,24–28
In particular, the influences of substituting the Al3+ ion in
pure cordierite with different metal ions, such as Ga3+,
Eu3+, P3+, Fe3+, or B3+, have been previously investi-
gated.29–33
The aim of this study was to prepare a-cordierite
doped with different amounts of Mo6+ ions via a facile
combined coprecipitation and solid-state routes. In this
proposed wok, each two Al3+ ions will be replaced by
certain concentration of one Mo6+ ion to maintain the
electrical neutrality of the whole compound. In addition,
the effect of Mo6+ ion content on both the structural and
2 International Journal of Applied Ceramic Technology—Sanad, et al.
morphological characteristics will be studied. Moreover,
the prepared ceramic pellets will be evaluated for sinter-
ing, mechanical, and electrical properties as well as corre-
lation of these measured results to the obtained
characteristics will be provided in this study. The reason
for choosing MoO3 as dopant is attributed to its high
value of both thermal expansion coefficient
(a = 5.3 9 10 5 per K)34 and electrical resistivity
(1010 O cm) 35 giving rise to a new cordierite-MoO3
system of broaden thermal and electrical properties for
electronic packaging devices and insulators. As far as we
know, such particular system has not been previously
investigated.
Experimental Procedure
All the chemicals used in this study, such as (magne-
sium chloride hexahydrate Sigma–Aldrich 99.9%,
sodium aluminate Sigma–Aldrich 99.9%, sodium silicate
pentahydrate Sigma–Aldrich 99.9%, hydrochloric acid
ADWIC 37%, molybdic acid H2MoO4 “MoO3.H2O”
Sigma–Aldrich 99%), were of analytical grade. Deionized
water was used in the whole work.
Cordierite gel is synthesized by adding dilute hydro-
chloric acid solution to the solutions mixed of magne-
sium chloride, sodium aluminate, and sodium silicate
(stoichiometrically mixed together achieving the
2MgO:2Al2O3:5SiO2 ratio) till adjusting the pH range
at 7–7.5 to coprecipitate the solution mixture together.
The aqueous suspensions are gently stirred for 15 min to
achieve a good homogeneity and to attain a stable pH
conditions. The obtained gel is then filtered, washed
thoroughly with deionized water, and dried overnight at
105°C in the oven. On the other hand, doped cordierite
precursors are prepared by adding the adequate amount
of molybdic acid powder (x) to the dried pure cordierite
gel from 0.05 to 0.15, which substitute two Al3+ ions
(2 x). The formed precursor mixtures are grinded in a
ball mill for 30 min with a moderate speed to attain a
good distribution conditions. All the prepared precursors
are annealed at 1300°C for 3 h at rate of 5°C/min. The
annealed cordierite samples are grinded again in an agate
mortar with a pestle. Pellets of cordierite samples are
prepared by uniaxially dry-pressing the powders in a 15-
mm-diameter steel die at a pressure of three tons. Pellets
are sintered at 1300°C for 5 h with heating rate of 5°
per min.
X-ray powder diffraction (XRD) was carried out on
a model Bruker AXS diffractometer (D8-ADVANCE,
Karlsruhe, Germany) with Cu Ka (k = 1.54056  A) radi-
ation, operating at 40 kV and 40 mA. The diffraction
2014
data were recorded for 2h values between 10° and 70°,
and the scanning rate was 3° per min or 0.02°/0.4 s. Ther-
mal analysis (TG/DTA) was performed under air atmo-
sphere from room temperature to 1300°C with a heating
rate of 10°C/min using (TGA, Model Q50, V6.1 series;
TA Instruments, New Castle, DE). Scanning electron
microscopy was investigated by a SEM (JEOL-JSM-5410;
Tokyo, Japan). Infrared absorption spectroscopy (FT-IR)
was performed by JASCO 3600 spectrophotometer (Eas-
ton, MD). The density and porosity of each sintered sam-
ple were measured by Archimedes method. The
expansion-shrinkage measurements were achieved using an
Adamel Lhomargy 1/128 inch apparatus (Instrument SA,
Longjumeau, Roissy en Brie, France). Microhardness tests
were evaluated by means of a Vickers Microhardness Tes-
ter, INDENTEC-HWDN-7 Japan (2 kg normal load
applied for 15 s), as an average of six measurements. An
electrometer and DC power supply (Agilent-4339B, Palo
Alto, CA) were used for electrical resistivity measurement
for the experimental studies. A constant DC voltage (V) of
about 1.5 volts was applied from a battery across the sam-
ple. Dielectric properties were measured using a network
impedance analyzer (Agilent-E4991A) that is responsible
for the generation and reception of signals in the frequency
range from 1 MHz to 3 GHz.
Results and Discussion
The phase structures of the powders are investigated
by X-ray diffraction analysis (XRD). Figure 1 shows the
Fig. 1. XRD patterns of cordierite nanopowders with various
Mo6+ ion contents annealed at 1300 °C for 3 h [a-cordierite (*),
sapphirine (+), enstatite (●), forsterite (♦), sillimanite (■), molyb-
denum oxides Mo5O14(▲) and MoO3 (△)].
www.ceramics.org/ACT Molybdenum-Doped Cordierite Ceramics 3

