Ceramics International 47 (2021) 1229–1237

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Ceramics International
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CaO doped ZnO–Bi2O3 varistors: Grain growth mechanism, structure and

electrical properties
K. Hembram a, b, *, T.N. Rao a, R.S. Srinivasa b, A.R. Kulkarni b
a
Center for Nanomaterials, International Advanced Research Center for Powder Metallurgy & New Materials (ARCI), Balapur PO, Hyderabad, 500005, A.P., India
b
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, the impact of CaO doping on the microstructure, phase and electrical properties of the ZnO–Bi2O3
CaO doping system was studied. The powder was synthesized by the solution combustion route. Reduction in the crystallite
ZnO Varistor size of ZnO from 23 nm to 17 nm of the powder sample with CaO doping was noted. Conventional sintering was
Grain growth
used to consolidate the powders. Solid state reacted compositions revealed, from X-ray diffraction, formation of
Microstructure
Electrical properties
two phases (a) Ca4Bi6O13 at 750 ◦ C and (b) Ca0.89Bi3.11O5.56 at 900 ◦ C. An increase in density from 4.21 to 5.45
gcc− 1 and a decrease in grain size from 4.50 to 1.54 μm with increasing CaO doping were also observed. A grain
growth mechanism in the ZnO–Bi2O3–CaO system was proposed. The breakdown field increased up to 1 wt %
CaO (27 kV cm− 1) and after that decreased. Impedance spectroscopic investigation, in the temperature range of
100300 ◦ C and frequency range of 0.1 Hz -1M Hz, exhibited two relaxations. These were attributed to defects
formed. The two-stage activation energy of conductivity was noticed, which was similar to that observed in
complex ZnO varistor systems.

1. Introduction
ZnO varistor is a non-linear device whose function is to sense and
control the surge voltage applied across the terminals; it is used exten­
sively for over-voltage protection [1]. Commercially ZnO varistor is
fabricated using powder metallurgy processing involving mixing
micron-sized ZnO powder with various additives ~4 mol % followed by
pressing and liquid phase sintering at temperatures in the range
1100–1400 ◦ C, which results into grain size of 10–25 μm. Non-linear
behavior of a ZnO–Bi2O3 varistor is attributed to segregation of Bi2O3
at the grain boundaries which make grain boundaries highly insulating
(1010-1012 Ωcm) and ZnO grains core become conducting (0.1–10 Ωcm),
the substantial difference in impedance of grains and grain boundaries
resulting in Double Schottky Barriers (DSB) formations [1–3]. A number
of attempts were made to replace Bi2O3, with Pr6O11 [4], V2O5 [5], and
CuO2 [6]; did not show significant enhancement in non-linear behavior
over commercial ones. Furthermore, various materials such as SnO2 [7],
TiO2 [8], SrTiO3 [9], WO3 [10] and CuCaTiO3 [11] are also being
investigated as an alternative to ZnO based varistor. However,
ZnO–Bi2O3 varistors are still commercially favored due to a combination
of excellent electrical properties at a lower cost [12]. It is well known
that grain size and grain boundary engineering play a crucial role in
achieving a varistor’s performance parameter and design. Bi2O3 melts
relatively at a lower temperature (650 ◦ C) and insulates the grain
boundaries of ZnO, which results in electrically insulating grain
boundary responsible for non-linear behavior [13]. Bi2O3 also encour­
ages grain growth of ZnO, which deteriorates the properties of a varistor.
Controlling the grain growth and microstructure is essential, and this is
normally achieved through the addition of dopants, for example, Sb2O3.
ZrO2 [14], WO3 [15], SiO2 [16,17], Al2O3 [18]B2O3 [19] CaO [20],and
rare earth oxides (Dy, Sc, Y) [21–23]. However, the influence of CaO
addition on ZnO–Bi2O3 varistor characteristics was reported only
recently [20].
It was evident that the major portion of CaO reacts with Bi2O3 that
forms the bismuth calcium oxide complex phase. However, due to the
complexity of the system in a previous study [20], the influence of CaO
addition on structure, grain growth mechanism and properties of
varistor was not fully understood [2,24,25]. In this study, an effort has
been made to understand the influence of CaO addition on the micro­
structure and electrical properties of the ZnO–Bi2O3 system. Different
concentration (X = 0.00, 0.25, 1.00 and 2.50 wt %) of CaO doped (95-X)
ZnO–5Bi2O3 powders were made by solution combustion synthesis

* Corresponding author. Center for Nanomaterials, International Advanced Research Center for Powder Metallurgy & New Materials (ARCI), Balapur PO,
Hyderabad, 500005, A.P., India.
E-mail address: kaliyan@arci.res.in (K. Hembram).

https://doi.org/10.1016/j.ceramint.2020.08.242
Received 24 June 2020; Received in revised form 14 August 2020; Accepted 26 August 2020
Available online 28 August 2020
0272-8842/© 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
K. Hembram et al. Ceramics International 47 (2021) 1229–1237

