Europâisches Patentamt

European Patent Office (ÏÏ) Publication number: 0 1 1 5 0 5 0

Office européen des brevets B1

© EUROPEAN PATENT SPECIFICATION

(§) Dateof publication of patent spécification: 11.03.87 © Int Cl.4: H 01 C 7 / 1 0

(ZJ) Application number: 83112992.9
® Dateoffiling; 22.12.83

(3) Varistor.

(§) Priority: 24.12.82 JP 226207/82 (73) Proprietor: Kabushiki Kaisha Toshiba

30.09.83 JP 180171/83 72, Horikawa-cho Saiwai-ku
Kawasaki-shi Kanagawa-ken 210 (JP)

(§) Date of publication of application:

08.08.84 Bulletin 84/32 (72) Inventor: Kanai, Hideyuki
c/o TOKYO SHIBAURA DENKI K.K. 72 Horikawa-
cho
(§) Publication of the grant of the patent: Saiwai-ku Kawasaki-shi Kanagawa-ken (JP)
11.03.87 Bulletin 87/11 Inventor: Furukawa, Osamu
c/o TOKYO SHIBAURA DENKI K.K. 72 Horikawa-
cho
(§) Designated Contracting States: Saiwai-ku Kawasaki-shi Kanagawa-ken (JP)
CH DE FRGB Ll NL SE Inventor: Imai, Motomasa
c/o TOKYO SHIBAURA DENKI K.K. 72 Horikawa-
cho
(§) Références cited: Saiwai-ku Kawasaki-shi Kanagawa-ken (JP)
EP-A-0 029 749 Inventor: Takahashi, Takashi
DE-B-2 842 287 c/o TOKYO SHIBAURA DENKI K.K. 72 Horikawa-
US-A-4165 351 cho
Cû Saiwai-ku Kawasaki-shi Kanagawa-ken (JP)
PATENTS ABSTRACTS OF JAPAN, vol. 1, no.
o 123, 17th October 1977, page 5098 E 77;
(3) Représentative: Hansen, Bernd, Dr.rer.nat. et al
CHEMICAL ABSTRACTS, vol. 87, 1977, page Hoffmann, Eitlé & Partner Patentanwalte
o 581, no. 61556d, Columbus Ohio (USA); Arabellastrasse 4
in D-8000 Mûnchen 81 (DE)
PATENTS ABSTRACTS OF JAPAN, vol. 2, no.
19, 8th February 1978, page 11102 E 77;
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
CL be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European patent convention).
LU
Courier Press, Leamington Spa, England.
BACKGROUND OF THE INVENTION
This invention relates to a varistor comprising a sintered body containing a zinc oxide (ZnO) as a
principal component. Particularly, it relates to a varistor having excellent life performance when a direct
current is applied.
Various kinds of varistors (i.e., voltage-current non-linear resistors) for which extensive researches
have been made include a varistor made of a sintered body containing ZnO as a principal component. In
the case of such a varistor, it has been attempted to secure the desired performances by adding various
kinds of auxiliary components.
Recently, researches and developments have been made on the direct current transmission, which,
different from the alternating current transmission, impose very severe conditions upon the varistor
because the electric field is applied to the non-linear resistor always in a single direction. Under the existing
state of the art, however, there has acquired no varistor having a direct current life performance excellent
enough to be endurable against such severe conditions. For instance, known varistors are those
comprising ZnO added with Bi203, CoO, Sb203, NiO and MnO as disclosed in Unexamined Patent
Publication (KOKAI) No. 119188/1974, those comprising znO added with B and Bi as disclosed in Patent
Publication (KOKOKU) No. 19472/1971 and those comprising ZnO added with a glass containing a boron
oxide as disclosed in Patent Publication (KOKOKU) No. 33842/1981, etc., every of which, however, does not
secure sufficient performance; for instance, they are poor in the life performance since the leakage current
at the application of the direct current increases with lapse of time and the thermal runaway is caused
thereby.
Sintered varistors are also known from CHEMICAL ABSTRACTS, Vol. 87, 1977, page 581, No. 61556d.
Sintered ZnO varistors are obtained by adding 0.01-0.25% borosilicate glass frit to ZnO. The glass frit is
obtained from a mixture containing 0.1-5 mol % Bi2O3, 0.1-5 mol % CoO, 0.1-5 mol % MnO, 0.5-5 mol
% NiO, 0.05-7 mol % Sb203, and 5-30 wt% AgzO.
Moreover, demands for the performances such as the voltage-current non-linearity and the life
performance have recently become severer as the ultra-high voltage (UHV) power transmission has made
progress.
Thus, demands for improvements of the performances such as the life performance and the non-
linearity have become larger year by year, and researches have been made everywhere in order to fulfil
such demands.
This invention, made on account of the foregoing, aims at providing a varistor having excellent direct
current life performance. It further aims at providing a varistor having excellent voltage-current non-
linearity.

