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CERAMICS
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Ceramics International 42 (2016) 5045–5052
www.elsevier.com/locate/ceramint

Effect of Fe2O3 content on the electrical resistivity of aluminous porcelain

applied to electrical insulators
D.H. Pivaa,b,n, R.H. Pivaa, J. Venturinib, J. Ramonb, V. Caldasb, M.R. Morellia, C.P. Bergmannb
a
Federal University of São Carlos, PPG-CEM, São Carlos, SP, Brazil
b
Federal University of Rio Grande do Sul, PPGE3M, Porto Alegre, RS, Brazil
Received 14 October 2015; received in revised form 28 November 2015; accepted 1 December 2015
Available online 10 December 2015

Abstract

In general, the presence of Fe2O3 is claimed to reduce the insulating behavior of electrical porcelains, even if a rigorous proof has not yet been
reported. The purpose of this study was to evaluate the real influence of Fe2O3 content on the electrical resistivity of a standard aluminous
porcelain widely used in insulators. The electrical resistivity for the composition with 3 wt% Fe2O3 was higher than those found for standard
aluminous porcelain, which was discussed in terms of the concentration of glassy and mullite phases. A reduction in the electrical resistivity was
only observed in porcelain samples containing over 3 wt% Fe2O3. The presence of hematite phase was considered responsible for this reduction.
These results suggest that low-cost raw materials with greater Fe2O3 content should not extensively affect the insulating properties and could
therefore be used in manufacturing aluminous electrical porcelain.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Dielectric properties; Aluminous porcelain; Impedance spectroscopy; Fe2O3; Electrical insulators

1. Introduction Usually, electrical porcelains are composed of quartz,

Triaxial porcelains have been used for decades as electrical
insulators in power transmission and distribution lines due to
their dielectric properties (e.g. high resistivity, low dielectric
loss), high mechanical strength and their ability to maintain
these properties for a long time under severe conditions, such
as humid, hot and saline environments [1]. However, due to
the elevated costs of the manufacturing process and pure raw
materials [2–4], porcelains have become less attractive for
applications as electrical insulators, whereas some alternative
products such as polymers, glasses and composite insulators
[2,5–7] have come under consideration as low-cost alternative
materials. Therefore, research on the reduction of production
costs is an urgent task for porcelain insulator companies.
n
Correspondence to: Laboratory of Ceramic Synthesis and Formulation,
Federal University of São Carlos, São Carlos, SP, Brazil.
Tel.: þ 55 16 3351 8508.
E-mail address: diogenespiva@gmail.com (D.H. Piva).
feldspar and clay [8]. Frequently in high voltage porcelain,
quartz is replaced by calcined alumina in order to increase the
mechanical strength of the sintered body [9]. When adequately
heat treated, these raw materials form a glassy matrix contain-
ing quartz/α-alumina, mullite and remaining porosity [10].
Since the presence of these phases strongly affects the
properties of electrical porcelains, a proper selection of raw
materials is of paramount importance for the definition of the
characteristics of the final product. Currently, a prerequisite for
selecting raw materials for porcelain insulators is a low
concentration of transition metal oxides such as TiO2, Fe2O3,
Cr2O3 [1,11]. It is well known that the presence of such metal
oxides in ceramic materials changes their electrical behavior
causing mainly an increase in condutivity due to small polaron
hopping conduction mechanisms [12]. In fact, recently, several
investigations have focused on determining the correlations
between composition and electrical properties of electrical
porcelains [8,13–18]. However, studies on the electrical

http://dx.doi.org/10.1016/j.ceramint.2015.12.016
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
5046 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052