(SCS). The phase, microstructure, electrical and dielectric properties of 2.3. I–V measurement
the sintered samples are investigated. A grain growth mechanism is
proposed for the system. I–V characteristics were measured on a circumference insulated
sintered pellet samples using by 5 KV DC (Rectifiers and Electronics,
2. Experimental and characterizations Delhi, India) breakdown tester at 25 ◦ C. The sample holder, made in-
house, was used for measurements. The breakdown field (Bf) was
2.1. Powder synthesis and consolidations calculated at a current density of 1 mA/cm2. The coefficient of nonlin­
earity (α) was calculated: α = (1/logE2-logE1); E2 > E1, where E1 is the
Zinc nitrate hexahydrate (99% Alfa-Asear make), Calcium nitrate field at current density J1 (0.1 mA/cm2) whereas E2 is the field at current
tetrahydrate (99.9%, Alfa-Asear make), and Cobalt nitrate hexahydrate density J2 (1 mA/cm2).
(>99 %, Sigma make) were mixed in double-distilled water (Sol.-1). To
get complete transparent solution Bismuth nitrate pentahydrate (99%, 2.4. Impedance and dielectric measurements
Sigma make) was heated (100–150 ◦ C) in dilute nitric acid (99.9%,
Renkem make) (Sol.-2). The Sol.-2 and to Sol.-1 were mixed, followed by Complex impedance and dielectric properties measurements were
heating around 100 ◦ C to make a transparent solution. 0.23 mol% of performed on pellets (1 mm thick and 8 mm diameter) with silver
sucrose (98%, Renkem make) was added to the final solution. The electrodes coated on both the sides of the pellet, by impedance analyzer
resulting solution was heated to a temperature in the range of (Novocontrol, Alpha) in the frequency range of 0.1 Hz -1 MHz in the
180–200 ◦ C and stirred until it catches fire. The CaO doped (95-X) wide range of temperatures at 25 ◦ C intervals with an amplitude bias
ZnO–5Bi2O3-XCaO (X = 0.00, 0.25, 1.00, and 2.50) powders were syn­ voltage of 1Vrms− 1. The measurements were performed in the cooling
thesized and calcined at 750 ◦ C for 1 h. The powders were consolidated cycle for better temperature stability. The temperature was controlled
into a 10 mm pellet at the pressure of 150 MPa in a die. The pellets were through a Eurotherm temperature controller. Impedance data were
sintered at two-step sintering (as depicted in Figure S-1): (1) heating up analyzed by using software ZSimpWin 3.21. The impedance data were
to 900 ◦ C and hold it for 0.5 h, then decrease to 825 ◦ C and hold it again analyzed in different formalisms for detailed interpretation.
for 4 h followed by cooling (designated as S-1). (2) Heating up to
1000 ◦ C and hold it for 0.5 h, then decrease to 825 ◦ C and hold it for 4 h
3. Results and discussion
followed by cooling (designated as S-2). (3) Heating up to 1100 ◦ C and
hold it for 0.5 h, then decrease to 825 ◦ C and hold it for 4 h followed by
3.1. Phase and composition analysis of the powder samples
cooling (designated as S-3). The rate of cooling and heating was kept
2 ◦ C min− 1 up to 725 ◦ C and then furnace cooling for all the pellet
A comparison of XRD patterns (at room temperature) of undoped
samples.
(UDZB) and CaO doped (CDZB) powder specimens heated at 750 ◦ C-1h
is shown in Fig. 1. ZnO Wurtzite (JCPDS card no. # 13–7122) and
2.2. Phase and microstructure evaluation
α-Bi2O3 (JCPDS card no. # 52–1007) phases were detected in UDZB
powder sample. Phases of ZnO, Ca4Bi6O13 (JCPDS card no. # 48–0217)
Phases in the powder and sintered samples were studied using
were noticed in the CDZB powder samples. The formation of phases in
Powder X-ray Diffraction (Bruker D8 advance) using CuKα radiation.
CDZB samples is explained elsewhere [27] using ½Bi2O3–CaO phase
Compositions of calcined powders were checked by ICP-OES (Varian
Liberty) analysis. The powders were dissolved in nitric acid to make a
0.1 M solution, and the percentage of elements present in the samples
was estimated. Thermal analysis of the sample was carried out by STA
449 Jupiter (Netzsch GmbH, Germany) with a heating rate of 10 ◦ Cmin-1
from room temperature (RT)-1200 ◦ C in air. Green pellet densities were
measured by weight and dimension analysis technique, whereas sin­
tered samples densities measured by the Archimedes method.
Morphology and microstructure of the powder and sintered specimens
were analyzed by FE-SEM (S-4300-SE/N, Hitachi), and qualitative
composition (elemental analysis) of both the samples were analyzed by
EDS (EDAX, USA) attached to the unit. The average ZnO grain size was
measured by Olympus analySIS software using the following relation­
ship: G = 1.56L, where G is the average ZnO grain size, and L is the
average grain boundary intercept length [26]. The microstructure and
morphology of the powder and sintered samples were studied by TEM
(200 KV, FEI). The powder samples were sonicated for 10–15 min in
ethanol before putting 2–3 drops on a copper grid. Bright-field TEM
images were used for the crystallite size estimation of the powders.
Qualitative compositional (elemental analysis) of the specimens were
also carried out by EDS attached to TEM. SAED studies for the sintered
samples were carried out by TEM attached to the unit. The thickness of
the TEM sample for the sintered sample was reduced using the Isomet
cutter. A 3 mm dimple was prepared by GATAN, 601 ultrasonic cutter on
200 μm thick specimen. The thickness of the sample was reduced to
approximately 60 μm by 2000 no. emery paper flowed by ion milled for
9–10 h at an energy of 4 KeV and angle at 11◦ till a tiny hole was
generated (GATAN, Mod. No. 691). The TEM sample was cleaned (1.5
KeV) for 10–15 min just before analysis. The ’d’ spacing is calculated
from the formula R d = Lλ, where R is the spot spacing, L is the camera Fig. 1. XRD patterns of UDZB and CDZB powder samples calcined at 750 ◦ C for
length, and λ is the electron beam wavelength. 1 h.