effect of Al2O3 substitution by MoO3 on the phase com-

Molybdenum
position of Mo(x)Al4(2 x)Mg2Si5O18 annealed at 1300°C

(MoO3)
for 3 h with x varying from 0.00 to 0.15. The results of

oxide
the XRD patterns indicated that the highly crystalline a-

—
—
—
10
cordierite (ICDD: 89-1485) is identified as single phase

Table I. XRD Features and Semiquantitative Phase Analysis Results for Cordierite Samples Annealed at 1300°C for 3 h
for the pure sample. In addition, the substitution of

Molybdenum
2Al3+ by 5% Mo6+ results in the evolution of sapphirine
(ICDD: 21-0549) and enstatite (ICDD: 75-1093) as

(Mo5O14)
major phases whereas forsterite (ICDD: 85-1363) and

oxide
sillimanite (ICDD: 74-0274) as minor phases. The rea-

—
—
10
son of disappearing a-cordierite phase and evolution of

6
the above-mentioned phases is attributed to the change

Sillimanite
(Al2SiO5)
in the bulk stoichiometric composition that may modi-
fied by severe infiltration–metasomatism, interaction with
melt, or partial melting due to the incorporation of

—
10
—
—
MoO3.36–39 By insertion of 10% MoO3, the a-cordierite
phase is identified as the predominant phase and associ-

(Mg2SiO4)
Forsterite
ated with the formation of sapphirine, enstatite, and
Mo4O19 (ICDD: 81-1264) as impurity phases. More-
over, the addition of 15% MoO3 leads to the detection

—
15
—
—
of a-cordierite phase as the main phase accompanied
with MoO3 (ICDD: 80-0347) and Mo4O19 phases as

(MgSiO3)
Enstatite
impurity phases. The absence of molybdenum oxide
phases at 5% is due to its very small concentration,

—
35
20
—
which is not detectable and may constitute a consider-
able amount but in an amorphous phase. The incorpora-

(Mg3.5Al9Si1.5O20)
tion of Mo6+ ion in the crystal lattice of a-cordierite
Crystalline phases percentage (%)

may be verified by two facts: first, change of the sample

color from white to pale yellow at room temperature
Sapphirine

and converts to gray at sintering temperature. The gray

color becomes darker with increase in Mo concentration.
Second, the change in the relative intensities of the charac-
—
40
25
4
teristic diffraction peaks of pure a-cordierite [(100),
(110), (002), (102), (112), (202), (211), (212), (220), and
(Mg2Al4Si5O18)