SUMMARY OF THE INVENTION

According to this .invention, there is provided a varistor made of a sintered body comprising;
a basic component comprising a zinc oxide (ZnO) as a principal component and, as auxiliary
components, bismuth (Bi), cobalt (Co), manganese (Mn), antimony (Sb) and nickel (Ni) in an amount, when
calculated in terms of Bi203, Coz03, MnO, Sb203 and NiO, respectively, of Bi203: 0.1 to 5 mol %, C0203: 0.1
to 5 mol %, MnO: 0.1 to 5 mol %, Sb2O3: 0.1 to 5 mol % and NiO: 0.1 to 5 mol %; and
an additional component comprising boron (B) in an amount, when calculated in terms of Bz03, of
0.001 to 1 wt % based on said basic component.
In another embodiment of this invention, the above basic component may further comprise at least
one of aluminum (Al), indium (In) and gallium (Ga) in a prescribed amount and the above additional
component may be i) boron (B) with or without further addition of at least one of silver (Ag) and silicon (Si);
in a prescribed amount or ii); a glass containing boron (B) in a prescribed amount.
This invention will be described below in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Figs. 1, 2, 3, and 5 each show performance curves of varistors; and
Figs. 4(a) to 4(d) are X-ray diffraction patterns identifying crystal structures.

DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

A first embodiment of this invention is a varistor made of a sintered body comprising;
a basic component comprising a zinc oxide (ZnO) as a principal component and, as auxiliary
components, bismuth (Bi), cobalt (Co), manganese (Mn), antimony (Sb) and nickel (Ni) in an amount, when
calculated in terms of Bi203, CO2O3, MnO, Sb203 and NiO, respectively, of Bi203: 0.1 to 5 mol %, C0203: 0.1
to 5 mol %, MnO: 0.1 to 5 mol %, Sb203: 0.1 to 5 mol % and NiO: 0.1 to 5 mol %; and
an additional component comprising boron (B) in an amount, when calculated in terms of B2O3, of
0.001 to 1 wt % based on said basic component.
By assuming the composition comprising Bi203, Coz03, MnO, Sb203 and NiO to which B has been
added as in the above, the direct current life performance is improved remarkably. Also, the life
 performance at the application of an alternating current and the non-linearity as well are particularly
excellent.
The reason why the content of each of Bi203, Co203, MnO, Sb203 and NiO is defined in this
embodiment to range from 0.1 to 5 mol % is that the non-linearity and the life performance become
deteriorated if it ranges otherwise. The performances are improved by adding B to the above basic
components. In particular, the direct current life performance is dramatically improved. More specifically
speaking, when only the basic components are present, the leakage current increases with lapse of time in
the application of a direct current, causing the thermal runaway, thereby making it impossible to use a
varistor for the direct current transmission, but, by the addition of B in an amount, calculated in terms of
B2O3, of 0.001 to 1 wt %, the direct current life performance is improved because of a small increase in the
leakage current with lapse of time. If the amount is less than 0.001 wt %, no effect of the addition of B will
be present; the direct current life performance is particularly improved by the addition thereof in an
amount of 0.001 wt % or more. If it exceeds 1 wt %, not only the direct current life performance but also the
alternating current life performance and the non-linearity will become deteriorated on the contrary.
The content of each of the above components are expressed in terms of a calculated value, and
therefore they may be added in the form of every kind of carbonates, etc. For instance, the boron may be
added in various kinds of forms such as B2O3, H3BO3, HB02, B2(OH)4, ZnB40,, AgBO2, ammonium borate,
Ag2B4O7' BaB4O7, Mg(BO2)2·8H2O, MnB4O7·8H2O, BiBO3, Ni3(BO3)2, Ni2B2O5, etc.
Taking account of homogeneous mixing of the raw materials, it is preferred that the boron component
takes the form readily soluble in water and is mixed as an aqueous solution. As the boron readily soluble in
water, there may be mentioned, for example H3B03, HBO2, B2(OH)4, ZnB40,, ammonium borate, AgBO2,
Ag2B4O7, etc.
According to a second embodiment of this invention, the non-linearity can be still improved by the
further addition of at least one of Al, In and Ga to the basic component. In this embodiment, the additional
component may comprise B with or without further addition of at least one of Ag and Si.
Namely, the second embodiment is a varistor made of a sintering body comprising;
a basic component comprising a zinc oxide (ZnO) as a principal component and, as auxiliary
components, bismuth (Bi), cobalt (Co), manganese (Mn), antimony (Sb) and nickel (Ni) in an amount, when
calculated in terms of Bi2O3, CO2O3, MnO, Sb2O3 and NiO, respectively, of Bi2O3: 0.1 to 5 mol %, C0203: 0.1
to 5 mol %, MnO: 0.1 to 5 mol %, Sb203: 0.1 to 5 mol % and NiO: 0.1 to 5 mol %; and further at least one
selected from the group consisting of aluminium (Al), indium (In) and gallium (Ga) in an amount, when
calculated in terms of Al3+, ln3+ and Ga3+, respectively, of from 0.0001 to 0.05 mol %; and
the above additional component comprising the boron (B) only.
In this embodiment, the additional component may further comprise at least one selected from the
group consisting silver (Ag) and silicon (Si) in an amount, when calculated in terms of Ag20 and Si02, of
from 0.002 to 0.2 wt % and 0.001 to 0.1 wt %, respectively, based on said basic component.
The addition of Al3+, In3+ and Ca3+' becomes effective when added in the amount of not more than 0.05
mol %. The Al3+ et al may be added in a trace amount to produce effective results, and, in particular, in an
amount of not less than 0.0001 mol % to give excellent effects. When they are added too much, the
performances become deteriorated on the contrary. The addition of Al3+ et al produces great effects
particularly to the improvement of the non-linearity. Since the effect in the improvement in performances
can be achieved by the addition thereof in a very small amount as mentioned above, it is also preferred that
they are mixed or added in the form of an aqueous solution of a water soluble compound such as nitrate.
The content of Ag20 and SiO2 is defined in this invention to range from 0.002 to 0.2 wt % and 0.001 to
0.1 wt %, respectively. This is because the improvement of the life performance is hardly effective and even
the non-linearity becomes deteriorated on the contrary when it exceeds the above range. The Ag20 and
SiO2 each may be added solely in order to be effective in improving the life performance, but can be added
in combination of the both of them in order to be more effective.
The content of B2O3 when added in combination with Ag2O and/or SiO2 should preferably range from
0.002 to 0.2 wt % based on the basic component.
In a third embodiment of this invention, a glass containing a prescribed amount of boron (B) may be
used as the additional component mentioned in the above second embodiment. Namely, the third
embodiment is a varistor made of a sintered body comprising;
a basic component comprising a zinc oxide (ZnO) as a principal component and, as auxiliary
components, bismuth (Bi), cobalt (Co), manganese (Mn), antimony (Sb) and nickel (Ni) in an amount, when
calculated in terms of Bi203, CO2O3, MnO, Sb203 and NiO, respectively, of Bi203: 0.1 to 5 mol %, C0203: 0.1
to 5 mol %, MnO: 0.1 to 5 mol %, Sb203: 0.1 to 5 mol % and NiO: 0.1 to 5 mol %; and further at least one
selected from the group consisting of aluminum (Al), indium (In) and gallium (Ga) in an amount, when
calculated in terms of AI3+, In3+ and Ga3+, respectively, of from 0.0001 to 0.05 mol %; and
an additional component comprising a glass containing boron (B) in an amount, when calculated in
terms of B2O3, of from 0.001 to 1 wt % based on said basic component.
The same effects as in the second embodiment of this invention can be obtained by adding the B-
containing glass to the above-mentioned basic component comprising Bi203, Co203, MnO, Sb203, NiO, and
at least one of AI, In and Ga. To be added is a glass containing B in an amount, when calculated in terms of
B2O3, of from 0.001 to 1 wt %, whereby the direct current life performance is also improved because of a
small increase in the leakage current with lapse of time. If the amount is less than 0.001 wt %, no effect of
the addition of the B-containing glass will be present; the direct current life performance is particularly
improved by the addition thereof in an amount of 0.001 wt %-or more. If it exceeds 1 wt %, not only the
direct current life performance but also the alternating current life performance and the non-linearity will
become deteriorated on the contrary.
Even when the basic component contains no Al3+, In3+, and/or Ga3+, the life performance can be
improved to a certain extent by the addition of B or B-containing glass, but in such a case, the non-linearity
becomes deteriorated and moreover the capacity of energy dissipation is seriously lowered.
When a varistor is used for a device such as a lightening arrester, designed for the purpose of
absorbing a large surge, it is required for it to have good capability of energy dissipation. In general, in
orderto represent the energy dissipation capability of a varistor by a definite value, employed is the energy
dissipation capability per unit volume when a rectangular current wave of 2 ms is applied. JEC (Standard of
the Japanese Electrotechnical Committee)-203, page 43, for example, discloses a typical test method
therefor.
When the energy dissipation capability is small, flash-over or puncture is caused by the application of a
large current impulse to a resistor, resulting in no achievement of the object of absorbing the surge and
further resulting in remarkable lowering of the performances of the arrester and the like. The energy
dissipation capability becomes smaller in the varistor of a system containing no Al3+, ln3+, and/or Ga3+.
Crystal structure has been examined with respect to the Bi203 contained in the varistor according to
this invention. As a result, the a-phase (orthorhombic lattice) was found to have been formed. Proportion of
the a-phase in the total Bi203 is variable depending on the production conditions such as temperature and
composition. Thus, the variation of performances depending on the proportion of the a-phase was
examined. As a result, it was found that the direct current life performance becomes especially excellent
when the amount of the a-phase in the total amount of the Bi203 exceeds 10%, and more preferably, 30%. It
was also found that the energy dissipation capacity becomes stable in a desired value when the a-phase
exceeds 50%. This tendency was present when the composition was selected within the scope of this
invention. It was the case also in the system where the Al3+, ln3+ and/or Ga3+ were contained additionally.
However, the a-phase was not formed when the basic components were comprised differently. For
instance, the a-phase was not formed when the B203 was added to and contained in a
ZnO-Bi2O3-CO2O3-MnO-NiO-Sb2O3 system to which added were Cr203 and Si02; besides, both the
non-linearity and the life performances were not improved.
Meanwhile, the a-phase tends to be transformed to the other phase by means of a heat treatment.
Accordingly, it is preferred that a step involving such a heating that may cause the transformation of the
crystal phase is not applied.
As described above, it is possible according to this invention to produce a varistor having excellent
direct current life performance. The varistor according to this invention is excellent in the non-linearity and
the alternating current life performance, too.
Accordingly, the varistor of this invention is useful in a lightning arrester as a surge absorber for the
direct current high voltage transmission. It is also useful for an alternating current transmission. It is
particularly suitable for use in UHV power transmission. Moreover, it brings about great advantages in the
production thereof, such as reduction of production cost and the like, because both the varistors for the
direct current and the alternating current can be produced on the same assembly line. It is also useful as an
element for electronic equipments of private use as it is excellent in every performance.
This invention will be described in greater detail by the following Examples.