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could be an excellent candidate for grain boundary phase in ZnO varistor

since the compound contains more oxygen as a result of which increase
in barrier strength of the device is possible, and that would lead to
improvement in the properties [29,30]. The detailed study of ZBC (X =
1.00) was carried out because it demonstrated better varistor properties
than other compositions.
Fig. 2(a) shows a comparison of XRD patterns for the powder (X =
1.000) samples calcined at different temperatures in the range of
750–950 ◦ C for 1 h to understand the grain boundary phase formations.
Interestingly, when as-synthesized powder was calcined at ≤ 650 ◦ C for
1 h, a single Wurtzite ZnO phase was obtained (Figure S-2(a)). However,
when the powder was heated to ≥ 750 ◦ C for 1 h, the Ca4Bi6O13 phase
along with ZnO and ≥ 950 ◦ C for 1 h Ca0.89Bi3.11O5.56 and Ca4Bi6O13
phase along with ZnO was observed (Fig. 2(b)).
For a better understanding of the phase formation of the materials
and supplement the XRD results, thermal analysis of the gel was carried
out. The results are shown in Fig. 2(c). Endothermic peak at 395 ◦ C is an
indication of completion of combustion and formation of ZnO phase;
two endothermic peaks at 750 and 865 ◦ C correspond to Ca4Bi6O13 and
Ca0.89Bi3.11O5.56 phases which suggest that in both cases the secondary
phase formation take place at a temperature below 900 ◦ C. Weight loss
of 30 wt% up to 395 ◦ C is due to the burning of organic and nitrate
compounds, and weight loss of ~10 wt% up to 1200 ◦ C is due to
evaporation of bismuth species [24,43].
The compositions of all the powder samples calcined at 750 ◦ C for 1 h
are given in Table 1. The compositions of the powder samples were
within the experimental error after the synthesis and calcination pro­
cess. As discussed above, the XRD of the powders and thermal analysis of

Fig. 2. (a) XRD patterns of X = 1.00 powder samples calcined at different

Table 1
temperatures for 1 h and (b) Thermograph of a mixture of (Zn, Bi, Ca nitrates,
Compositional analysis by ICP-OES of powder samples calcined at 750 ◦ C for 1 h.
and fuel) gel of X = 1.00 sample.
Sample ID Composition in wt. %

diagram. Less than 10 mol. % CaO yields Ca2Bi4O12 and Bi2O3 phases, ZnO Bi2O3 CaO
and above 10 mol.% Ca4Bi6O13,Ca3Bi8O15, and Ca2Bi2O4 phases are X = 0.00 95.20 4.79 –
reported [27,28]. The composition used for the present study favors the X = 0.25 95.15 4.50 0.21
Ca4Bi6O13 phase formation because the percentage of CaO is marginally X = 1.00 94.25 4.80 0.80
X = 2.50 92.75 4.70 2.54
higher than 20 mol. % of Bi2O3 and CaO phases [27,28]. The Ca4Bi6O13

Fig. 3. Bright-field TEM images; insets are crystallite size histogram of powder samples having different compositions; calcined at 750 ◦ C for 1 h.

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Fig. 4. (a) Impact of CaO addition on the crystallite size of powder samples. (b) Influence of calcination temperature on crystallite size of X = 1.00 powder samples.

Fig. 5. (a) A comparison of XRD patterns for UDZB and CDZB sintered samples and (b) zoom in view of grain boundary phase.

Fig. 6. (a) Backscattered-SEM (thermally-etched) images; insets are grain size distribution histogram of sintered samples. (b) Influence of CaO doping on the grain
size of sintered samples.

the gel, liquid phase formation at temperature ~750 ◦ C is observed. A
little deviation of the composition could be due to segregation resulting
from liquid phase formation [31]. These powder samples were com­
pacted and sintered into pellets without any further purification and
modification.
3.2. Morphological studies of powder samples
Fig. 3 shows the bright-field TEM images; the insets are the crystallite
size distribution histograms of the powder samples calcined at 750 ◦ C for
1 h. An impact of CaO doping on the crystallite size of ZnO for the
powder sample is shown in Fig. 4(a) and the influence of calcination

