1 s2.0 S135063072100039X Main

Engineering Failure Analysis 122 (2021) 105251
Contents lists available at ScienceDirect
Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal
On the relationship between modification of Bi2O3 by Sb and type

of grain boundaries in ZnO-based varistors
Joanna Warycha a, *, Witold Mielcarek b, Grzegorz Lesiuk a
a
Wroclaw University of Science and Technology, Faculty of Mechanical Engineering, PL-50-370 Wrocław, Poland
b
Electrotechnical Institute, Wroclaw, Poland
A R T I C L E I N F O A B S T R A C T
Keywords: The possibility of eliminating of electrically inactive areas from varistor body with maintaining
Modified microstructure varistor electrical parameters can be achieved by modifying Bi2O3 in such a way that a Bi-rich
Nonlinear properties layer which surrounds the grains of ZnO is as thin as possible and by minimizing of the
Semiconductor materials
amount of additives so as not to form electrically inactive areas in varistor. It has been proven that
Sb2O3
ZnO varistors
modification of Bi2O3 with small quantities of other MeO results in significant changes in the
varistor structure, thereby gaining the uniform distribution of the intergranular phase. The work
contains the results on which Sb2O3 were added in an amount of 15 mol%. After mixing with
Bi2O3 they were sintered and shivered. Modified Bi2O3 was added to the varistor bulk in quan
tities of 1.0, 0.3, 0.2 and 0.1 mol% to study the varistor properties. The best results were obtained
for the varistor doped with 0.3 mol% Bi2O3 modified by Sb, which has the best compatibility with
the mathematically model calculated by statistical methods describing 100% of conductive grain
boundaries. The obtained results of the varistors microstructure modification led additionally to
reduce amounts of additives for about 30% and thus to lower at about 10% of production costs.
1. Introduction
Surges cause overvoltages in the power supply system in various mechanical measurements chains [1–5] due to discharges,
inductive phenomena, switch operation or faults. To minimize the probability of human injury and electrical and electronic system
failures, electrical power systems within a given construction should have adequate potential compensation. Surge protection devices
(SPD) are used to obtain such potential equalization. Varistors are a widespread form of SPD. They are affected by their ageing due to
the amount and amplitude of stress and other factors such as overheating, contamination and humidity. The commercial metal oxide
varistors (MOV) are mainly composed of zinc oxide, which constitutes more than 95 mol% of varistor bulk, and additives responsible
for the nonlinear current-voltage relationships characterizing varistor. The second, after zinc oxide, an essential component of the
varistor is bismuth oxide, having several polymorphic forms occurring in the varistor. Bismuth oxide can form a microstructure by
creating several solid solutions and compounds with other metal oxides. It creates a liquid phase responsible for the zinc oxide’s grains
growth and the transport other dopants during sintering. The melting point of zinc oxide is 1975 ◦ C and of pure bismuth oxide is
825 ◦ C. ZnO’s addition lowers the melting point of bismuth oxide to 740 ◦ C, which significantly accelerates the sintering process. The
liquid phase of bismuth oxide actively influences the sintering process, facilitates transport between the zinc oxide grains, separating
them simultaneously [6].
* Corresponding author.
E-mail addresses: Joanna.Warycha@pwr.edu.pl (J. Warycha), w.mielcarek@wp.pl (W. Mielcarek), Grzegorz.Lesiuk@pwr.edu.pl (G. Lesiuk).
https://doi.org/10.1016/j.engfailanal.2021.105251
Received 10 October 2020; Received in revised form 2 January 2021; Accepted 14 January 2021
Available online 26 January 2021
1350-6307/© 2021 Elsevier Ltd. All rights reserved.
J. Warycha et al. Engineering Failure Analysis 122 (2021) 105251
Fig. 1. Typical U-I characteristics for varistors; A – leakage region, B – normal varistor operating condition, C – high current (saturation) region.
The third fundamental component of the varistor is antimony oxide, which promotes homogenization of grain size of ZnO,
inhibiting their growth, contributes to the increase of the varistor voltage, improves the dielectric properties, improves the non-
linearity coefficient and directs of the chemical reactions in the varistor [7–11]. Varistors have been used for several dozen years
in surge arresters, and are characterized by high energy absorption capacity with high non-linearity coefficients which ensure the high
protection efficiency. Active elements are the grain boundaries of zinc oxide, on which potential barriers are formed. They are
separated by a layer of bismuth oxide, not thicker than 2 nm. As show theoretical calculations, only 0.11 mol% (0.35% vol.) [12] of
bismuth oxide is enough to obtain such a layer. However, due to the low penetration of intergranular areas as well as a tendency to
form agglomerates, in typical technology should be added about ten times more amount of bismuth oxide. Its excess along with zinc-
antimony spinel Zn7Sb2O12 creates areas which are conduction excluded, and therefore unnecessary from the point of the varistor’s
operating principle. Their volume may be at least over ten percent in varistor, and the number of inactive grain boundaries may be
several dozen percent. The elimination of the electrically inactive areas of the varistor and increasing the number of homo-junctions
(effective ZnO grains contact) by improving the grain boundaries penetration is possible by modifying the properties of bismuth oxide
via doping it with other metal oxides [13–15]. Doping can be represented by Sb2O3, [16], ZrO2 [17], WO3 [18], SiO2 [19,20],
Al2O3 [21], CaO [22,23], rare earth oxides (Dy, Sc, Y) [24,25,26], and others. The other way is developing ZnO varistor with a simple
composition with fewer dopants, which enables easy processing and low cost [27–32]. Efforts are also being made to prepare Sb2O3
free varistors having lower sintering temperature and a simple microstructure [33,34].
2. Materials and methods
In Varistors, the relationship between current (I) and voltage (U) (see Fig. 1) is nonlinear – expressed in a power-law relationship:
I = kU α (1)
Where:
k – constant,
α – exponent associated with the type of boundary junctions between grains, expressed as:
logII21
α= (2)
logUU21
The exponent α indicates low and high-nonlinear characteristics of I = U. For α > 30 describe more likely grain contacts.
However, in Sb2O3 free ZnO varistors, the coefficient of non-linearity (α) greater than 55 has not yet been achieved. The ZnO
varistor with a composition with only three dopants (Bi2O3, CaO, Co3O4) from nanopowders (90 nm) has been developed, where the
2
improvement of breakdown field and leakage current is due to grain boundary phases of Ca4Bi6O13 and Ca0.89Bi3.11O5.56 and small
grain size. Increase in α is due to Co3O4 doping in ZnO grains. Increased conductivity with increasing Co3O4 concentration is due to the
increase in carrier concentration; the decreases beyond 2.50 wt% are attributed to a reduction in the samples’ mobility [32].
As the most important in Varistor properties is the number of grain boundaries of zinc oxide. S. Boggs and H. Andoh [35], developed
the mathematically model calculated using statistical methods to determine the approximate amount of inactive grain boundaries in
studied varistors.
In this work, it was assumed that constant grain sizes of hypothetical varistors and a specified number of active grain boundaries
through which the current passes in going from one electrode to the other.
If the ZnO element thickness is T, the average grain thickness is s. The minimum average number of grain boundaries between the
electrodes is L. Suppose the probability of a grain boundary being non-conducting is P. The grains are a cube with constant length, then
to a first approximation. In that case, the mean number of active grain boundaries (B) through which the current passes between
electrodes is:
( )
P
B=L× 1+ (3)
1− P
Where:
B – number of active grain boundaries