Example 1
Mixed to ZnO were Bi203, Co203, MnO, Sb203, NiO in the desired compositional proportions, to which
added was an aqueous solution in which H3B03 as a compound containing B was dissolved in the desired
proportion. After mixing of these, PVA was added as a binder to effect the granulation, and then disk-like
compact bodies were formed. Each of these bodies was dried and thereafter sintered at 1100 to 1300°C for
about 2 hours and, further, both surfaces thereof were polished to form a sintered body having diameter of
20 mm and thickness of 2 mm.
On both sides of each of the samples thus formed a pair of electrodes were formed by means of
spraying of fused AI to make varistors having the composition shown in Table 1, and performances thereof
were examined. Results are shown in Table 1. Also shown in the Table 1 are comparative examples for the
varistors having the composition outside this invention. In Table 1, the voltage-current non-linearity is
indicated in terms of V2kA/V1mA and the life performace in terms of L400· The content of B is indicated in parts
by weight based on the basic components and calculated in terms of B203.
l(400) designates, while a sorounding temperature is maintained at 90°C, a leakage current measured at a
room temperature after continuous application of a voltage of 0.75 X VtmA for 400 hours in the case of D.C.,
or a leakage current measured at a room temperature after continuous application of a voltage of
0.85 x V1mA in the case of A.C. 1(0) designates an initial value, and L400 indicates the ratio of I (400) and I (0).
Mark X in the Table indicates that the thermal runaway took place in 400 hours.
 As is apparent from Table 1, it is noted that the examples of this invention show superior
performances, in particular, have excellent life performance. As will be seen from the comparative
examples (Sample Nos. 20 to 29), the effect of the addition of B is not achieved when the basic components
have the composition outside this invention and both the direct current life performance and the
alternating current life performance become extremely inferior. Also, as will be seen from another
comparative example (Sample No. 30), the effect of the addition of B is not present when it is added in a too
small amount and the thermal runaway takes place at the application of the alternating current. When it is
added in a too large amount (Sample No. 31), every performance becomes deteriorated on the contrary.
Further, changes in the leakage current as time lapses were examined with respect to a varistor having
the composition of Sample No. 17. The changes in the leakage current as time lapses is indicated by I(t)/I(0).
Measurements were carried out in the same manner as in the measurements of the foregoing 1(400)/1(0).
Results are shown in Fig. 1, wherein the solid line (A) indicates the case where D.C. was applied and the
dotted line (B) the case where A.C. was applied.
As is apparent from Fig. 1, it is noted that the I(t)/I(o) shows substantially constant value in the case of
A.C. application and, in the case of D.C. application, it is saturated after lapse of about 300 hours, showing
excellent performance. Thus the life performance is very excellent because of little changes in the leakage
current.
For comparison, data in the cases where the boron was added in the form of glass are also shown
together in Fig. 1. Namely, the cases where a bismuth borosilicate glass was added and the boron content
to the whole was controlled to that similar to Sample No. 17; the solid line (C) designates the direct current
life performance and the dotted line (D) the alternating current life performance.
As is apparent from Fig. 1, the leakage current increases with lapse of time in the case of direct current
and there is found a tendency that the thermal runaway may take place with further lapse of time. In the
case of alternating current, there is shown a tendency that the leakage current increases after lapse of about
300 hours.
Thus, it is noted that the performances become superior by adding B in the form other than the glass.
When it is added in the form of glass, the performances are considered to be inversely affected because of
the contents of components other than the boron being in excessive amounts.
As explained in the foregoing, it is possible according to this invention to obtain a varistor which is
excellent, in particular, in the direct current life performance, It is also excellent in the non-linearity and the
alternating current life performance.

Example 2
Examples where Al3+ was added will be given in the following: ZnO, Bi2O3, Co2O3, MnO, Sb2O3, NiO,
AI(NO3)3 9H20 and a compound containing B were mixed and varistors having the composition shown in
Table 2 were produced in the same procedures as in Example 1. Performances thereof were also examined
to obtain the results shown in Table 2.
 As is apparent from Table 2, the non-linearity is improved by adding Al3+ to the system, as compared
with the cases shown in Table 1. Also in the Al3+-containing system, the thermal runaway takes place when
the content of B is too small, as in the cases shown in Table 1. When it is too large, every life performance
and the non-linearity as well become also deteriorated.
When compared numerically, the improvement in the non-linearity may appear to be small, but, in
practical use, the numerically small improvement produces a great effect.
Further, shown in Fig. 2 are changes in the life performances (where solid line: D.C., dotted line: A.C.)
when the B201 contents are changed with respect to the samples having the composition of Sample No. 32.
As is apparent from Fig. 2, the life performances are excellent in both the cases of D.C. and A.C. when
the B203 content is in the range of from 0.001 to 1.0 wt %. When it is less than 0.001 wt %, the deterioration
of D.C. life performance becomes remarkable although that of A.C. life performance is kept in a small
degree. When it exceeds 1 wt %, the deteriorations of both the D.C. and A.C. life performances become
remarkable. The same tendency was seen also in the varistor of the system where the Al3+ was not
contained.