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temperature on the crystallite size of ZnO for ZBC (X = 1.00) powder
sample is shown in Fig. 4(b).
A decrease in crystallite size with increasing CaO doping was
observed until X = 1.00. Thereafter, a slight increase can be seen clearly.
Uniform distribution and decrease in crystallite size with CaO doping
are due to grain boundary phase formation of Ca4Bi6O13 at the surface of
ZnO. Bright-field TEM images (insets are particle size distribution and
dark field TEM images) of ZBC (X = 1.00) powder sample calcined at
different temperatures are shown in Figure S-2(b). As expected, it can be
seen that crystallite size increased from 16 nm (550 ◦ C) to 650 nm
(850 ◦ C) with increasing temperature. However, an abnormal increase
in grain size for the powder calcined at 850 ◦ C for 1 h is attributed to
liquid phase formation, as discussed earlier.
3.3. Phase and microstructure studies of sintered samples
3.3.1. Phase analysis
Fig. 5 (a–b) show the comparison of XRD patterns with zoomed-in
view on 2θ values in the range of 25–31◦ of UDZB and CDZB samples
sintered by S-2. The phases of α- Bi2O3 (JCPDS card no. # 41–1449) and
ZnO (JCPDS card no. # 13–7122) were clearly noticed in UDZB sintered
sample whereas the secondary phase of Ca4Bi6O13 (JCPDS card no. #
48–0217) and Ca0.89Bi3.11O5.56 (JCPDS card no. # 40–0317) along with
ZnO matrix phase were observed in case of CDZB sintered samples. The
intensity of XRD peaks for Ca0.89Bi3.11O5.56 phase is higher than the
Ca4Bi6O13 phase of X = 1.00 compared to X = 2.50 CDZB, suggesting
that Ca0.89Bi3.11O5.56 phase favored the lower concentration of CaO.
Phase formation of these sintered samples also could be explained by the
1/2Bi2O3–CaO phase diagram, as discussed in the earlier section [27,
28]. The Ca4Bi6O13 and Ca0.89Bi3.11O5.56 phases appeared in the tem­
perature range 750–900 ◦ C (Fig. 6); the present findings are in good
agreement with earlier studies [27,28]. However, the influence of these
secondary phases in ZnO varistor is hitherto unreported, except in our
previous study [20]. It is believed that a few monolayer thin oxygen rich
grain boundary phase between two ZnO grains is good enough to exhibit
ZnO varistor action, which helps in improving tunneling and switching
of charge carriers through the double Schottky barrier (DSB), resulting
in a better coefficient of nonlinearity [30,32]. Therefore, small amount
of Ca4Bi6O13 and Ca0.89Bi3.11O5.56 grain boundary phases are ideal for
high performance ZnO varistor.
Fig. 7. (a) Bright-field and (b) Dark-field TEM images at the same location; (c) EDS of grain boundary phase confirming presence of Bi, Ca, O and Zn elements (white
oval), (d) HR-TEM image at the inter-granular area, (e) SAED pattern from zone axes [001] and [011], confirming an FCC structure (a = ~0.55 nm) of
Ca0.89Bi3.11O5.56 phase of X = 0.00 sintered sample.
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Ceramics International 47 (2021) 1229–1237
3.3.2. Microstructure analysis
FE-SEM images of polished and thermally etched UDZB and CDZB
samples sintered by S-2 are depicted in Fig. 6 (a). The insets of Fig. 6 (a)
show ZnO grain size distribution histogram. The influence of CaO
doping on grain size is depicted in Fig. 6 (b). To confirm the liquid phase
distribution throughout the samples, FESEM and EDS were carried out
on the fracture surface of all sintered samples, as shown in Figure S-3(a)
and (b). It is clearly seen that the liquid phase is homogeneously
distributed throughout the microstructure, and a thin layer is covered on
the ZnO grains, and the bulk of liquid phases are segregated at triple
junctions and grain boundaries. The liquid phase in the samples
increased as the concentration of CaO is increased. Decrease in grain size
from 4.45 to 1.54 μm and narrow grain size distribution with larger CaO
addition till X = 1.00 sintered sample, thereafter increase in grain size
due to the formation of a more liquid phase. It may be noted that the
homogenous distribution of grain boundary phase Ca4Bi6O13 and
Ca0.89Bi3.11O5.56 throughout the microstructure of the sintered samples.
The round shape of ZnO grain suggests that a liquid phase is formed
during sintering, which is well known for ZnO–Bi2O3 based varistor
composition [33,34]. The effect of sintering temperature on ZnO grain
size (X = 1.00) is shown in Figure S-4. An increase in grain size and
liquid phase with CaO doping are observed. Grain growth retardation is
attributed to an increase in viscosity of liquid phase and Zener pining by
grain boundary phases of Ca4Bi6O13 and Ca0.89Bi3.11O5.56. Grain growth
of ZnO with increasing sintering temperature, which is attributed to the
formation of a more liquid phase as expected [35].
3.3.3. TEM, EDS and SAED studies of sintered specimen
Fig. 7 (a) and (b) display the bright-field and dark-field TEM images
of X = 1.00 sintered sample, respectively. The EDS of grain boundary
phase (white oval, as shown in dark-field TEM image) is shown in Fig. 7
(c). HR-TEM image of the grain boundary interface is shown in Fig. 7(d).
The SAED patterns at the inter-granular area (oval marked in Fig. 7(b))
from zone axes [001] and [011] of the sample are shown in Fig. 7 (e) and
(f), respectively. Spot EDS analysis from the white location confirms that
the grain boundary contains Bi, Ca, Zn and O species. HR-TEM image
shows a ~2 nm amorphous grain boundary similar to that of commercial
ZnO varistors [42,52]. The SAED patterns (hkl) planes corresponding to
(020), (220) and (220) from zone axis [001], and (200), (111)) and
(111) from zone axis [011] which turns out be a FCC structure (a =
K. Hembram et al. Ceramics International 47 (2021) 1229–1237

Fig. 8. A grain growth mechanism comparison with commercial and CaO doped ZnO varistor system.

~0.55 nm). The grain boundary phase is confirmed to be

Ca0.89Bi3.11O5.56 (JCPDS No # 40–0317) phase. The phase confirmation
by SAED is in good agreement with the XRD results.

3.4. Understanding the grain growth mechanism

Before elucidating the grain growth mechanism of the CaO doped

Fig. 9. Influence of CaO addition on I–V characteristics; inset is the influence of
I–V characteristics on sintering temperature for X = 0.00 samples.
ZnO–Bi2O3 system, it is necessary to revisit the traditional Sb2O3 added
ZnO–Bi2O3 system and compare it with this new system. It is well known
that the densification in a ZnO varistor is due to the liquid phase sin­
tering. Bismuth oxide liquid phase is arranged by a diffusion process due
to solution precipitation and grain boundary reactions, as shown in
Fig. 8(a) [35–37]. Generally, Sb2O3 is added as a grain growth inhibitor,
which forms spinel (Zn7Sb2O12) and pyrochlore (Bi3Zn2Sb3O14) during
heating, creating the Zener drag and inhibiting ZnO grain growth [38].
Grain size is inversely proportional to the concentration of the spinel
phase. It is also evident that a small amount of Sb2O3 (< 75 ppm) pro­
duces a coarse-grained microstructure rather than smaller grain in ZnO
based varistor system [39]. In this system, ZnO grain growth retardation
is due to Ca4Bi6O13 and Ca0.89Bi3.11O5.56 phases at the grain boundary of
ZnO grain and their interface. The ZnO grain growth inhibition is
attributed to pinning by a small solute particle (~ 5 nm) and an increase