L – number of grain boundaries
L = T/S (4)
T – thickness of ZnO Varistor

s – grain size
P – the probability of a grain boundary being non-conducting
Increasing the number of non-conducting grain boundaries increases the current density in the remaining grain boundaries and
results in more excellent grain boundary power dissipation and temperature rise when an active grain boundary is near a cavity in the
element.
This work presents two ways of investigation to reach the technology of varistor with the best grain boundary properties: modi
fication of the bismuth oxide properties via doping it with other metal oxides and reducing amounts of additives of the varistor. Typical
examples devoted to investigations are shown in Fig. 2 and Table 1.
Antimony oxide, the component of the varistor, was selected for the bismuth oxide modification’s research. The selection was
Fig. 2. The commercial varistors.
Table 1
The Commercial Varistors with Their Chemical Compositions and Current-Voltage Parameters, Typical, Commercial (measured).
Varistor Bi2O3 Sb2O3 Co2O3 MnO Cr2O3 NiO ZnO U1mA/1mm [V] α
Typical 1.00 1.00 0.50 0.50 0.40 0.80 95.80 – –
Commercial 1 0.52 0.65 0.67 0.65 0.097 0.59 96.76 216 31.9
Commercial 2 0.701 0.73 0.598 0.317 0.291 1.054 96.31 225 44.3
Commercial 3 0.51 0.68 0.44 0.73 0.065 0.83 95.05 188 44.4
3
Table 2
The Composition of the Varistor Bulk Doped with Modified Bismuth Oxide, in mol%.
Varistor Bi2O3 (BiSb)2O3 Sb2O3 Co2O3 MnO Cr2O3 NiO ZnO
WBi_1 1.0 – 1.0 0.5 0.5 0.4 0.8 95.8