Example 3
It is possible to obtain the same effects with the case of the Al3+ addition by adding In3+ or Ga3+. Table
3 shows performances of varistors prepared by adding at least one components of Al(NO3)3·9H2O,
ln(N03)3·3H20 and Ga(NO3)3·xH2O according to the same procedures as in Example 2.
 As is apparent from Table 3, the system in which B2O3 is contained to the basic components
comprising ZnO, Bi203, C0203, MnO, Sb303, NiO and at least one kind of AL3+, Ga3+ and ln3+, can be
effective for not only the improvement in the life performance, particularly the direct current performance,
which attributes to the addition of B203, but also the improvement in the non-linearity. On the contrary,
however, all the performances become determinated when the contents of Al3+, Ga3+ and ln3+ are too
large.

Example 4
ZnO, Bi203, CO2O3, MnO, Sb203, NiO, and at least one of Al(N03)3·9H2O, ln(NO3)3H20, Ga(NO3)3·xH2O,
and also B203 and at least one of Ag20 and Si02 were mixed and varistors having the composition shown in
Tables 4 and 4a were produced in the same manner as in Example 1. The performances thereof were also
examined. Results are shown in Tables 4 and 4a. Also shown in the Tables are comparative examples for
the varistors having the composition outside this invention. In Tables, the voltage-current non-linearity is
indicated in terms of V1kA/V1mA and the life performance in terms of L200.

wherein the voltage V (after 200 hours) is measured at room temperature after 95% of V1mA has been
continuously applied for 200 hours at temperature of 150°C. The voltage in the above formula indicate
sinusoidal peak voltage of 50 Hz when a current of 1 mA flows.
Mark X in the Tables indicates that the thermal runaway took place within 200 hours.
 As is seen from Table 4, Sample Nos. 121 to 192 which are examples of this invention show that both
the non-linearity (V1kA/V1mA and the life performance (L200) thereof are superior to those of Sample Nos.
205 to 207 which are comparative examples.
Sample Nos. 121 to 123 contain B203 and neither Ag20 nor Si02; Sample Nos. 130 to 147 B2O3 and
either Ag20 and Si02; Sample Nos. 157 to 192 B2O3 and both Ag20 and Si02. It can be seen from these
examples that the more kinds of these components are added, the better the life performance is improved.
However, as will be seen from Sample Nos. 205 to 207 which are comparative examples, the improvement
of the life performance is not effective and moreover even the non-linearity is impaired when the contents
of these components are excessive.
Sample Nos. 208 to 227 shown in Table 4a contain at least one of Al3+3, Ga3+ and ln3+, from which it is
seen that the life performance is also improved.

Example 5
ZnO, Bi203, Co203, MnO, Sb203, NiO, Al(NO3)3·9H2O and B-containing glass were mixed and varistors
having the composition shown in Table 5 were produced in the same procedures as in Example 1. The
performances thereof were also examined in the same manner as in Example 1. Results are shown in Table
5. Also shown in Table 5 are comparative examples for the varistors having the composition outside this
invention. In Table 5, the voltage current non-linearity is indicated in terms of V2kA/V1mA and the life
performance in terms of L400·
In Table 5, mark X indicates that the thermal runaway took place in 400 hours; symbols A to H denote
the kind of glass as identified below:

A: Ag20-B203-Si02-Bi203 glass
B: B2O1-SiO2-Bi2O3 glass
C: ZnO-B2O3-SiO2 glass
D: PbO-B2O3-Bi2O3 glass
E: PbO-B2O3 glass
F: ZnO-B2O3-V205 glass
G: ZnO-B2O3-V2O5-SiO2 glass
H: B2O3-SiO2-BaO-MgO-Al2O3 glass
 As is apparent from Table 5, examples of this invention show smaller D.C. L400 value as being excellent
in the direct life performance. It is also apparent therefrom that other performances such as the alternating
current life performance (A.C. L400) and non-liniarity (V2kA/V1mA) are also excellent.
As is seen from comparative examples of Sample Nos. 338 and 339, the D.C. life performance becomes
inferior when the content of glass is too small, and when it is too large not only the D.C. life performance
but also the A.C. life performance and the non-linearity become inferior.
As is also seen from comparative examples of Sample Nos. 340 and 341, even when the glass were
contained in the desired amount, the non-linearity becomes remarkably inferior if the content of A1 is
outside the range of this invention. In particular, when the A1 is not contained, the heat runaway takes
place in both the cases of A.C. and D.C. When the A1 content is too small, the life performance becomes
inferior although not so remarkable as in the case of a large A1 content.
When the content of A1 is outside the range of this invention, there is remarkable lowering of energy
dissipation capability. Table 6 shows the energy dissipation capability of varistors having the composition
of Sample No. 316 with varied content of A1. Similarly, Fig. 3 shows a characteristic curve for the energy
dissipation capability.
As will be seen from Table 6 and Fig. 3, the energy dissipation capability is around 250 J/cm3 when the
A, content is inside the invention, but it is 200 J/cm3 or lower when the content is outside the invention.
Substantially the same restults as shown in Fig. 3 were obtained in the varistors reported in Examples
2, 3 and 4 where B was added not in the form of the B-containing glass.