(312)] in comparison with the doped cordierite, especially

a-cordierite

the peaks corresponds to the plane 100. The changes in

the relative intensity of the plane 100 at 2h = 28.4° are
depicted in Table I. This gives clear evidences that the
100
—
45
80

vacant Al sites are occupied by the incorporated Mo6+

ions. Furthermore, the occupancy of Al sites shows quanti-
Crystal.

tatively the explanation of the behavior.40,41

119.4

116.3
(nm)

89.7

On the other hand, the crystallite size is estimated

Size

from the most intense peaks of a-cordierite phase based

on Scherrer equation, D = 0.90k/bCosh, where D is the
plane (100),

average grain size, k is the X-ray wavelength, h and b

Rel. Int.

are the diffraction angle and full-width half-maximum

(FWHM) of an observed peak, respectively. The strong-
37.1
71.9
99.7
(%)
100

est peak at 2h = 29° is used to calculate the average crys-

tallite size of these nanoparticles. The variation in
Ion (%)

percentage of each crystalline phase is determined from

Mo6+

the semiquantitative phase analysis of annealed samples

10
15

and listed in Table I. The results showed that the

0
5
4 International Journal of Applied Ceramic Technology—Sanad, et al.
Fig. 2. DTA curves of cordierite precursors in the presence and
absence of Mo6+ ions.
average crystallite size of cordierite is decreased from
119.4 nm to 89.7 and 116.3 nm with rising Mo6+ ion
content from 0.0 to 10 and 15%. The contraction in the
crystallite size of cordierite content could be related to
the fast rate of crystallization, which gives insufficient
time for crystal growth.
Figure 2 reveals the DSC thermograms of two cor-
dierite samples. The black-colored curve represents the
characteristic thermogram for pure cordierite sample
whereas the red-colored one represents cordierite thermo-
gram-doped cordierite with 15% MoO3. It is noticed
that the endothermal shifts in the DTA baseline of the
doped sample are shifted to lower temperature range
(750–850°C) instead of (800–900°C) for pure sample,
which indicates the acceleration in glass transition of the
gel resulting in minimizing the crystallization tempera-
ture of l-cordierite in doped cordierite sample as illus-
trated in Fig. 2.42 Such thermal behavior evinces the
acceleration of crystallization rate resulting in decreasing
the average crystallite size as indicated before in Table I.
The FT-IR absorption spectra of the cordierite sam-
ples annealed at 1300°C for 3 h are shown in Fig. 3.
The characteristic peaks of a-cordierite are found at
Table II. Ionic Radii, Valence State, and Electronic Configuration of the Cations Replaced in Cordierite
Metal Electronic
ion Valence configuration
3+
Al 3+ 2p6
Mo6+ 6+ 4p6
2014
Fig. 3. FT-IR spectra of the produced cordierite nanopowders
annealed at 1300 °C for 3 h.
1112, 1057, 923, 825, 712, 634, 610, 528, 466, and
432 cm-1 for the pure sample. In addition, all the spec-
tra obtained for the doped samples are similar in their
overall envelope. However, a consistent loss of resolution
with Mo6+ ions insertion is apparent. This trend is
strongly observed at low concentration of MoO3 (5%),
which show considerably less fine details in their infrared
spectra than those shown at higher MoO3 concentrations
(10 and 15%). Such obtained FT-IR results confirmed
the XRD results for the investigated samples. Table II
reveals the physical and coordination characteristics of
the substituted metal ions.
Figure 4 represents SEM images of the polished sur-
face of cordierite pellets containing 0.0–15% MoO3 sin-
tered at 1300°C for 5 h. The pure sample has highly
porous fluffy and spongy surface. On the other hand,
the incorporation of Mo6+ ion to the cordierite structure
leads to increase the interconnected micropores and cap-
illaries to be distributed as large group collections, partic-
ularly at 5 and 10% MoO3. Meanwhile, increasing the
amount of Mo6+ ions up to 15% leads to smaller pores
sizes and more surface homogeneity, which becomes
similar to that morphology of the pure sample. These
Ionic radii (pm)
Tetrahedral Octahedral
site site
(4-coordinate) (6-coordinate)
39 53.5
55 73
www.ceramics.org/ACT Molybdenum-Doped Cordierite Ceramics 5