WBiSb_1 – 1.0 1.0 0.5 0.5 0.4 0.8 95.8
WBi_03 0.3 – 0.3 0.4 0.16 0.13 0.23 98.4
WBiSb_03 – 0.3 0.3 0.4 0.16 0.13 0.23 98.4
WBi_02 0.2 – 0.33 0.4 0.16 0.13 0.23 98.5
WBiSb_02 – 0.2 0.33 0.4 0.16 0.13 0.23 98.5
WBi_01 0.12 – 0.33 0.4 0.16 0.13 0.23 98.6
WBiSb_01 – 0.12 0.33 0.4 0.16 0.13 0.23 98.6
where:
WBi_1 - varistor with the 1 mol% of unmodified bismuth oxide
WBiSb_1 - varistor with the 1 mol% of modified Sb bismuth oxide
WBi_03 - varistor with the 0.3 mol% of unmodified bismuth oxide
WBiSb_03 - varistor with the 0.3 mol% of modified Sb bismuth oxide
Fig. 3. SEM images (Tescan) of the two commercial varistors microstructure (a) Commercial 1, (b) Commercial 3, (A – spinel phase, B – bismuth
phase, C – zinc phase).
motivated by decreasing the number of ingredients in the varistor bulk as well as not introducing new ones as materials for samples
preparation, chemically pure ingredients were used.
Modification of bismuth oxide was prepared using the description of the technology:
The oxide Sb2O3, in the amount of 15 mol% was added and mixed with bismuth oxide in the amount of 85 mol%. Such a mixed pre-
samples - (BiSb)2O3 (with composition 15% Sb2O3 / 85% Bi2O3) were sintered at 810 ◦ C by the rise of temperature − 3◦ /min), then
grinded and sieved.
Besides the other ingredients, modified bismuth oxide was added to the varistor bulk, in quantities of 1.0, 0.3, 0.2, 0.1 mol%,
instead bismuth oxide, used in typical varistors. The chemical composition of the varistors presented in this work is shown in Table 2.
The base amount of bismuth oxide added to the varistor bulk was 1 mol%, which is the typical amount of Bi2O3 used in commercial
varistors.
The samples were made using typical ceramics methods in the form of pellets and sintered in 1250 ◦ C. The prepared varistors were
10 mm in diameter and 2 mm thick.
The modified varistors’ current-voltage characteristics were measured using a current generator SPEB-1, in the range of 10 μA −
100 A. The influence of Bi2O3 modification on the electrical properties of varistor was also studied.
To observe the effects of modification and to assess possible mechanisms of interaction between varistor’s components, the
TESCAN (VEGA II SBH) scanning electron microscope with EDS microanalyzer of chemical composition (Oxford Instruments) was
used.
The crystalline phases were studied using the powder diffractometer DRON II with high-temperature X-ray attachment.
4
Table 3
Morphological Analysis of Two Commercial Varistors Phases.
Varistor Phases – Commercial 1 Varistor Phases – Commercial 3
Elements A - Light B - White C - Dark XRD analysis of A - Light B - White C - Dark XRD analysis of
grey – –bismuth grey – zinc the varistor’s free grey – –bismuth grey – zinc the varistor’s free
spinel phase [%at.] phase [% surface spinel phase [%at.] phase [% surface
phase [% at.] phase [% at.]
at.] at.]
O 61.79 57.09 54.11 ZnO 61.74 59.80 58.59 ZnO