Example 6
The same effects were obtainable when at least one of the Al3+, ln3+ and Ga3+ were used and tested in
the same manner as in Example 5. Results are shown in Table 7.
 As is apparent from Table 7, the employment of In and Ga gives the same effect as in the employment
of Al. Thus, the varistors having, in particular, excellent D.C. life performance can be obtained by the
addition of the B-containing glass.

Example 7
Bi203 phases in the sintered body were further examined. Bi203 can exist in the sintered body by
assuming various phases such as a-phase (orthorhombic lattice), β-phase (tetragonal lattice), y-phase
(body-centred cubic structure) and δ-phase (face-centred cubic structure), whose interplanar spacings are
similar to each other. The proportion of these phases varies depending on the composition of the sintered
body and'the conditions for the production of the same. Moreover, it is difficult to identify the crystal phase
because a solid solution is formed with the additives such as Sb, Mn, Co, Ni, B, Si, Ag and so on whereby
the crystal lattice are distorted. To give a reference, Figs. 4(a) to 4(d) show X-ray diffraction patterns of the
@-phase, β-phase, γ-phase and δ-phase, respectively, when Cu Ka radiation was used. Although the peak
positions deviate from those shown in the ASTM (American Society for Testing Materials) Powder
Diffraction Data File, depending on the kinds and contents of the additives, there can be recognized
characteristic profiles wherein the a-phase thas three peaks at around 28 = 27 to 29° and the y-phase a
small peak at around 26 = 31°. These facts or data were taken into account to identify the crystal phase.
Fig. 5 shows the relationship between the amount of a-phase and the life performance of the varistors
produced in the same procedures as in the foregoing and by use of materials having the composition
comprising ZnO as a principal component and, as auxiliary components, 0.1 to 5 mol% each of Bi203,
Co203, MnO, Sb2O3 and NiO, and 0.0001 to 0.05 mol% of Al(NO3)3·9H2O when calculated in terms of Al3+, to
which added was 0 to 1.0 wt% of the H3BO3 when calculated in terms of B203. In Fig. 5, solid line designates
the direct current life performance and dotted line the alternating life performance.
The amount of a-phase was determined by Ra shown below:

wherein;
I(a): Maximum intensity by X-ray diffraction
l(β): "
I(γ):
l(δ):

As is seen from Fig. 5, the life performances in both the direct current and the alternating current are
improved as the value Ra becomes larger.
In particular, when a direct current is applied, L400 is improved at Ra>10 and it becomes substantially
constant at R@≥30. When Ra is too small, the thermal runaway takes place in the case of D.C. application.
Ra = 0, when no B is added. The a-phase begins to exist as the B is added. From a view point of the content
of B, the Ra becomes almost 100 when it is in the range of 0.02 to 0.1 wt% being calculated in terms of B2O3,
which is a preferable range.
The a-phase of Bi203 becomes present by the addition of a trace amount of B as mentioned above, but
the Bi203 becomes amorphous if B is contained in a too large amount.
A.C. L400 is also improved, though not so remarkably as in D.C. L400' as the a-phase increases,
particularly when Ra?30.
Thus, the varistors having very good life performance can be obtained when Ra>10, especially when
R@≥30. The same tendency was seen also in the varistor of the system where Al3+ was not contained.
Furthermore, as also shown in fig. 5 by chain line, the energy dissipation capability can be improved at
around R@≥50, in particular, it becomes stable in a desired state at around R@≥60.
Table 8 shows Ra(%) of the samples having various composition of B. The sample numbers
correspond to the examples and the comparative examples described in the foregoing. A.C. L400 and D.C.
L400 also designate the same values mentioned in the foregoing.
 As is seen from Table 8, excellent performances are obtained when Ra is not less than 10%. No
a-phase is produced in Sample Nos. 36 and 66 which are comparative examples.