Fig. 10. (a) Normalized Cole-Cole plots and the data are fitted to a two parallel RC circuit model (inset); (b) Electrical modulus plots and the data are fitted into two
semicircles, and insert is the frequency dependent Z′′ and M′′ plots for UDZB and CDZB sintered samples.

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Table 3
Electrical, dielectric (200 ◦ C and 50 Hz) properties and Ea of sintered specimens.
Sample ID Cgb1 (pF) Rgb1 (MΩ-cm) Cgb2 (pF) Rgb2 (MΩ-cm) ε’ (200 ◦ C, 50 Hz) Tan δ (200 ◦ C & 50 Hz) Ea. (eV)

Region I Region I

X = 0.00 089 0.136 102 3.21 1163 ± 10 6.13 ± 0.5 0.56 1.01
X = 0.25 101 0.055 104 3.31 1037 ± 10 6.66 ± 0.5 0.62 0.79
X = 1.00 136 0.325 514 6.11 0444 ± 10 5.45 ± 0.5 0.61 0.85
X = 2.50 154 4.610 554 22.10 0395 ± 10 4.65 ± 0.5 0.84 0.97

in viscosity of the liquid phase, as shown in Fig. 8 (b). Neither inverse properties compared to other samples; this is due to the small grain size
grain boundary nor spinel and pyrochlore phase formation was observed and narrow grain size distribution of ZnO. The X = 1.00 sample was
in any of the present sintered samples. For SiO2 doped ZnO varistor, the sintered at different temperatures to optimize sintering parameters. The
ZnSiO4 phase is responsible for increasing the viscosity of the liquid breakdown field (Bf) of 26.6 kVcm− 1 with a moderate coefficient of
phase and inhibiting the ZnO grain growth [40,41]. In the present study, nonlinearity of 7 was obtained sample sintered by S-1 sample. Excep­
even a small (X = 0.25) doping of CaO also retarded grain growth, and tional high breakdown voltage is due to the uniform distribution of
the effect is significant. Therefore, it can be inferred that the grain
growth retardation is more dominated by an increase in the liquid
Table 2
phase’s viscosity rather than Zener pining by secondary grain boundary
The grain size, density and electrical properties of sintered pellet specimens.
phases. The impression of the present study is that the grain growth
Sample ID Grain Size Density Breakdown field Coefficient of
pinning for CaO doped ZnO varistor is similar to that of SiO2 [41,42].
(μm) (gcc− 1) (kVcm− 1) nonlinearity

X = 0.00 4.50 ± 5.23 ± 01.72 ± 0.50 02.90 ± 0.5

3.5. Electrical properties studies of sintered samples 0.50 0.05
X = 0.25 4.40 ± 5.40 ± 02.70 ± 0.50 03.15 ± 0.5
3.5.1. I–V characteristics 0.50 0.05
Fig. 9 shows the comparison I–V characteristic of UDZB and CDZB X = 1.00 1.54 ± 5.32 ± 12.88 ± 1.00 12.00 ± 1
(S-2) 0.25 0.05
sintered samples; inset is the X = 1.00 sample sintered at different
S-3 3.91 ± 5.01 ± 02.60 ± 0.50 08.58 ± 1
temperatures. The summary of varistor properties for all the samples is 0.50 0.08
given in Table 2. An increase in breakdown field with increasing CaO S-1 1.35 ± 5.21 ± 26.60 ± 5.00 06.65 ± 1
addition till X = 1.00 12.88 kVcm− 1 thereafter decrease was observed. 0.25 0.05
The coefficient of nonlinearity as high as 12 was obtained for X = 1.00 X = 2.50 4.75 ± 5.43 ± 07.78 ± 3.00 3.00 ± 0.5
0.50 0.05
sintered sample. The X = 1.00 sample exhibited better varistor

Fig. 11. Frequency dependent (a) dielectric constant, (b) tan δ (inset is the tan δ at higher frequencies region) at 200 ◦ C; (c) Temperature dependent exponent and
(d) Arrhenius plot of DC conductivity for UDZB and CDZB sintered samples.