Cr 4.15 0.22 – Zn2.33Sb0.67O4 1.84 0.44 0.63 Zn2.33Sb0.67O4
Mn 0.75 – – 0.95 – –
Co 1.71 0.57 0.69 Bi2O3 1.26 0.46 0.66 β Bi2O3
Ni – – – 2.53 – 0.67
Zn 25.08 33.87 45.20 24.05 25.98 37.55
Sb 6.51 0.31 – 7.63 0.52 1.90
Bi – 7.93 – – 12.79 –
Fig. 4. SEM images (Tescan) of the microstructure of varistors with 1 mol% a) unmodified bismuth oxide - WBi_1, b) bismuth oxide modified by Sb
- WBiSb_1.
To determine the approximate amount of inactive grain boundaries, the characteristics of the non-linearity coefficient α for selected
varistors were compared with S. Boggs and H. Andoh [35] by statistical methods constant grain sizes of hypothetical varistors at a
specified number of inactive grain boundaries. Characteristics calculated statistically and experimentally measured were normalized
for height and location.
3. Results
3.1. Microstructure and chemical microanalysis of the commercial varistor
In the research, the samples of two commercial varistors were prepared to use them to compare the effects of the bismuth oxide
modification. As can be seen in Fig. 3, Varistors are characterized by a zinc oxide grains matrix with a size of up to 20 μm. The
intergranular phase contains white areas - enriched with Bi and light grey - containing spinel. The chemical composition of the
intergranular phases is shown in Table 3.
The white phase (B) consists mainly of bismuth and zinc in a significant amount, and Sb and Cr dissolved in the crystalline lattice β
Bi2O3. Light grey phase (A) contains mainly Zn, O, Sb, which form zinc-antimony spinel and small amounts of Ni, Co, Bi, Cr, Mn.
3.2. Microstructure and chemical microanalysis of the modified varistor
The initial modification of bismuth oxide is crucial for uniform distribution of intergranular phases - this effect occurs only when
metal oxide (in this case, antimony oxide) is added to bismuth oxide. When bismuth oxide is added directly to the mass, large clusters
of intergranular phases, which can be seen in the unmodified sample, act here as the reference sample.
Modification bismuth oxide aimed to obtain a free of the intergranular phase of varistors microstructure, unnecessary from the
point of the varistor operation principle, was started with 1 mol% modified Bi2O3 [36,37].
Varistors with 1 mol% of unmodified bismuth oxide are characterized by a zinc oxide grains matrix with a size of up to 20 μm. The
intergranular phase forms clusters with similar 20 μm sizes (Fig. 4a). The intergranular phase contains areas enriched with Bi and
spinel (light grey phase - A).
5
Table 4
Morphological Analysis of Varistor Phases with 1 mol% Unmodified and Modified by Sb Bismuth Oxide.
Varistor Phases with 1 mol% Unmodified Bismuth Oxide - WBi_1 Varistor Phases with 1 mol% Bismuth Oxide Modified by Sb -
WBiSb_1
at.] at.]
O 70.26 66.34 67.20 ZnO 64.21 57.0 58.20 ZnO

Cr 1.72 0.43 – Zn2.33Sb0.67O4 2.14 2.19 – Zn2.33Sb0.67O4
Mn 0.70 – – 0.82 0.78 –
Co 0.58 – – β Bi2O3 0.57 0.76 1.79 Bi2O3
Ni 1.44 – – 1.37 1.53 –
Zn 18.69 13.27 33.80 24.32 29.96 40.01
Sb 5.46 0.76 – 6.29 5.88 –
Bi 0.16 19.2 – 0.29 6.7 –
Fig. 5. SEM images (Tescan) of the microstructure of varistors with 0.3 mol% a) unmodified bismuth oxide - WBi_03, b) bismuth oxide modified by
Sb - WBiSb_03.
Table 5
Morphological Analysis of Varistor Phases with 0.3 mol% Unmodified and Modified by Sb Bismuth Oxide.
Varistor Phases with 0.3 mol% Unmodified Bismuth Oxide - WBi_03 Varistor Phases with 0.3 mol% Bismuth Oxide Modified by Sb -
WBiSb_03
at.] at.]
O 38.31 42.10 26.59 ZnO 64.60 67.63 53.56 ZnO

Cr 7.04 5.64 – Zn2.33Sb0.67O4 2.82 – – Zn2.33Sb0.67O4
Mn 2.09 1.37 0.36 0.91 0.54 – β Bi2O3
Co 1.57 1.42 0.75 1.18 0.80 0.43
Ni 4.58 3.83 0.58 0.86 0,63 –
Zn 39.12 35.33 71.47 25.05 18.16 46.01
Sb 7.29 5.38 0.26 7.15 4.14 –
Bi – 4.94 – 0.25 8.09 –
6
The varistor with 1 mol% bismuth oxide of modified by antimony is characterized by zinc oxide grains size, which does not exceed
10 μm (Fig. 4b). The bismuth - rich phase (B) does not form clusters but small intergranular areas. A light grey spinel phase (A) is also
visible, usually between several grain boundaries. The chemical compositions of the varistors are shown in Table 4.
As the X-ray analysis results, the primary phase of varistors doped with 1 mol% of modified bismuth oxide is crystalline ZnO and
antimony zinc spinel. In contrast, bismuth oxide crystallized in the intergranular spaces and at the ZnO - ZnO grain boundaries.
The bismuth matrix contains mainly bismuth and significant amounts of zinc dissolved in the crystal lattice of β - Bi2O3. The zinc -
antimony spinel phase, contains essential components of the varistor.
Varistor with a dopant of 1 mol% of modified bismuth oxide shows positive changes in the varistor’s microstructure and is
characterized by good current-voltage properties. Because one of the objectives was to reduce the content of additives in the varistor
bulk, varistors with the impoverished amount of components and a decreased range of modified Bi2O3 − 0.3 mol% were prepared.
The varistor with the 0.3 mol% of unmodified bismuth oxide (Fig. 5a and Table 5) is still characterized by large clusters of
intergranular phases (light grey phase - A) of Zn − 40%, Sb − 7%, O − 38% forming zinc-antimony spinel and small amounts of other
additives. The white phase - B is the bismuth-rich matrix and dissolved the varistor components, mainly Zn and Sb. The dark grey - C
phase is zinc oxide grains with dimensions up to 15 μm and small amounts of elements dissolved in them, such as Sb, Cr, Mn, Co, Ni.
Fig. 5b shows a uniform microstructure with zinc oxide grains up to 30 μm, in which cobalt oxide is dissolved. The single inter
granular areas contain grains of antimony zinc spinel with a similar grain size surrounded by a liquid phase rich in bismuth oxide.
Bi2O3 also forms a layer surrounding the zinc oxide grains. The analysis of the microstructure shows a large amount of Zn (over 25%),
Sb (about 7%), and O (about 64%) in the light grey phase (A), which form Zn7Sb2O12 zinc antimony spinel, and additives: Bi, Cr, Mn,
Co, Ni. The white phase (B) mostly consists of O (over 67%), Bi (over 8%), Zn (about 18%), Sb (over 4%) and a small amount of Ni, Mn,
Co. The dark grey phase (C) is a grain of zinc oxide and dissolved a small amount of cobalt.
Sb - WBiSb_02 varistors.
Table 6
WBiSb_02
at.] at.]
O 38.87 27.87 25.61 ZnO 30.50 29.98 21.29 ZnO