1. A varistor of a sintered body comprising:

a basic component comprising a zinc oxide (ZnO) as a principal component and, as auxiliary
components, bismuth (Bi), cobalt (Co), manganese (Mn), antimony (Sb) and nickel (Ni) in an amount, when
calculated in terms of Bi203, Co203, MnO, Sb2O3 and NiO, respectively, of Bi203: 0.1 to 5 mol%, CO2O3: 0.1
to 5 mol%, MnO: 0.1 to 5 mol%, Sb203: 0.1 to 5 mol% and NiO: 0.1 to 5 mol%; and
an additional component comprising boron (B) in an amount, when calculated in terms of B203m of
0.001 to 1 wt% based on said basic component.
2. The varistor according to Claim 1, wherein the sintered body comprises said basic component which
further comprises at least one selected from the group consisting of aluminum (Al), indium (In) and gallium
(Ga) in an amount, when calculated in terms of Al3+, ln3+ and Ga3+, respectively, of from 0.0001 to 0.05
mol%.
3. The varistor according to Claim 2, wherein the additional component further comprises at least one
selected from the group consisting of silver (Ag) and silicon (Si) in an amount, when calculated in terms of
Ag20 and Si02, of from 0.002 to 0.2 wt% and 0.001 to 0.1 wt%, respectively, based on said basic
component.
4. The varistor according to Claim 2, wherein said additional component is a glass.
5. The varistor according to Claim 3, wherein said boron is added in an amount, when calculated in
terms of B203, of from 0.002 to 0.2 wt% based on said basic component.
6. The varistor according to Claim 1, wherein said boron is added in the form of the compounds or
mixtures selected from the group consisting of B203, H3BO3, HB02, B2(OH)4, ZnB407, AgB02, ammonium
borate, Ag2B4O7 BaB4O7, Mg(BO2)2·8H2O, MnB407.8H20, BiB03, Ni3(BO3)2 and Ni2B20s.
7. The varistor according to Claim 2, wherein said boron is added in the form of the compounds or
mixtures selected from the group consisting of B203, H3BO3, HB02, B2(OH)4, ZnB407, AgB02, ammonium
borate, Ag2B4O7, BaB407, Mg(BO2)2·8H2O, MnB0407.8H20, BiB03, Ni3(B03)2 and Ni2B2O5.
8, The varistor according to Claim 2, wherein said aluminum, indium and gallium is added in the form
of Al(NO3)3·9H2O, ln(NO3)3·9H2O and Ga(NO3)3.·xH2O, respectively.
9. The varistor according to Claim 4, wherein said glass containing boron is selected from the group
consisting of Ag2O-B2O3-SiO2-Bi2O3 glass, B203-Si02-Bi203 glass, ZnO-B2O3-SiO2 glass,
PbO-B2O3-Bi2O3 glass, PbO-B2O3 glass, ZnO-B2O3-V2O5 glass, ZnO-B2O3-V2O5-SiO2 glass and
B2O3-SiO2-BaO-MgO-Al2O3 glass.
10. A varistor which comprises Bi203 having not less than 10% of a-phase.
11. The varistor according to Claim 10, said a-phase is not less than 30%.
12. The varistor according to Claim 10, wherein said a-phase is not less than 50%.
13. The varistor according to Claim 10, wherein said a-phase is substantially 100%.
 1. Varistor, hergestellt aus einem Sinterkörper, umfassend:
eine Grundkomponente, umfassend ein Zinkoxid (ZnO) als Hauptkomponente, und als Hilfskom-
ponenten Wismut (Bi), Kobalt (Co), Mangan (Mn), Antimon (Sb) und Nickel (Ni) in einer Menge, berechnet
als Bi203, CO2O3, MnO, Sb203 bzw. NiO, von Bi2O3: 0,1 bis 5 Mol.%, C0203: 0,1 bis 5 Mol.%, MnO: 0,1 bis 5
Mol.%, Sb203: 0,1 bis 5 Mol.% und NiO: 0,1 bis 5 Mol.%, und
eine zusätzliche Komponente, umfassend Bor (B) in einer Menge, berechnet als B203, von 0,001 bis
Gew.%, bezogen auf die Grundkomponente.
2. Varistor gemäss Anspruch 1, bei dem der Sinterkörper die Grundkomponente umfasst, die weiterhin
wenigstens eines, ausgewählt aus der Gruppe, bestehend aus Aluminium (AI), Indium (In) und Gallium
(Ga) in einer Menge, berechnet als Al3+, ln3+ bzw. Ga3+, von 0,0001 bis 0,05 Mol.% umfasst.
3. Varistor gemäss Anspruch 2, bei dem die zusätzliche Komponente weiterhin wenigstens eines,
ausgewählt aus der Gruppe, bestehend aus Silber (Ag) und Silicium (Si) in einer Menge, berechnet als
Ag20 und Si02, von 0,002 bis 0,2 Gew.% bzw. 0,001 bis 0,1 Gew.%, bezogen auf die Grundkomponente,
umfasst.
4. Varistor gemäss Anspruch 2, bei dem die zusätzliche Komponente ein Glas ist.
5. Varistor gemäss Anspruch 3, bei dem Bor in einer Menge, berechnet als B203, von 0,002 bis 0,2
Gew.%, bezogen auf die Grundkomponente, zugegeben wird.
6. Varistor gemäss Anspruch 1, bei dem das Bor in Form von Verbindungen oder Mischungen, aus-
gewählt aus der Gruppe, bestehend aus B2O3, H3BO3, HBO2, B2(OH)4, ZnB407, AgB02, Ammoniumborat,
Ag2B4O7, BaB4O7, Mg(BO2)2·8H2O, MnB4O7.8H2O, BiB03, Ni3(BO3)2 und Ni2B2O5, zugegeben wird.
7. Varistor gemäss Anspruch 2, bei dem das Bor in Form von Verbindungen oder Mischungen, aus-
gewählt aus der Gruppe, bestehend aus B203, H3B03, HB02, B2(OH)4, ZnB407, AgB02, Ammoniumborat,
Ag2B4O7, BaB407, Mg(B02)2.8H20, MnB407.8H20, BiB03, Ni3(BO3)2 und Ni2B2O5, zugegeben wird.
8. Varistor gemäss Anspruch 2, bei dem das Aluminium, Indium und Gallium in Form von
Al(N03)3.9H20, ln(NO3)3.9H2O, bzw. Ga(NO3)3.xH2O zugegeben wird.
9. Varistor gemäss Anspruch 4, bei dem das Bor enthaltende Glas ausgewählt ist aus der Gruppe,
bestehend aus Ag2O-B2O3-SiO2-Bi2O3-Glas, B2O3-SiO2-Bi2O3-Glas, ZnO-B2O3-SiO2-Glas,
PbO-B2O3-Bi2O3-Glas, PbO-B203-Glas, ZnO-B203-V20s-Glas, ZnO-B203-V20s-Si02-Glas und
B2O3-SiO2-BaO-MgO-Al2O3-Glas.
10. Varistor, welcher Bi2O3 mit nicht weniger als 10% alpha-Phase umfasst.
11. Varistor gemäss Anspruch 10, wobei die alpha-Phase nicht weniger als 30% beträgt.
12. Varistor gemäss Anspruch 10, bei dem die alpha-Phase nicht weniger als 50% beträgt.
13. Varistor gemäss Anspruch 10, bei dem die alpha-Phase im wesentlichen 100% beträgt.