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K. Hembram et al.
secondary phases of Ca4Bi6O13 and Ca0.89Bi3.11O5.56 at the grain
boundary and interface area and smaller ZnO grain size. The Bf is an
order of magnitude higher than the commercial ZnO varistor [32,43].
3.5.2. Impedance and electrical modulus studies
Fig. 10 (a) shows normalized impedance plots fitted to a two parallel
RC circuit model, and (b) electrical modulus and inset is the frequency
dependent Z′′ and M′′ plot at 200 ◦ C for sintered (S-2) samples. The
impedance plots are elongated semicircular shaped whereas electric
modulus plots show two semicircles for all the samples, thereby justi­
fying the two parallel RC circuit model for data interpretation. The Z′′
versus f plots show one relaxation peak whereas M′′ versus f plots show
two relaxation peaks, one at lower (500 Hz) frequency regime and
another at higher frequency region (2 × 105 Hz) (lower concentration
CaO) sintered samples. However, as the concentration of CaO increased
to X = 2.50, the second relaxation peak moves beyond 1 MHz due to
small capacitance values. It is to be noted that the same trend was
observed in the complex composition of ZnO varistor as well [20,44,45].
The electrical properties of fitted data are shown in Table 3. An increase
in grain boundary resistivity (Rgb1 and Rgb2) with increasing CaO doping
was observed. An increase in capacitance (Cgb1 and Cgb2) values with
increasing CaO concentration was noted. Resistivity and capacitance
increased are attributed to decreases in carrier concentrations of the
samples, as reported in our previous studies [46,47].
3.6. Dielectric studies
To correlate the I–V and impedance results, and to appreciate the
influence of CaO doping on the electrical properties of sintered samples,
the complex impedance raw data are analyzed. Complex impedance
data are analyzed using the relationship [48,49]:
[ ]− 1 [ ]− 1
1 1
Z * = Z ’ − Z ’’ = + jωCg + + jωCgb1
Rg Rgb1
+ [1/ (Rgb2 + Ao (jω)n )]− 1
(1)
Where ω and n are the angular frequency and depression of impedance
plots, the capacitance and resistance of grain boundary type 1 (GB1) and
grain boundary type 2 (GB2) are assigned as Cgb1, Rgb1, Cgb2 and Rgb2.
Relaxation takes place when ωRC = 1. GB1 is assigned to resistance
having lower values, whereas GB2 is to the highest resistance compo­
nent. Fig. 11 (a–b) displays the frequency dependent tan δ and ε′ for
different compositions of sintered (S-2) specimens at 200 ◦ C and 50 Hz,
are summarized in Table 3. Decrease in dielectric constant with
increasing frequency; the value remains almost constant beyond 105 Hz.
Tan δ decreases with increasing frequency around 103 Hz, and beyond
that, it remains constant. A decrease in dielectric constant with
increasing CaO doping was observed [Table- 3], it is due to the fact that
dielectric constant decreases with a decrease in grain size [50]. It may be
noted that a decrease in Tan δ with increasing CaO addition is due to a
reduction in carrier concentration of the samples.
3.7. Conductivity studies
The activation energy of DC conductivity is calculated using a rela­
tionship:
Ea
σ dc = σo exp (2)
kT
Where σo is the pre-exponential factor, Ea is the activation energy, and k
is the Boltzmann’s constant. Frequency dependent AC conductivity are
fitted to the Jonscher’s law at different temperature and extracted the
exponent “n” and DC conductivity values of the samples [51]. The “n”
and Arrhenius plots for DC conductivity are shown in Fig. 11 (c–d). The
“n” values are in the range of 0.90–0.30 at 125–450 ◦ C, which suggests
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Ceramics International 47 (2021) 1229–1237
that the conduction of charge carrier is due to long-range hopping [51].
It is clearly seen that two stages of Ea in the Arrhenius plot, the Ea is in
the range 0.80–1.01 eV for region II, the Ea is in the range 0.30–0.60 eV
for region I, the trend of these values are similar to that of complex ZnO
varistor system [44,52,53]. It may be noted that the Ea values for these
compositions are very much close to the complex varistor composition.
It is known that all traps at grain boundaries are due to Bi2O3 and are
responsible for the varistor effect; other dopants are added to enhance
properties of the ZnO–Bi2O3 based varistors [54].
4. Conclusions
Understanding of CaO doping on microstructure, phase and prop­
erties in a simple ZnO–Bi2O3 system was established. A reduction in
crystallite size from 23 to 17 nm for the powder was observed with CaO
doping. The phase formation of Ca4Bi6O13 and Ca0.89Bi3.11O5.56 at a
temperature of 750 ◦ C and 900 ◦ C was observed. An increase in density
from 4.21 to 5.45 gcc− 1 and a decrease in grain size from 4.50 to 1.54 μm
due to CaO doping were discerned. This is due to grain growth retar­