resistivity as a function of Fe2O3 are scarce in the literature
and, to our knowledge, very few studies on the acceptable limit
of this impurity have ever been reported [19]. Since the
presence of these impurities in pastes for porcelain production
has a practical effect in decreasing firing temperature [20] and
reducing the cost of raw materials, the use of raw materials
with higher Fe2O3 concentrations should lead to great eco-
nomic benefits.
The goal of this study is to assess the influence of the Fe2O3
content on the electrical resistivity of aluminous porcelain.
Impedance spectroscopy (IS) was used for the electrical
caracterization along with the Rietveld refinement method to
quantify the phase contents in the porcelain bodies. Micro-
structural characteristics were investigated using Scanning
electron microscopy (SEM).
2. Experimental
Four different mixtures were prepared by adding increasing
amounts of Fe2O3 to a standard aluminous porcelain composi-
tion containing 30% feldspar, 30% kaolin, and 40% calcined
alumina. The compositions of the reference and Fe2O3-
containing aluminous porcelains prepared in this study, as
well as batch names, are given in Table 1. The chemical
composition of the formulations is given in Table 2. In order to
prepare the mixture of powders, the raw materials were dry-
mixed using a ball mill, moistened by spraying with distilled
water (5.0 wt%) and sieved through a 250-mesh sieve in order
to reduce the size of the agglomerates prior to compaction.
Pellet-shaped samples (10 mm in diameter and 2 mm in length)
were prepared via uniaxial pressing under 125 MPa. Samples
were subsequently dried at 110 1C until the moisture content
was reduced to less than 0.5%. Based on thermal analysis
Table 1
Composition (in wt%) and batch names of pure and Fe2O3-containing alumina
porcelains.
Raw materials Formulations
P0Fe P3Fe P5Fe
Calcined alumina 40.0 38.8 38.0
Kaolin 30.0 29.1 28.5
Feldspar 30.0 29.1 28.5
Hematite 0.0 3.0 5.0
results, [19] the samples with compositions P0Fe, P3Fe, P5Fe
and P8Fe were fired at 1300, 1250 and 1200 1C (for the last
two compositions) respectively, in an electric furnace. The
heating and cooling rates for all samples were 10 1C min  1
and soak times were 2 h.
The crystalline phases of fired samples were identified using
XRD (PANalytical, X'Pert PRO MPD) equipped with a Cu-Kα
radiation source (1.5406 Å) operated at 40 kV and 40 mA.
XRD analyses of powdered samples (sieved o 45 μm) were
carried out at 10r 2θ r 801 at a scanning speed of 0.051/min.
Quantitative phase analyses of the samples were performed
using XRD data and Rietveld refinement. The powdered
samples were mixed with 15 wt% zincite as an internal
standard. For the Rietveld refinement the XRD data was
collected using a MiniFlex 300 Rigaku diffractometer
equipped with Cu-Kα source, working at 40 kV and 15 mA.
The scans were performed between 10 and 801 (2θ) with step
size of 0.021 and a counting time of 6 s per step. Crystalline
and amorphous content quantification was performed using the
GSAS package [21] and its graphical interface EXPGUI [22].
The amorphous fraction was calculated following the method
described by Gualtieri et al. [23]. The source of structure data
was the International Crystal Structure Database (ICSD) [24].
SEM images were obtained using an FEI Magellan 400 L
with an accelerating voltage of 25 kV. For the SEM analysis
the samples were successively polished with 600 and 1200
grade SiC papers, etched for 2 min in a 10% HF solution and
subsequently gold coated.
For the electrical measurements, the surfaces of the sintered
discs were polished and covered with Pt paste on both sides of
the sample as electrode. Samples were thereafter heat treated at
400 1C for 15 min in order to ensure good contact between the
conductive Pt layer and the surface of the sample. Impedance
Spectroscopy (IS) measurements were carried out using an
impedance analyzer (Metrohm Autolab PGSTAT30) applying
a sinusoidal potential of amplitude 0.5 V at a frequency range
of 10  1–106 Hz and recording 5 data points per frequency
decade. The measurements were performed initially at 251 and
subsequently between 300 and 700 1C. All measurements were
P8Fe
performed in air atmosphere with a temperature interval
between each impedance measurement of 50 1C. The heating
36.8 rate was 10 1C/min. In order to reduce the thermal fluctuations
27.6 in the sample the temperature was kept fixed for 5 min before
27.6
8.0
each measurement. The analysis of the spectra using Autolab
NOVA fitting software provided information such as the

Table 2
Chemical composition of formulations investigated in this work [19].