Cr 6.82 1.86 – Zn2.33Sb0.67O4 2.82 0.78 – Zn2.33Sb0.67O4
Mn 1.49 0.64 – BiO 0.79 – – (BiSb)2O3
Co 1.43 0.91 0.61 1.73 1.00 0.72
Ni 3.84 1.17 0.29 1.54 0.53 –
Zn 41.50 65.23 73.50 55.37 59.44 77.98
Sb 6.06 1.50 – 7.25 4.81 –
Bi – 0.82 – – 3.45 –
7
According to the X-ray analysis, the primary phase of varistors doped with 0.3 mol% of modified bismuth oxide is crystalline ZnO
and antimony - zinc spinel and crystalline bismuth oxide in the form of β.
An exception is a varistor doped with unmodified bismuth oxide, which does not have Bi2O3 on the varistor’s surface, possibly due
to the evaporation of bismuth oxide from the surface.
Fig. 6a and Table 6 show the varistor’s microstructure with 0.2 mol% of unmodified bismuth oxide, which is characterized by zinc
oxide grains up to 15 μm and clusters of intergranular phases containing bismuth and dissolved in it components of the varistor as well
as the light gray phase - A – represented by Sb − 6%, Zn − 41% and small amounts of additives.
The microstructure of modified (0.2 mol %) varistor’s (Fig. 6b) shows densely packed ZnO grains with dimensions of 10–15 μm and
small amounts of fine clusters of spinel grains up to several micrometres. There are single spinel grains placed at the border of ZnO -
ZnO grains and inside them, represented by Sb − 7%, Zn − 55%, and small amounts of additives.
As shown by X-ray analysis, the ZnO and spinel phases dominate the surface of the varistors. The varistor with Sb-modified bismuth
oxide additionally contains an antimony-bismuth compound with the structure Bi2O3.
The varistor research shows that it is possible to investigate the lower limit of the number of modified Bi2O3 added to the varistor
bulk. For this purpose, varistors with the 0.1 mol% modified bismuth oxide were used, whose chemical composition is shown below.
In the varistor with 0.1 mol% of unmodified bismuth oxide (Fig. 7a) there are large undesirable clusters (up to 70 μm) of inter
granular phases. In contrast, the varistor with modified by Sb (Fig. 7b) is characterized by densely packed ZnO grains (up to 10 μm)
with dissolved in them cobalt oxide, small clusters (up to 25 μm) of zinc antimony spinel, and thin layer rich of modified bismuth where
are dissolved products of the reaction between varistor components. The high content of zinc oxide from the bismuth phase may
indicate the adulteration of results by neighbouring elements due to the bismuth matrix’s small size.
As shown by X-ray analysis, the varistors’ surface is dominated by the ZnO phase and the antimony-zinc spinel phase. Varistors with
Bi2O3 modified by Sb additionally contain an antimony-cobalt compound with an antimony-zinc spinel structure. Table 7
Sb - WBiSb_01 varistors.
Table 7
WBiSb_01
at.] at.]
O 36.76 36.80 26.47 ZnO 28.60 24.63 21.29 ZnO