dation caused by an increase in viscosity of the liquid phase and Zener
pinning mechanism due to the presence of Ca4Bi6O13 and
Ca0.89Bi3.11O5.56 grain boundary secondary phases. Increase in break­
down field having CaO content till 1wt.% (as high as 27 Kvcm− 1)
thereafter decrease was observed. The coefficient of nonlinearity as high
as 12 for 1 wt% CaO sample was obtained without transition metal oxide
doping. Two defect relaxations in a wide range of temperature and
frequency ranges were observed similar to that of commercial ZnO
varistor. In the case of ≥ 1 wt% samples, the carrier traps development
are due to the presence of Ca4Bi6O13 and Ca0.89Bi3.11O5.56 grain
boundary phases. Two stage activation energy of conductivity was dis­
cerned; 0.30–0.60 eV (Region I) and 0.80–1.01 eV (Region I). The
activation energy of DC conductivity values is similar to that of the
complex ZnO varistor system.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
One of the author like to extend gratitude to DST-SERB, Govt. of
India (Grant No. SB/EMEQ-221/2013), for partially supporting this
work. Director ARCI is duly acknowledged for giving permission to
publish the manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ceramint.2020.08.242.
References
[1] M. Matsuoka, Nonohmic properties of zinc oxide ceramics, Jpn. J. Appl. Phys. 10
(1971) 736.
[2] T.K. Gupta, Application of zinc oxide varistors, J. Am. Ceram. Soc. 73 (1990)
1817–1840.
[3] D. Clarke, Varistor ceramics, J. Am. Ceram. Soc. 82 (1999) 485–502.
[4] S. Bachir, C. Sandouly, J. Kossanyi, J.C. Ronfard-Haret, Rare earth-doped
polycrystalline zinc oxide electroluminescent ceramics, J. Phys. Chem. Solid. 57
(1996) 1869–1879.
[5] J.K. Tsai, T.B. Wu, Non-ohmic characteristics of ZnO-V2O5 ceramics, J. Appl. Phys.
76 (1994) 4817–4822.
[6] T.R.N. Kutty, N. Raghu, Varistors based on polycrystalline ZnO:Cu, Appl. Phys.
Lett. 54 (1989) 1796–1798.
[7] P.R. Bueno, S.A. Pianaro, E.C. Pereira, L.O.S. Bulhões, E. Longo, J.A. Varela,
Investigation of the electrical properties of SnO2 varistor system using impedance
spectroscopy, J. Appl. Phys. 84 (1998) 3700–3705.
K. Hembram et al.
[8] M.F. Yan, W.W. Rhodes, Preparation and properties of TiO2 varistors, Appl. Phys.
Lett. 40 (1982) 536–537.
[9] T.R.N. Kutty, S. Philip, Low voltage varistors based on SrTiO3 ceramics, Mater. Sci.
Eng., B 33 (1995) 58–66.
[10] V. Makarov, M. Trontelj, Novel varistor material based on tungsten oxide, J. Mater.
Sci. Lett. 13 (1994) 937–939.
[11] S.Y. Chung, I.D. Kim, S.J. Kang, Strong non-linear current-voltage behaviour in
perovskite-derivative calcium copper titanate, Nat. Mater. 3 (2004) 774–778.
[12] J. Li, S. Li, P. Cheng, M. Alim, Advances in ZnO–Bi2O3 based varistors, J. Mater.
Sci. Mater. Electron. 26 (2015) 4782–4809.
[13] D.R. Clarke, Grian-boundary segregation in a commercial ZnO-based varistor S,
J. Appl. Phys. 50 (1979) 6829–6832.
[14] Y. Akiyama, M. Takada, A. Fukumori, Y. Sato, S. Yoshikado, Effect of ZrO2 addition
on tolerance characteristics of the electrical degradation of ZnO varistors, Electr.
Eng. Jpn. 179 (2012) 11–19.
[15] X. Xiao, L. Zheng, L. Cheng, T. Tian, X. Ruan, M. Podlogar, et al., Influence of WO3-
doping on the microstructure and electrical properties of ZnO–Bi2O3 varistor
ceramics sintered at 950◦ C, J. Am. Ceram. Soc. 98 (2015) 1356–1363.
[16] H. Bai, M. Zhang, Z. Xu, R. Chu, J. Hao, H. Li, et al., The effect of SiO2 on electrical
properties of low-temperature-sintered ZnO–Bi2O3–TiO2–Co2O3–MnO2-based
ceramics, J. Am. Ceram. Soc. 100 (2017) 1057–1064.
[17] Z-h Wu, J-h Fang, D. Xu, Q-d Zhong, L-y Shi, Effect of SiO2 addition on the
microstructure and electrical properties of ZnO-based varistors, Int. J. Miner.
Metall. Mater. 17 (2010) 86–91.
[18] L.-H. Cheng, L.-Y. Zheng, L. Meng, G.-R. Li, Y. Gu, F.-P. Zhang, et al., Electrical
properties of Al2O3-doped ZnO varistors prepared by sol–gel process for device
miniaturization, Ceram. Int. 38 (Supplement 1) (2012) S457–S461.
[19] L. Cheng, G. Li, K. Yuan, L. Meng, L. Zheng, Improvement in nonlinear properties
and electrical stability of ZnO varistors with B2O3 additives by nano-coating
method, J. Am. Ceram. Soc. 95 (2012) 1004–1010.
[20] K. Hembram, T.N. Rao, M. Ramakrishana, R.S. Srinivasa, A.R. Kulkarni, Influence
of CaO doping on phase, microstructure, electrical and dielectric properties of ZnO
varistors, J. Alloys Compd. 817 (2020) 152700.
[21] G-h Chen, J-l Li, Y. Yang, C-l Yuan, C-r Zhou, Microstructure and electrical
properties of Dy2O3-doped ZnO–Bi2O3 based varistor ceramics, Mater. Res. Bull. 50
(2014) 141–147.
[22] P. Williams, O.L. Krivanek, G. Thomas, M. Yodogawa, Microstructure-property
relationships of rare-earth–zinc-oxide varistors, J. Appl. Phys. 51 (1980)
3930–3934.
[23] D. Xu, X. Cheng, H. Yuan, J. Yang, Y. Lin, Microstructure and electrical properties