Formulation Chemical composition (wt%)

Al2O3 SiO2 Fe2O3 CaO Na2O K2O MnO MgO TiO2 P2O5

P0Fe 57.38 38.84 0.29 0.26 1.74 1.20 0.01 0.03 0.08 0.17
P3Fe 55.60 37.63 3.39 0.26 1.68 1.17 0.01 0.03 0.08 0.17
P5Fe 54.41 36.83 5.44 0.25 1.65 1.14 0.01 0.03 0.08 0.16
P8Fe 52.64 35.63 8.52 0.24 1.59 1.11 0.01 0.03 0.07 0.16
 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052
resistance (R) and capacitance (C) of the sample. The
resistivity (ρ) and activation energy (Ea) are obtained as
follows:
A:R
ρ¼ ð1Þ
l P0Fe
 
ρ
E a ¼ kTln ð2Þ
ρ0
where A and l are the area and thickness of the sample,
respectively, and ρ0, k and T are pre-exponential constant,
Boltzmann constant (8.62  10  5 eV) and absolute tempera-
ture, respectively.
3. Results and discussion
3.1. Phase characterization
XRD results reveal that α-alumina, quartz, and mullite are the
three main crystalline phases present in all sintered porcelain.
However, when the Fe2O3 content reached over 3 wt% a fourth
phase, hematite, was also detected. Fig. 1(a) shows the XRD
pattern in the 30–401 (2θ) range obtained from the powdered
samples. The two peaks corresponding to the hematite phase
appeared in the XRD pattern of the P5Fe sample and the intensity
of these peaks increased for the P8Fe samples. According to
McConville and Lee [25], hematite can remain present in Fe2O3-
containing stoneware after firing at 1300 1C, or it may recrystallize
during the cooling from the liquid phase when the latter is saturated
with Fe ions. Since no extra peak is observed for the P3Fe sample,
we can conclude that for this composition all Fe2O3 has dissolved
in the melt phase during the sintering and formed a solid solution
with the other phases.
The Rietveld plot for the sample P0Fe is shown in Fig. 1(b),
whereas the results of the Rietveld analysis for all the samples
are shown in Table 3. For all refined patterns, the Rwp value lies
around 15%, indicating good fits [26]. As can be seen in Table 3,
Fig. 1. (a) X-ray diffraction pattern of the formulations showing the presence
of the hematite phase peaks (H) for the Fe2O3-containing formulation higher
than 3 wt% and (b) Rietveld refinement plots for the sample P0Fe with zincite
added as an internal standard to perform amorphous quantitative phase
analysis. (markers of the peaks of each crystalline phase are: (A) α-alumina,
(M) mullite, (Q) quartz, and (Z) zincite).
5047
Table 3
Rietveld refinement for aluminous porcelain containing different amounts of
Fe2O3.
Sample α-Alumina Mullite α-Quartz Hematite Amorphous phase
40.5 14.9 12.8 – 31.8
P3Fe 39.0 16.8 6.5 – 37.7
P5Fe 38.2 15.8 7.2 2.2 36.6
P8Fe 37.1 16.0 6.9 6.0 34.0
the α-alumina content does not change in relation to the initial
formulations (see Table 1). This unaltered concentra-
tion of α-alumina is an expected result since the sintering
temperature of the porcelains herein studied are o1300 1C and
α-alumina grains have a very low dissolution rate in feldspathic
glass at temperatures up to 1450 1C [27]. The Rietveld
refinement results show that the addition of Fe2O3 leads to a
reduction in quartz content from 12.8 wt% to 6.9 wt% for the
samples P0Fe and P8Fe, respectively. The amount of amor-
phous phase increased in formulations containing Fe2O3, reach-
ing a maximum for the P3Fe sample (37.7 wt%). Previous
authors have demonstrated that Fe2O3 induces further liquid
phase formation during the sintering of clays [28]. Furthermore,
the densification process of porcelain bodies has been found to
be enhanced in the presence of Fe2O3 [19]. This phenomenon
can be explained by a reduction in the temperature of formation
of the first liquid phase. Moreover, iron oxide acts towards
reducing the viscosity and surface tension of the formed liquid,
improving the contact between grain and melt phase and
increasing dissolution of quartz particles. The reduction
observed in the fraction of amorphous phase in the samples
P5Fe and P8Fe can be attributed to their lower concentration of
feldspar (substituted by Fe2O3 in the initial formulation) and
lower sintering temperature. The addition of Fe2O3 is accom-
panied by an increase in the produced amount of mullite for all