Cr – 5.69 0.25 Zn2.33Sb0.67O4 3.01 0.41 – Zn2.33Sb0.67O4
Mn 7.63 1.45 0.22 0.82 – –
Co 1.69 1.35 0.73 2.11 0.89 0.72
Ni 1.45 4.58 0.60 1.41 – –
Zn 5.19 43.10 71.50 56.49 71.72 77.98
Sb 39.90 5.64 0.23 7.26 1.07 –
Bi 7.38 1.39 – 0.29 1.29 –
8
350
70
300 60 alfaWBiSb_1
alfaWBi_1
alfaCommercial
250
Nonlinearity Coefficient
Voltage U[V] 50
200 40
150 WBiSb_1 30
WBi_1
100 Commercial 20
10
50
0
0 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100
1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100
Current I[A]
Current I[A]
(a) (b)
350 70
alfaWBiSb_03
300 60 alfaWBi_03
alfaCommercial
250 50
Voltage U[V]
200 40
WBiSb_03
150 WBi_03 30
Commercial
100 20
50 10
0 0
1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100
Current I[A] Current I[A]
(c) (d)
400 70
alfaCommercial
350 Commercial 60 alfaWBiSb_02
WBiSb_02 alfaWBi_02
300 WBi_02
50
250
Voltage U[V]
40
200
30
150
100 20
50 10
0 0
1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100
(e) (f)
700 70
600 60
WBiSb_01 alfaWBiSb_01
500 50
WBi_01 alfaBi_01
Commercial alfaCommercial
400
Voltage U[V]
40
300 30
200 20
100 10
0
0
1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0,01 0,1 1 10 100
(g) (h)
(caption on next page)
9
Fig. 8. (a) Current - voltage characteristics, (b) non-linear coefficients α versus current intensity - for varistors doped with 1.0 mol% of modified
bismuth oxide; (c) current - voltage characteristics, (d) non-linear coefficients α versus current intensity - varistors with the addition of 0.3 mol%
bismuth oxide; (e) current - voltage characteristics, (f) non-linear coefficient α versus current intensity - of the varistors doped with 0.2 mol%
bismuth oxide; (g) current - voltage characteristics, (h) non-linear coefficient α versus current intensity - varistors doped with 0.1 mol% bis
muth oxide.
Table 8
Characteristic Parameters of Modified Varistors.
Samples U1mA α/1mA αmax/A U100A U100A/ U1mA
Commercial 199.5 56.3 59.8/0.007 280.8 1.4