(a) (e)

(b) (f)

(c) (g)

(d) (h)

Fig. 4. SEM micrographs of cordierite ceramics at various Mo6+ ion contents sintered at 1300 for 5 h (a, e) pure sample, (b, f) 5% Mo6+,
(c, g) 10% Mo6+, (d, h) 15% Mo6+ content.

observations in the surface texture of cordierite ceramics
are in consistency with their bulk density and porosity
measurements as will be deeply discussed in the next sec-
tion.
Figure 5 shows the variations in bulk density and
total porosity of the cordierite samples with change in
the Mo6+ ion content (0.0–15%). It is found that the
bulk density of doped cordierite sample with 5% Mo6+
ion decreased by 22.8% of the theoretical density (2.6 g/
cm3), while the total porosity increased from 70 to
76.8%. The increase in the porosity of cordierite ceram-
ics may be related to the premature melting of MoO3
6 International Journal of Applied Ceramic Technology—Sanad, et al. 2014

78 0.85 Table III indicates the effect of Mo6+ ion content

on both sintering and mechanical properties of sintered
0.80
76 cordierite samples. It is observed that the shrinkage is

Bulk denisty (gm cm-1)

slightly affected by Mo6+ ion insertion, which evinces the
Total porosity (%)

74
72
70
68
0 5 10
6+
Mo ion Content (%)
Fig. 5. Effect of Mo6+ ion content on the sintering properties
(bulk density and total porosity) of cordierite nanocomposites
sintered at 1300 for 5 h.
particles at 800°C forming localized hot zones of higher
temperatures, which dissolute some cordierite particles
resulting in large pore sizes. Increasing the amount of
MoO3 up to 15% leads to increase the bulk density by
2.5% and decrease the total porosity to 69.2%. This is
because at high concentrations of MoO3, one part is
incorporated in the crystal lattice itself and the other part
adsorbed on the surface of cordierite particles as eluci-
dated by the detection of MoO3 phase from XRD
results.
0.75
vacancies occupation by Mo6+ ions. The mean values of
measured microhardness of cordierite ceramic pellets are
0.70
depicted in Table III. It is found that the hardness value
0.65
of pure sample is dropped from 7.13 GPa to minimum
value of 2.33 GPa at 10% Mo6+ ion content. The
0.60 obtained results are coherently accompanied to the pro-
nounced changes in the porosities of sintered samples.
0.55 Table IV depicts the effect of Mo6+ ion content on
15
the electrical resistivity (q) of cordierite samples. It is
known that in ceramic materials, the presence of lattice
defects, such as vacancies and interstitials in the struc-
ture, reduces its DC resistance and vice versa.43 It is
obvious that the electrical resistivity (q) of cordierite
ceramics decreased by 95.9% with increasing the Mo6+
ion amount up to 15%. Such observation of decreasing
the insulating properties by addition of MoO3 is
assigned to the increase in the total porosity, which coin-
cided with most of published papers.
The dielectric properties of materials are used to
describe electrical energy storage, dissipation, and energy
transfer. Therefore, dielectric relaxation of molybdenum-
doped cordierite ceramics is studied by the variation in
the real part of permittivity over a wide range of fre-
quencies (1 MHz–3 GHz) as illustrated in Fig. 6.