compositions (see Table 3). This result displays the effect of
iron oxide as a mineralizer, which had been observed previously
by other authors [29,30]. The role of Fe in mullite formation
was studied by Schneider et al. [29] who showed that Fe3 þ can
replace Al3 þ in the A1O6 mullite octahedra. Therefore, the
reported results suggest that dissolution of the iron oxide in
the molten phase during sintering provided large quantities of
Fe3 þ ion, thus favoring the nucleation of mullite in the Fe2O3-
containing porcelain.
3.2. Microstructure
SEM images of the etched P0Fe, P3Fe and P8Fe samples are
shown in Fig. 2. A dense microstructure with a few closed
porosity is observed for all the compositions (Fig. 2(a)–(c)).
However, the closed porosity concentration decreased in the
samples containing Fe2O3 due to a more pronounced devel-
opment of liquid phase, which leads to decreasing porosity and
enhances the densification process [31]. Rietveld refinements
(Table 3) show that formulations containing Fe2O3 have a
greater fraction of amorphous phase, a consequence of the
5048 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052
Fig. 2. SEM images of the aluminous porcelain containing different concentrations of Fe2O3. (a) and (d) P0Fe, (b) and (e) P3Fe, (c) and (f) P8Fe. (G: glassy phase,
Q: quartz, M: mullite, H: hematite, P: porosity, C: clay relict.)
Fig. 3. Impedance spectra for all samples measured at 25 1C. Straight lines
represent the fitted curve.
higher concentration of liquid phase during firing. Unlike
samples P5Fe (not shown) and P8Fe (Fig. 2(c)), an iron-rich
region (white contrast) was not detected in the sample P3Fe
(Fig. 2(e)). This observation confirms that hematite dissolved
completely and formed a solid solution with the other phases
as previously indicated by Rietveld refinement. The micro-
structure analysis further revealed that quartz grains were
larger and rather angular in nature in the sample P0Fe (Fig.
2(a), inside) while they tend to become smaller and round in
specimens with increasing Fe2O3 content (Fig. 2(b) and (c),
inside). This result evidences the aggressive effect of Fe-
containing liquid phase in the process of quartz dissolution
during firing.
Higher magnification micrographs for the samples P0Fe,
P3Fe and P8Fe are shown in (Fig. 2(d)–(f)), respectively.
Acicular secondary mullite crystals are clearly observed in all
the samples. In the P0Fe sample (Fig. 2(d)), secondary mullite
was formed mainly in regions in which the liquid phase was
well mixed with clay relict, which is in accordance with the
observations of Iqba and William [10]. However, in the Fe2O3-
containing samples (Fig. 2(e) and (f)), mullite crystals were
observed in higher concentrations in the glassy phase. This
result suggests that the increase in mullite percentage in Fe2O3-
containing compositions determined by Rietveld refinement
(Table 3) takes place mainly due to the secondary mullite
crystallization from the melt phase.
3.3. Impedance analysis
The complex impedance plots ( Z″ versus Z0 ) at room
temperature for all the samples is shown in Fig. 3. It can be
seen that all spectra exhibit a tendency toward forming a single
semicircle. The intercept of the semicircles on the real axis
increases for the sample P3Fe and then decreases for the P5Fe
and P8Fe samples, demonstrating that the electrical resistivity
decreases for formulations containing over 3 wt% of Fe2O3.
Indeed, while the sample P0Fe displayed a ρ  8  1011 Ω cm,
the sample P3Fe exhibited a ρ 1.1  1012 Ω cm. For the P5Fe
and P8Fe samples, the ρ values were of 7.6  1011 and
7.2  1011 Ω cm, respectively. Although only the sample
P3Fe exibited ρ values Z 1012 Ω cm, falling in the category
of good insulators [1], all observed ρ values are in agreement
 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052
Fig. 4. Impedance spectra for the samples (a) P0Fe, (b) P3Fe, (c) P5Fe and
(d) P8Fe at 550 1C. Cb, Ccg and Ce are the true capacitances (in F cm  2) of
bulk, crystal-glass interface and electrode, respectively. (The arrow shows the
direction of increasing frequency.)
with those found in literature for electrical aluminous porce-