WBi_1 213.6 58.0 58.0/0.001 349.2 1.6
4
WBiSb_1 215.8 52.4 53.2−/3.44*10 323.5 1.5
WBi_03 190.9 28.2 41.7/0.01 365.1 1.9
4
WBiSb_03 180.7 47.3 51.3−/1.53*10 281.1 1.5
WBi_02 196.1 15.5 15.8/0.02 419.7 2.1
WBiSb_02 228.1 24.5 40.9/0.1 375.1 1.6
WBi_01 419.0 8.5 8.5/0.001 680.0/0.04 >1.6
WBiSb_01 184.6 23.7 32.3/0.009 312.0/10 >1.6
3.3. Current-voltage characteristics of varistors doped with modified bismuth oxide
Varistors doped with modified bismuth oxide were electrically tested using direct current in the range of 10 μA – 5 mA and pulse
current from 5 mA to 100 A. The unit voltages (voltage per 1 mm varistor thickness at 1 mA current), protection, and nonlinear
coefficients were calculated. The modified varistors were compared with a varistor doped unmodified bismuth oxide and a commercial
varistor commonly used in electrical equipment. The results are shown in Fig. 8 and Table 8.
The varistor modification with 1.0 and 0.3 mol% of bismuth oxide doped Sb did not significantly differ in the varistor’s current-
voltage characteristics compared with the commercial varistor with unmodified bismuth oxide.
Whereas the decreased amount of bismuth oxide added to the varistor bulk in amount 0.2 mol% and 0.1 mol% influence a sig
nificant voltage increase at higher currents: up to around 400 V/mm for 0.2 mol% and even to 680 V/mm for 0.1 mol%.
Addition bismuth oxide added to the varistor bulk in an amount of 0.1 mol% caused deterioration of the varistor’s nonlinear
properties.
The unit nominal voltages (1.0 mol% and 0.2 mol% varistors) are of the range of 200–400 V/mm, in the same time for the 0.3 mol%
varistors, the nominal voltages are slightly less: unmodified varistor and varistor with the bismuth oxide modified by antimony oxide is
190 and 180 V/mm, respectively.
The nonlinear coefficient α for varistor dopped by 1.0 mol% modified bismuth oxide by Sb is 53.2, and for 0.3 mol% is 51.3. Those
varistors have a protection coefficient (U100A/U1mA) equal to 1.5, which is a favourable phenomenon. Still, only 0.3 mol% varistors are
characterized by a microstructure with minimized amounts of secondary phases compared to the commercial and the unmodified
varistors.
The varistors with the 0.2 mol% and 0.1 mol% modified bismuth oxide by Sb have a protection factor of 1.6 and > 1.6. The value of
the non-linearity coefficient α for this varistor is 40.9 and 32.3, respectively.
4. Conclusions
New technology of ZnO varistors with reduced content of additives (to 1.45 mol% in varistor bulk) has been developed. The best
results were obtained for the varistor with reduced to 0.3 mol% of the modified bismuth oxide amount. A microstructure with
minimized secondary phases characterizes the varistor with the addition of modifying antimony.
The bismuth oxide matrix composition includes bismuth, significant amounts of zinc, antimony, and other elements included in the
varistor mass.
Modification of bismuth oxide slightly differentiates the varistor’s current-voltage characteristics, and the unit voltage is 180.7 V/
mm, protection factor − 1.5, which is a favourable phenomenon non-linearity α is 51.3. According to the mathematical model pro
posed by authors, the proposed varistor’s grain boundaries correspond with 100% of conductive grain boundaries [35].
This research results show advantageous both from an economic point of view, due to reduced amounts of additives for about 30%.
Thus, the 10% lower production costs and from an environmental perspective, because dopants added to varistors are usually oxides of
heavy metals.
The new composition with fewer dopants, easy, typical processing and low cost make this a potential commercial exploitation
component in a wide range of surge protection applications.
Funding
This work was supported by the Polish Ministry of Science and Higher Education [N N510 344534].
10
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.
References
[1] V. Kumar, S. Diyaley, S. Chakraborty, Teaching-learning-based parametric optimization of an electrical discharge machining process, Facta Univ., Ser.: Mech.
Eng. 18 (2) (2020) 281–300.
[2] L. Kruszka, M. Magier, M. Zielenkiewicz, Experimental analysis of visco-plasticproperties of the aluminium and tungsten alloys by means of hopkinson
barstechnique, Appl. Mech. Mater. 566 (2014) 110–115.
[3] K. Krasuski, A. Ciećko, G. Grunwald, D. Wierzbicki, Assessment of velocity accuracy of aircraft in the dynamic tests using GNSS sensors, Facta Univ., Ser.: Mech.
Eng. 18 (2) (2020) 301–313.
[4] K. Saravanakumar, B.S. Lakshminarayanan, V. Arumugam, C. Santulli, A. Pavlovic, C. Fragassa, Quasi-static indentation behavior of GFRP with milled glass
fiber filler monitored by acoustic emission, Facta Univ., Ser.: Mech. Eng. 17 (3) (2019) 425–443.
[5] C. Fragassa, G. Minak, A. Pavlovic, Measuring deformations in the telescopic boom under static and dynamic load conditions, Facta Univ., Ser.: Mech. Eng. 18
(2) (2020) 315–328.
[6] A. Peigney, A. Rousset, Phase transformations and melting effects during the sintering of bismuth-doped zinc oxide powders, J. Am. Ceram. Soc. 79 (8) (1996)
2113–2126.
[7] A. Gubański, W. Mielcarek, G. Paściak, Pomiary prądów TSD warystora, Presented at Postępy w elektrotechnologi”, Materiały konferencyjne. Szklarska Poręba,
Poland, 14-16.09.1994.
[8] T. Kimura, H. Kajiyama, J. Kim, T. Yamaguchi, Effect of inclusion size on the densification of ZnO-Zn7Sb2O12, J. Am. Ceram. Soc. 72 (1) (1989) 140–141.
[9] S. Ezhivalavan, T.R. Kutty, Effect of antimony oxide stochiometry on the non-linearity of zinc oxide varistor ceramics, Mater. Chem. Phys. 49 (3) (1997)
258–269.
[10] Miao Xin, Liming Zhang, Yi Chang, Yunsheng Xia, Luchao Ren, Xianfu Luo, Hongqing Zhou Influence of Sb2O3-ZnO additives on sintering characteristics and
dielectric properties of (Mg0.95Ca0.05)TiO3 microwave ceramics, Ceram. Int. 44(14) (2018) 17107–17112.
[11] R. Nasser, W.H. Othmen, H. Elhouichet, Effect of Sb doping on the electrical and dielectric properties of ZnO nanocrystals”, Ceram. Int. 45 (6) (2019)
8000–8007.
[12] E. Olsson, L.K. Falk, G.L. Dunlop, R. Osterlund, The microstructure of a ZnO varistor material, J. Mater. Sci. 20 (1985) 4091–4098.
[13] T.K. Gupta, Application of zinc oxide varistors, J. Am. Ceram. Soc. 73 (1990) 1817–1840.
[14] J. Li, S. Li, P. Cheng, M. Alim, Advances in ZnO–Bi2O3 based varistors, J. Mater. Sci. 26 (2015) 4782–4809.
[15] N. Raidl, P. Supancic, R. Danzer, M. Hofstätter, Piezotronically modified double Schottky barriers in ZnO varistors, Adv. Mater. 27 (2015) 2031–2035.
[16] F. Cui, X.u. Zhijun, R. Chu, X. He, X. Guo, G. Li, Low temperature sintering ZnO - Bi2O3 based varistor ceramics with low electrical breakdown voltage and high
nonlinear coefficient, Ceram. Int. 17 (October 2020), https://doi.org/10.1016/j.ceramint.2020.09.288.
[17] 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.
[18] 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.
[19] 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.
[20] 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.
[21] 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.
[22] 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.
[23] K. Hembram, T.N. Rao, R.S. Srinivasa, A.R. Kulkarni, CaO doped ZnO–Bi2O3 varistors: Grain growth mechanism, structure and electrical properties, Ceram. Int.
47 (1) (2021) 1229–1237.
[24] 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.
[25] 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.
[26] 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.
[27] N. Daneu, N. Novak Gramc, A. Rečnik, M. Maček Kržmanc, S. Bernik, Shock-sintering of low-voltage ZnO-based varistor ceramics with Bi4Ti3O12 additions,
J. Eur. Ceram. Soc. 33 (2013) 335–344.
[28] A. Rečnik, S. Bernik, N. Daneu, Microstructural engineering of ZnO-based varistor ceramics, J. Mater. Sci. 47 (2012) 1655–1668.
[29] W. Mielcarek, K. Prociow, BaBiO2.77 as a promoter of the varistor property in zinc oxide ceramics, J. Eur. Ceram. Soc. 21 (2001) 711–717.
[30] F. Stucki, F. Greuter, Key role of oxygen at zinc oxide varistor grain boundaries, Appl. Phys. Lett. 57 (1990) 446–448.
[31] T.R.N. Kutty, S. Ezhilvalavan, The influence of Bi2O3 non-stoichiometry on the nonlinear property of ZnO varistors, Mater. Chem. Phys. 38 (1994) 267–276.
[32] 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.
[33] S.N. Bai, T.Y. Tseng, Influence of sintering temperature on electrical properties of ZnO varistors, J. Appl. Phys. 74 (1993) 695–703.
[34] A. Smith, G. Gasgnier, P. Abélard, Voltage-current characteristics of a simple zinc oxide varistor containing magnesia, J. Am. Ceram. Soc. 73 (1990) 1098–1099.
[35] S. Boggs, A. Andoh, A statistical approach to prediction of ZnO arrester element characteristics, IEEE Trans. Power Delivery 16 (4) (2001) 604–610.
[36] J. Warycha, W. Mielcarek, K. Prociów, Improvement of varistor microstructure by Bi2O3 modification. Presented at Interdisciplinary PhD Workshop IIPhDW’09,
Szklarska Poręba, Poland 10–13.05.2009, Published in Recent Advances in Numerical Modelling (2009) 45–50.
[37] J. Warycha, W. Mielcarek, K. Prociów, Potentialities of modification of metal oxide varistor microstructures, Materiały elektrotechniczne 37 (2009) 86–98.
11