Table III. Effect of Mo6+ ion Content on Sintering and Mechanical Properties of Mo-doped Cordierite Ceramics
Sintered at 1300°C for 5 h
Total Mechanical
Mo6+ ion Bulk density porosity Shrinkage hardness
content (%) (g/cm3) (%) (%) (GPa)
0 0.79 70 22.64 7.13
5 0.61 76.8 21.15 4.63
10 0.75 71.5 22.22 2.33
15 0.81 69.2 21.99 3.86

Table IV. Effect of Mo6+ ion Content on DC and AC Electrical Properties of Mo-Doped Cordierite Ceramics
Sintered at 1300°C for 5 h
Dielectric permittivity (έ) Loss tangent (tan d)
Mo6+ ion DC resistivity q
content (%) (O cm) At 1 MHz At 1 GHz At 1 MHz At 1 GHz
0 16.56 9 109 21.8 34.3 0.000 0.019
5 1.61 9 109 20.9 38.1 0.008 0.030
10 5.47 9 109 17.9 32.5 0.015 0.032
15 0.68 9 109 20.2 39.6 0.001 0.061
www.ceramics.org/ACT Molybdenum-Doped Cordierite Ceramics 7

0.07 0.020

0.06

Dielectric loss tangent (1 MHz)

Dielectric loss tangent (1 GHz)
0.016

0.05
0.012

0.04

0.008
0.03

0.004
0.02

0.01 0.000
0 5 10 15
6+
Mo ion Content (%)

Fig. 6. Variation in the dielectric permittivity versus the fre-
quency at different Mo6+ ion contents in cordierite ceramics. Inset
change in dielectric loss versus the frequency at different Mo6+ ion
contents.
It is known that the dielectric permittivity of the
sample strongly depends on its density.7,44,45 Thereby,
the higher the density, the higher the dielectric permit-
tivity. In spite of the sample density, the phase constitu-
ents or the content of a-cordierite is one of the
important factors affecting the dielectric permittivity. In
other words, with increasing the a-cordierite content, the
dielectric permittivity of the sintered sample is
decreased.7,46 In addition, the dielectric loss is propor-
tional to the magnitude of porosity in the sintered sam-
ples.7,45,47
Figure 7 shows the effect of Mo6+ ion content on
dielectric permittivity (έ) of sintered cordierite samples at
1300°C for 5 h. Based on the above facts, it is clearly
noticed that dielectric permittivity (έ) values of doped
42
Fig. 8. Effect of Mo6+ ion content on dielectric loss tangent loss
(tan d) of sintered mullite samples at 1300 °C for 5 h.
cordierite samples decreased than that of the pure cordie-
rite sample, especially in the radiowave frequency region
(1 MHz). Meanwhile, the obtained increase in the values
of dielectric permittivity (έ) at higher frequency range
(1 GHz) can be attributed to high periodical reversal of
field at the interface, which reduces the contribution of
charge carriers to the dielectric permittivity and finally it
saturates at higher frequencies giving rise to dielectric
permittivity.
On the other hand, the change in the dielectric loss
tangent (tan d) with Mo6+ ion content is plotted in
Fig. 8. It is noticed that the dielectric loss (tan d) is line-
arly increased with increasing in Mo6+ ion content at
both frequency ranges (1 MHz and 1 GHz). The
increase in values of dielectric loss (tan d) is due to the
higher introduction of lattice defects to the host lattice
by Mo6+ ions as well as the production of oxygen ion
vacancies more than that found with the pure cordierite
composition.40,41,48 Table IV summarizes the obtained
22.0
DC and AC electrical measurements of all cordierite
21.5 samples sintered at 1300°C for 5 h. In general, such sur-
Dielectric permittivity (1 MHz)

prising investigation exhibits better utilization for the

Dielectric permittivity (1 GHz)