lains [32].
IS formalism enables us to separate the contribuitions of the
various electroactive regions of a material [33]. However, the
impedance spectra at room temperature (Fig. 3) precluded the
identification of the fundamental contributions of each phase to
the overall electrical behavior of the porcelain. According to
previously reported impedance measurement results [34,35] a
single depressed semicircle corresponding to the continuous
glassy matrix is expected in highly vitrified materials such as
porcelain. Nevertheless, the complex impedance plots measured
5049
at high temperature (550 1C) in (Fig. 4(a)–(d)) show two well-
defined semicircles (at high and intermediate/low frequency
region) for the samples P0Fe, P3Fe and P5Fe. In addition to the
high and intermediate/low frequency semicircles, a third semi-
circle in the low frequency region for the sample P8Fe is also
observed. Each semicicle in an impedance spectrum consists of
a resistance R and a constant phase element (Q). The true
capacitance values C of the semicircles at 550 1C were obtained
from the equation C¼ (R1  nQ)1/n, where n is an empirical
exponent [36]. The true capacitance values of the distributed
responses were thus calculated to be in the order of 10  12 F
cm  2 for the higher frequency response and 10  9 F cm  2 for
the intermediate/low frequency response. According to Irvine et
al. [37], low capacitances are usually associated to phases with
large volumetric fractions (bulk), while higher capacitances are
commonly related to smaller regions, e.g. grain boundaries or
interfacial regions. Porcelains typically consist of three different
electroactive regions, i.e., the glass matrix, crystalline phases,
and crystal-glass interface. Nevertheless, only two semicircles
have been found in the impedance spectra in Fig. 4. According
to Rodrigues et al. [38] a mixed contribution in impedance
responses may arise if the phases present have similar dielectric
constants, as in the case of the phases present in porcelain
materials [1]. Therefore, from the analysis of the capacitances, it
is reasonable to assume that the first semicircle at high
frequency originated from the bulk (glassyþ crystalline phases)
response (RbQb) and the second semicircle at intermediate/low
frequency from the crystal-glass interface response (RcgQcg).
The third semicircle in the low frequency range for the sample
P8Fe was atributed to the resistence of the electrode phase
(ReQe) due to its high capacitance ( 10  7 F cm  2). The
resistive contribution of the electrode is small for all composi-
tions and appears only at high temperature when Rcg is low.
Moreover, the additional increase of Z in the lowest frequencies
for all samples represents the polarization at the electrode–
electrolyte interface [33].
As previously observed in the impedance spectra at room
temperature (Fig. 3), ρ increases for the sample containing
3 wt% Fe2O3 and decreases for the formulations containing
5 and 8 wt% Rb and Rcg in the sample P3Fe were larger than
those of P0Fe. Indeed, whereas P0Fe shows Rb and Rcg values
of 15  103 and 6.8  103 Ω cm, respectively,sample P3Fe
shows Rb and Rcg values of 17  103 and 10  103 Ω cm,
respectively. The Rietveld refinement results in Table 3 show
that the main difference between samples P0Fe and P3Fe was
the higher mullite and glassy phase content and smaller quartz
content present in the sample P3Fe. The larger glassy phase
fraction in sample P3Fe is considered to be responsible for the
increased Rb. The results are in agreement with those obtained
by Chaudhuri et al. [13] who reported that the resistivity of
porcelain increases with the growth of their glassy phase
fraction. Moreover, sample P3Fe showed greater Rcg than
P0Fe. Ribeiro et al. [35] suggested that an increase in mullite
content is the main factor contributing towards the improve-
ment of electrical resistivity of mullite-based ceramics, since
mullite particles allow larger interfacial contact areas with the
vitreous phase and thus a larger cross-section for blocking
5050 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052