1 s2.0 S135063072100039X Main

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1 s2.0 S135063072100039X Main

Uploaded by

Copyright:

Available Formats

Engineering Failure Analysis 122 (2021) 105251

Contents lists available at ScienceDirect

Engineering Failure Analysis

On the relationship between modification of Bi2O3 by Sb and type

2. Materials and methods

B – number of active grain boundaries

T – thickness of ZnO Varistor

Fig. 2. The commercial varistors.

WBi_1 1.0 – 1.0 0.5 0.5 0.4 0.8 95.8

O 61.79 57.09 54.11 ZnO 61.74 59.80 58.59 ZnO

3.1. Microstructure and chemical microanalysis of the commercial varistor

3.2. Microstructure and chemical microanalysis of the modified varistor

O 70.26 66.34 67.20 ZnO 64.21 57.0 58.20 ZnO

O 38.31 42.10 26.59 ZnO 64.60 67.63 53.56 ZnO

O 38.87 27.87 25.61 ZnO 30.50 29.98 21.29 ZnO

O 36.76 36.80 26.47 ZnO 28.60 24.63 21.29 ZnO

Commercial 199.5 56.3 59.8/0.007 280.8 1.4

3.3. Current-voltage characteristics of varistors doped with modified bismuth oxide

Declaration of Competing Interest

You might also like