40 21.0

20.5 cordierite-sintered samples to be conducted under both

38 20.0 continuous radiowave and microwave frequency ranges.
19.5

36 19.0
Conclusion
18.5

34 18.0
In a nutshell, the results can be summarized as the
17.5 following:
32 17.0 1. The XRD analysis results revealed that the a-cordie-
0 5 10 15
6+
rite phase is the predominant phase with addition of
Mo ion Content (%)
10–15% Mo6+ ion, while the addition of 5% Mo6+
Fig. 7. Effect of Mo6+ ion content on dielectric permittivity (έ) ion causes structure modification and the sapphirine
of sintered cordierite samples at 1300 °C for 5 h. becomes the predominant phase.
8 International Journal of Applied Ceramic Technology—Sanad, et al.
2. Thermal analysis of a-cordierite showed that the
crystallization temperatures of l-cordierite and a-cor-
dierite are clearly shifted to lower temperatures with
Mo6+ ion doping.
3. The FT-IR spectra of doped cordierite samples
showed similar overall envelope with lower transmit-
tance than the pure cordierite sample.
4. The surface morphological investigation of cordierite
ceramic samples indicated the development of the
porosity with Mo6+ intercalation, which changes the
microporous structure into a macroporous continu-
ous structure by obtaining large and small intercon-
nected pores.
5. The bulk density of 15% Mo6+ ion-doped cordierite
is 0.81 g/cm3, which is slightly lower than that of
the pure samples 0.79 g/cm3. The maximum total
porosity is achieved by doping 5% Mo6+ ion, which
equal 76.8%.
6. The electrical resistivity of was decreased with
increasing Mo6+ ion content as a result of increasing
the lattice defects and total porosity.
7. Doped cordierite sample with 10% Mo6+ ion
achieved the minimum values of dielectric permittiv-
ity (έ), which equal 17.9 at 1 MHz and 32.5 at
1 GHz.
8. The resultant porous Mo6+ ion-doped cordierite
ceramics have the advantages to be used either in
electronic packaging or catalytic filtering applications.
References
1. F. A. C. Oliveira and J. C. Fernandes, Ceram. Int., 28 79–91 (2002).
2. R. Goren, H. Gocmez, and C. Ozgur, Ceram. Int., 32 407–409 (2006).
3. R. Goren, C. Ozgur, and H. Gocmez, Ceram. Int., 32 53–56 (2006).
4. J. R. Gonzalez-Velesco, R. Ferret, R. Lopez-Fonseca and M. A. Gutierrez-
Ortiz, Powder Technol., 153 34–42 (2005).
5. C. Ghitulica, E. Andronescu, O. Nicola, A. Dicea, and M. Birsan, J. Eur.
Ceram. Soc., 27 711–713 (2007).
6. E. Yalamac and S. Akkurt, Ceram. Int., 32 825–832 (2006).
7. M. A. Camerucci, G. Urretavizcaya, M. S. Castro, and A. L. Cavalieri,
J. Eur. Ceram. Soc., 21 2917–2923 (2001).
8. D. U. Tulyaganov, M. E. Tukhtaev, J. I. Escalante, M. J. Ribeiro, and J. A.
Labrincha, J. Eur. Ceram. Soc., 22 1775–1782 (2002).
9. G. Chen, J. Alloy. Compd., 455 298–302 (2008).
2014
10. Z. Acimovic, L. Pavlovic, L. Trumbulovic, L. Andric, and M. Stamatovic,
Mater. Lett., 57 2651–2656 (2003).
11. A. Yamuna, S. Honda, K. Sumita, M. Yanagihara, S. Hashimoto, and H.
Awaij, Micro. Meso. Mater., 85 169–175 (2005).