Fig. 5. Frequency dependence of the imaginary part of the impedance ( Z00 ) for all samples at different temperatures.

effect at the interfaces. The decrease in Rb and Rcg for the

samples P5Fe and P8Fe can be attributed to the presence of
nonsolubilized highly-conductive hematite phase. According
to Harizanova et al. [39] the presence of hematite crystals in
glasses creates conduction paths and thus contributes to higher
conductivity. Furthermore, since the hematite–glass interface is
much more conductive than the quartz-, α-alumina- and
mullite–glass interfaces, we can expect that a substantial
increase in the hematite content in the samples P5Fe and
P8Fe would create a preferential electrical-transport pathway,
hence decreasing Rcg.
Fig. 5 shows the variation of the imaginary part of
impedance (–Z00 ) as a function of frequency at selected
temperatures. The curves show the existence of two distinct
relaxation mechnisms for the samples P0Fe, P3Fe and P5Fe. A Fig. 6. Activation energy and temperature dependence of the resistivity of
broad peak can also be observed at the spectra of sample P8Fe, aluminous. porcelain samples displayed in Arrhenius-type plot. Straight lines
corresponding to a contribution from a distinct relaxation represent the fitted Arrhenius dependence.
process. The first peak (for frequency  105 Hz) arises due
to the relaxation of the glassy and crystalline phases, whereas a
second peak (  104 Hz) is produced by the crystal-glass of Fe2O3 on the electrical resistivity of the samples, the ρ-value
interface relaxation. Fig. 5 shows that the all  Z00 maxima followed the order ρ-P3Fe 4 ρ-P0Fe 4ρ-P5Fe4 ρ-P8Fe for
decrease with increasing temperature, demostrating that the all studied temperatures. The resistivity of all samples
samples are becoming more conductive with increasing decreases with rising temperature, showing that the condution
temperature as consequence of the decrease of bulk (glassy processes of porcelain are thermally activated, as previously
and crystalline phases) and crystal-glass interface resistances. observed in Fig. 5. The results of resistivity herein reported
Additionally, the frequency of the high relaxation peak shifts corroborate previous results [19] in which minima of dielectric
towards higher frequencies with the increase in temperature. constant were observed for the composition containing 3 wt%
This shift arises due to the decrease in relaxation times, Fe2O3, since polarization and conduction are integrated into a
indicating that the charge carrier mobility is increasing with single continuous process [41]. The relative efficiency of
the rise in temperature [40]. Fe2O3 in diminishing the electrical resistivity of aluminous
porcelain can be estimated from the Ea values, calculated from
Eq. (2). The activation energy values decreased with the
3.4. Electrical resistivity presence of Fe2O3. In fact, Ea goes from 1.2 eV for the sample
P0Fe to 0.9 eV for the sample P8Fe. The tendency of
The resistivity of the samples extracted from the impedance decreasing activation energy with the Fe2O3 addition can be
spectroscopy data is plotted in Fig. 6 as a function of reciprocal attributed to the presence of hematite [42], an oxide with low
temperature in Arrhenius format. With respect to the influence activation energy which is present in samples P5Fe and P8Fe.
 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052
The values herein reported are in the usual range of 1.33–
0.79 eV for electrical porcelains reported by other authors
[13,43].
4. Conclusions
Based on the experimental results, the following conclusions
are drawn regarding Fe2O3-containing aluminous porcelain. IS
results reveal the mixed contribution of glassy and crystalline
phases for the bulk response and crystal-glass interface
contribution on the overall electrical behavior of the aluminous