of Y(NO3)3⋅6H2O-doped ZnO–Bi2O3-based varistor ceramics, J. Alloys Compd. 509
(2011) 9312–9317.
[24] M. Peiteado, M.A. de la Rubia, M.J. Velasco, F.J. Valle, A.C. Caballero, Bi2O3
vaporization from ZnO-based varistors, J. Eur. Ceram. Soc. 25 (2005) 1675–1680.
[25] R. Metz, H. Delalu, J.R. Vignalou, N. Achard, M. Elkhatib, Electrical properties of
varistors in relation to their true bismuth composition after sintering, Mater. Chem.
Phys. 63 (2000) 157–162.
[26] M.I. Mendelson, Average grain size in polycrystalline ceramics, J. Am. Ceram. Soc.
52 (1969) 443–446.
[27] R.S. Roth, N.M. Hwang, C.J. Rawn, B.P. Burton, J.J. Ritter, Phase equilibria in the
systems CaO–CuO and CaO-Bi2O3, J. Am. Ceram. Soc. 74 (1991) 2148–2151.
[28] E.Y. Vstavskaya, A.Y. Zuev, V.A. Cherepanov, The phase diagram of the bismuth-
calcium oxide system, Mater. Res. Bull. 29 (1994) 1233–1238.
[29] T.R.N. Kutty, S. Ezhilvalavan, The influence of Bi2O3 non-stoichiometry on the
non-linear property of ZnO varistors, Mater. Chem. Phys. 38 (1994) 267–276.
[30] F. Stucki, F. Greuter, Key role of oxygen at zinc oxide varistor grain boundaries,
Appl. Phys. Lett. 57 (1990) 446–448.
1237
Ceramics International 47 (2021) 1229–1237
[31] J.-R. Lee, Y.-M. Chiang, Bi segregation at ZnO grain boundaries in equilibrium with
Bi2O3-ZnO liquid, Solid State Ionics 75 (1995) 79–88.
[32] F. Greuter, Electrically active interfaces in ZnO varistors, Solid State Ionics 75
(1995) 67–78.
[33] E. Olsson, G.L. Dunlop, The effect of Bi2O3 content on the microstructure and
electrical properties of ZnO varistor materials, J. Appl. Phys. 66 (1989)
4317–4324.
[34] J.P. Gambino, W.D. Kingery, G.E. Pike, L.M. Levinson, H.R. Philipp, Effect of heat
treatments on the wetting behavior of bismuth-rich intergranular phases in ZnO:Bi:
Co varistors, J. Am. Ceram. Soc. 72 (1989) 642–645.
[35] T.M. Shaw, Liquid phase redistribution dueing liquid-phase sintering, J. Am.
Ceram. Soc. 69 (1986) 27–34.
[36] W.D. Kingery, Introduction to Ceramics, 1960.
[37] D. Dey, R.C. Bradt, Grain growth of ZnO during Bi2O3 liquid-phase sintering, J. Am.
Ceram. Soc. 75 (1992) 2529–2534.
[38] T. Senda, R.C. Bradt, Grain growth of zinc oxide during the sintering of zinc
oxide—antimony oxide ceramics, J. Am. Ceram. Soc. 74 (1991) 1296–1302.
[39] S. Bernik, N. Daneu, A. Rečnik, Inversion boundary induced grain growth in TiO2
or Sb2O3 doped ZnO-based varistor ceramics, J. Eur. Ceram. Soc. 24 (2004)
3703–3708.
[40] T. Takemura, M. Kobayashi, Y. Takada, K.E.N. Sato, Effects of antimony oxide on
the characteristics of ZnO varistors, J. Am. Ceram. Soc. 70 (1987) 237–241.
[41] H.-Q. Shao, X.-H. Gao, Z.-C. Cao, Effect of annealing on phase structure and
degradation of a zinc oxide varistor with Si-additive, J. Eur. Ceram. Soc. 17 (1997)
55–59.
[42] K. Eda, M. Inada, M. Matsuoka, Grain growth control in ZnO varistors using seed
grains, J. Appl. Phys. 54 (1983) 1095–1099.
[43] P. Durán, F. Capel, J. Tartaj, C. Moure, A strategic two-stage low-temperature
thermal processing leading to fully dense and fine-grained doped-ZnO varistors,
Adv. Mater. 14 (2002) 137–141.
[44] M. Andres-Verges, A.R. West, Impedance and modulus spectroscopy of ZnO
varistors, J. Electroceram. 1 (1997) 125–132.
[45] L.M. Levinson, H.R. Philipp, AC properties of metal-oxide varistors, J. Appl. Phys.
47 (1976) 1117–1122.
[46] M. Barsoum, M. Barsoum, Fundamentals of Ceramics, CRC press, 2002.
[47] Jacobs K.F. A. Kröger, North-Holland Publishing Company - Amsterdam/London
1973 American Elsevier Publishing Company, Inc. - New York 313 Seiten,
zahlreiche Abbildungen und Tabellen, Kunstleder Preis Dfl. 70.00. Krist. Tech., in:
The Chemistry of Imperfect Crystals, Preparation, Purification, Crystal Growth and
Phase Theory, 2nd Revised Edition 1-9, 1974. K67-K68
[48] K. Hembram, T.N. Rao, M. Ramakrishna, R.S. Srinivasa, A.R. Kulkarni, A novel
economical grain boundary engineered ultra-high performance ZnO varistor with
lesser dopants, J. Eur. Ceram. Soc. 38 (2018) 5021–5029.
[49] R. Tang, C. Jiang, W. Qian, J. Jian, X. Zhang, H. Wang, et al., Dielectric relaxation,
resonance and scaling behaviors in Sr3Co2Fe24O41 hexaferrite, Sci. Rep. 5 (2015)
13645.
[50] J. Wu, C.-W. Nan, Y. Lin, Y. Deng, Giant dielectric permittivity observed in Li and
Ti doped NiO, Phys. Rev. Lett. 89 (2002) 217601.
[51] A.K. Jonscher, The ‘universal’ dielectric response, Nature 267 (1977) 673–679.
[52] X. Zhao, R. Liao, N. Liang, L. Yang, J. Li, J. Li, Role of defects in determining the
electrical properties of ZnO ceramics, J. Appl. Phys. 116 (2014), 014103.
[53] M.A. Alim, Admittance-frequency response in zinc oxide varistor ceramics, J. Am.
Ceram. Soc. 72 (1989) 28–32.
[54] P. Cheng, S. Li, L. Zhang, J. Li, Characterization of intrinsic donor defects in ZnO
ceramics by dielectric spectroscopy, Appl. Phys. Lett. 93 (2008), 012902.