12. P. Rohan, K. Neufuss, J. Matejicek, J. Dubsky, L. Prchlik, and C. Holzgart-
ner, Ceram. Int., 30 597–603 (2004).
13. S. Tamborenea, A. D. Mazzoni, and E. F. Aglietti, Thermochim. Act, 411
219–224 (2004).
14. M. A. Camerucci, G. Urretavizcaya, and A. L. Cavalieri, J. Eur. Ceram. Soc.,
21 1195–1204 (2001).
15. R. Morrell, Proc. Br. Ceram. Soc., 28 53–71 (1979).
16. M. Majumder, S. Mukhopadhyay, O. Parkash, and D. Kumar, Ceram. Int.,
30 1067–1070 (2004).
17. T. Okamura and T. Kishino, Jpn. J. Appl. Phys., 37 5364–5366 (1998).
18. M. D. Karkhanavala and M. D. Hummel, J. Am. Ceram. Soc., 36 389–392
(1953).
19. G. V. Gibbs, Am. Mineral., 51 1068–1087 (1966).
20. A. Putnis, Contrib. Mineral. Petrol., 74 135–141 (1980).
21. E. P. Meagher and G. V. Gibbs, Can. Mineral., 15 43–49 (1977).
22. D. S. Goldman, G. R. Rossman, and W. A. Dollase, Am. Mineral., 62
1144–1157 (1977).
23. K. R. Selkregg and F. D. Bloss, Am. Mineral., 65 522–533 (1980).
24. G. Pourroy and S. Angelov, J. Mater. Sci., 27 6730–6734 (1992).
25. Z. M. Shi, K. M. Liang, and S. R. Gu, Mater. Lett., 51 68–72 (2001).
26. M. A. Villegasa and J. Alarco′ n, J. Eur. Ceram. Soc., 22 487–494 (2002).
27. Z. M. Shi, X. Bai, and X. F. Wang, Ceram. Int., 32 1253–1257 (2006).
28. G. Chen, J. Mater. Sci.: Mater. Electron., 18 492–498 (2007).
29. H. Ikawa, T. Otagiri, O. Imal, M. Suzuki, K. Urabe, and S. Udagawa,
J. Am. Ceram. Soc., 69 469–481 (1986).
30. B. Piriou, Y. F. Chen, and S. Vilminot, Eur. J. Solid State Inorg. Chem., 32
2191–2197 (1995).
31. S. Mei, J. Yang, and J. M. F. Ferreira, J. Eur. Ceram. Soc., 20 483–487
(2000).
32. W. Wei-qing, R. Yu-zhong, and Y. Yan, Chinese J. Struct. Chem, 24 483–
487 (2005).
33. E. M. A. Hamzawy and A. F. Ali, Mater. Character, 57 414–418 (2006).
34. J. E. Alfonso, R. Garzon, and L. C. Moreno, Physica B: Conden. Matter, 407
4001–4004 (2012).
35. M. S. Oh, et al. , J. Vac. Sci. Tech. A., 30 31501–31505 (2012).
36. Y. Pan and M. E. Fleet, Can. Precambrian Res., 74 73–79 (1995).
37. W. H. Peck and M. S. Smith, Can. J. Earth Sci., 42 1815–1828 (2005).
38. M. M. Raith, R. Rakotondrazafy, and P. Sengupta, J. Metamorph. Geol., 26
647–667 (2008).
39. S. C. Kruckenberg and D. L. Whitney, J. Metamorph. Geol., 29 425–444 (2011).
40. I. S. A. Farag, M. F. Kotkata, M. M. Selim, I. K. Battisha, and M. M.
El- Rafaay, Egyptian J. Solids, 27 233–243 (2004).
41. I. S. F. Ahmed, I. K. Battisha and M. M. El-Refaay, Indian J. Pure Appl.
Phys., 43 446–458 (2005).
42. G. A. Merkel, US Patient, 6 813 B1 (2002).
43. D. W. Richerson, Modern Ceramic Engineering: Properties, Processing, and Use
in Design, Marcel Dekker, Inc., New York, 1982.
44. L. S. Chen and S. L. Fu, Jpn. J. Appl. Phys., 31 3917–3921 (1992).
45. M. M. S. Sanad, M. M. Rashad, E. A. Abdel-Aal, and M. F. El-Shahat,
Ceram. Int., 39 1547–1554 (2013).
46. J.-M. Wu and H.-L. Huang, J. Mater. Res., 15 222–227 (2000).
47. S. J. Penn, et al. , J. Am. Ceram. Soc., 80 1885–1888 (1997).
48. A. K. Jonscher, Dielectric Relaxation in Solids, Chelsea Dielectrics Press, Lon-
don, 1982.