porcelains. The presence of hematite decreased the electric
resistivity. However, when all Fe2O3 was dissolved into the
melt phase and formed a solid solution with the other phases,
the resistivity was improved. This increase was attributed to an
increase in mullite and glassy phase fraction. This study
suggests that low-cost raw materials with greater Fe2O3
content can be used in manufacturing electrical porcelain
without compromising their insulating properties, hence lead-
ing to lower production costs, which could in turn make
porcelain insulators more economically competitive.
Acknowledgment
The authors acknowledge the CAPES and CNPq for the
scholarship and for the financial support provided for this
research.
References
[1] R.C. Buchanan, in: Ceramic Materials for Electronics-Processing, Proper-
ties, and Applications, 2nd ed., Dekker, New York, 1986.
[2] K. Sokolija, International Colloquium: Asset Management of Switching
Equipment and New Trends in Switching Technologies, 2003, pp. 86–98.
[3] L.S. Nasrat, A.F. Hamed, M.A. Hamid, S.H. Mansour, Study the
flashover voltage for outdoor polymer insulators under desert climatic
conditions, Egypt. J. Pet. 22 (2013) 1–8.
[4] M.H. Abderrazzaq, A.M. Abu Jalgif, Characterizing of corona rings applied to
composite insulators, Electr. Power Syst. Res. 95 (2013) 121–127.
[5] J. Mackevich, Polymer outdoor insulating materials – Part I: comparison
of porcelain and polymer electrical insulation, IEEE Electr. Insul. Mag.
13 (1997) 5–12.
[6] A. Prenleloup, T. Gmür, J. Botsis, K.O. Papailiou, K. Obrist, Stress and
failure analysis of crimped metal-composite joints used in electrical
insulators subjected to bending, Composites Part A – Appl. Sci. 40
(2009) 644–652.
[7] M. El-Shahat, H. Anis, Risk assessment of desert pollution on composite
high voltage insulators, J. Adv. Res. 5 (2014) 569–576.
[8] P.W. Olupot, S. Jonsson, J.K. Byaruhanga, Development and character-
ization of triaxial electrical porcelains from Ugandan ceramic minerals,
Ceram. Int. 36 (2010) 1455–1461.
[9] J.M. Amigó, F.J. Serrano, M. a Kojdecki, J. Bastida, V. Esteve, M.
M. Reventós, et al., X-ray diffraction microstructure analysis of mullite,
quartz and corundum in porcelain insulators, J. Eur. Ceram. Soc. 25
(2005) 1479–1486.
[10] Y. Iqbal, W.E. Lee, Fired porcelain microstructures revisited, J. Am.
Ceram. Soc. 90 (1999) 3584–3590.
[11] Y. Meng, G. Gong, Z. Wu, Z. Yin, Y. Xie, S. Liu, Fabrication and
microstructure investigation of ultra-high-strength porcelain insulator, J.
Eur. Ceram. Soc. 32 (2012) 3043–3049.
5051
[12] A.J. Bosman, H.J. van Daal, Small-polaron versus band conduction in
some transition-metal oxides, Adv. Phys. 19 (1970) 1–117.
[13] S.P. Chaudhuri, P. Sarkar, A.K. Chakraborty, Electrical resistivity of
porcelain in relation to constitution, Ceram. Int. 25 (1999) 91–99.
[14] J. Liebermann, About the important correlation between microstructure
properties and product quality of strength-stressed high-voltage insula-
tors, Interceram 53 (2013) 238–241.
[15] J. Liebermann, Microstructure properties and product quality of strength
stressed high-voltage insulators, Am. Ceram. Soc. Bull. 83 (2003) 39–46.
[16] N. Montoya, F.J. Serrano, M.M. Reventós, J.M. Amigo, J. Alarcón,
Effect of TiO2 on the mullite formation and mechanical properties of
alumina porcelain, J. Eur. Ceram. Soc. 30 (2010) 839–846.
[17] Z.D. Taszic, Improving the microstructural and physical properties of
alumina electrical porcelain with Cr2O3, MnO2 and ZnO additives, J.
Mater. Sci. 28 (1993) 5693–6701.
[18] S.P. Chaudhuri, P. Sarkar, Dielectric behaviour of porcelain in relation to
constitution, Ceram. Int. 26 (2000) 865–875.
[19] R.H. Piva, P. Vilarinho, M.R. Morelli, M.A. Fiori, O.R.K. Montedo,
Influence of Fe2O3 content on the dielectric behavior of aluminous
porcelain insulators, Ceram. Int. 39 (2013) 7323–7330.
[20] E. Kamseu, C. Leonelli, D.N. Boccaccini, P. Veronesi, P. Miselli,
G. Pellacani, et al., Characterization of porcelain compositions using
two china clays from Cameroon, Ceram. Int. 33 (2007) 851–857.
[21] R. Von Dreele, A. Larson, General structure analysis system (GSAS), Los
Alamos National Laboratory Report LAUR 86–748, 2000.
[22] B.H. Toby, EXPGUI, J. Appl. Crystallogr. 34 (2001) 210–213.
[23] A.F. Gualtieri, V. Riva, A. Bresciani, S. Maretti, M. Tamburini, A. Viani,
Accuracy in quantitative phase analysis of mixtures with large amorphous
contents. The case of stoneware ceramics and bricks, J. Appl. Crystallogr.
47 (2014) 835–846.
[24] FIZ Karlsruhe, International Crystal Stucture Data (ICSD), Karlsruhe,
Germany, 2000.
[25] C.J. McConville, W.E. Lee, Microstructural development on firing illite
and smectite clays compared with that in kaolinite, J. Am. Ceram. Soc. 88
(2005) 2267–2276.
[26] G.D. La Torre, M.A.G. Aranda, F. Jose, A.H. De Aza, S. De Aza,
Rietveld quantitative analysis of Buen Retiro porcelains, J. Am. Ceram.
Soc. 54 (2004) 449–454.
[27] W.M. Carty, U. Senapati, Porcelain-raw materials, processing, phase
evolution, and mechanical behavior, J. Am. Ceram. Soc. 81 (1998)
3–20.
[28] W.F. Cole, E.R. Segnit, High-temperature phases developed in some
kaolinite–mica–quartz clays, Trans. Br. Ceram. Soc. 62 (1963) 375–395.
[29] H. Schneider, H. Rager, Iron incorporation in mullite, Ceram. Int. 12
(1986) 117–125.
[30] S. Nibambin, A. Laurent, O.F. Josette, J. Jean Claude, L. Jean Paul,
B. Philippe, Role of iron in mullite formation from kaolins by Mössbauer
spectroscopy and Rietveld refinement, J. Am. Ceram. Soc. 86 (2003)
129–134.
[31] W.D. Kingery, in: Introduction to Ceramics, second ed., Jony Wiley,
New York, 1976.
[32] M.A. Silva, H.R. Paes, J.N.F. Holanda, Reuse of ornamental rock-cutting
waste in aluminous porcelain, J. Environ. Manag. 92 (2011) 936–940.
[33] D.C. Sinclair, Boletin de La Sociedad Espanola de Ceramica Y Vidrio,
65, 1995, pp. 55–66.
[34] M. Llusar, G. Monrós, C.M. Rodrigues, J.A. Labrincha, Study of zircon
or zirconia crystals addition in ceramic glazes by impedance spectro-
scopy, Ceram. Int. 31 (2005) 181–188.
[35] M.J. Ribeiro, J.C.C. Abrantes, J.M. Ferreira, J.A. Labrincha, Predicting
processing-sintering-related properties of mullite-alumina ceramic bodies
based on Al-rich anodising sludge by impedance spectroscopy, J. Eur.
Ceram. Soc. 24 (2004) 3841–3848.
[36] N. Narendar, G.C. Mather, P.A.N. Dias, D.P. Fagg, The importance of
phase purity in Ni–BaZr0.85Y0.15O3  δ cermet anodes – novel nitrate-free
combustion route and electrochemical study, RSC Adv. 3 (2013)
859–869.
5052 D.H. Piva et al. / Ceramics International 42 (2016) 5045–5052
[37] J.T.S. Irvine, D.C. Sinclair, A.R. West, Electroceramics: characterization
by impedance spectroscopy, Adv. Mater. 2 (1990) 132–138.
[38] C.M.S. Rodrigues, J.A. Labrincha, F.M.B. Marques, Study of yttria-
stabilized zirconia-glass composites by impedance spectroscopy, Solid-
State Sci. Technol. 144 (1997) 8–14.
[39] R. Harizanova, R. Keding, C. Rüssel, Electric conductivity of glasses in
the system Na2O/CaO/SiO2/Fe2O3, J. Non-Cryst. Solids 354 (2008)
65–71.
[40] S. Vinoth Rathan, G. Govindaraj, Thermal and electrical relaxation
studies in Li(4 þ x)TixNb1  xP3O12 (0.0rxr 1.0) phosphate glasses, Solid
State Sci. 12 (2010) 730–735.
[41] D. Sidebottom, B. Roling, K. Funke, Ionic conduction in solids:
comparing conductivity and modulus representations with regard to
scaling properties, Phys. Rev. B 63 (2000) 024301.
[42] M.V. Nikolic, M.P. Slankamenac, N. Nikolic, D.L. Sekulic, O.S. Aleksic,
M. Mitric, et al., Study of dielectric behavior and electrical properties of
hematite α-Fe2O3 doped with Zn, Sci. Sinter. 44 (2012) 307–321.
[43] A.Ş. Demirkiran, R. Artir, E. Avci, Electrical resistivity of porcelain
bodies with natural zeolite addition, Ceram. Int. 36 (2010) 917–921.