1. Varistance faite en un corps fritté comprenant:

un composant de base qui comprend de l'oxyde de zinc (ZnO) comme composant principal et, à titre de
composants auxiliaires, du bismuth (Bi), du cobalt (Co), du manganèse (Mn), de l'antimoine (Sb) et du
nickel (Ni), en quantité, calculée en Bi203, Co203, MnO, Sb203 et NiO, respectivement, de Bi203: 0,1 à 5
moles%, C0203: 0,1 à 5 moles%, MnO: 0,1 à 5 moles%, Sb2O3: 0,1 à 5 moles% et NiO: 0,1 à 5 moles%; et
un composant supplémentaire comprenant du bore (B) en une quantité, calculée en B203, de 0,001 à
1% en poids par rapport audit composant de base.
2. Varistance conforme à la revendication 1, dans laquelle le corps fritté comprend ledit composant de
base qui comprend en outre au moins un élément choisi dans le groupe constitué par l'aluminium (AI),
l'indium (In), et le gallium (Ga), en une quantité, calculée en Al3+, In3+ et Ga3+, respectivement, de 0,0001 à
0,05 mole%.
3. Varistance conforme à la revendication 2, dans laquelle le composant supplémentaire comprend en
outre au moins un élément choisi dans le groupe constitué par l'argent (Ag) et le silicium (Si), en une
quantité, calculée en Ag20 et Si02, de 0,002 à 0,2% en poids et de 0,001 à 0,1 % en poids, respectivement,
par rapport audit composant de base.
4. Varistance conforme à la revendication 2, dans laquelle ledit composant supplémentaire est un
verre.
5. Varistance conforme à la revendication 3, dans laquelle ledit bore est ajouté en une quantité,
calculée en B2O3, de 0,002 à 0,2% en poids par rapport port audit composant de base.
6. Varistance conforme à la revendication 1, dans laquelle le bore est ajouté sous forme de composés
ou mélanges choisis dans le groupe constitué par B203, H3BO3, HBO2, B2(OH)4, ZnB4O7, AgB02, borate
d'ammonium Ag2B4O7, BaB4O7, Mg(BO2)2.8H2O, MnB4O7.8H2O, BiBO3, Ni3(BO3)2 et Ni2B205.
7. Varistance conforme à la revendication 2, dans laquelle ledit bore est ajouté sous forme de
composés ou mélanges choisis dans le groupe comprenant: B203, H3BO3, HB02, B2(OH)4, ZnB407, AgB02,
borate d'ammonium, Ag2B4O7, BaB4O7, Mg(BO2)2.8H2O, MnB4O7.8H2O, BiBO3, Nl3(BO3)2 et Ni2B2O5.
8. Varistance conforme à la revendication 2, dans laquelle lesdits aluminium, indium et gallium sont
ajoutés sous forme de Al(NO3)3.9H2O, In(NO3)3.9H2O et Ga(NO3)3.xH2O, respectivement.
 9. Varistance conforme à la revendication 4, dans laquelle ledit verre contenant du bore est choisi dans
le groupe constitué par verre Ag2O-B2O3-SiO2-Bi2O3, verre B2O3-SiO2-Bi2O3, verre ZnO-B2O3-SiO2,
verre PbO-B2O3-Bi2O3, verre PbO-B2O3, verre ZnO-B2O3-V2O5, verre ZnO-82O3-V2O5-SiO2 et verre
B2O3-SiO2-BaD-MgD-Al2O3-
10. Varistance qui comprend Bi2O3, présent pour pas moins de 10% sous forme de phase alpha.
11. Varistance conforme à la revendication 10, dans laquelle ladite phase alpha ne représente pas
moins de 30%.
12. Varistance conforme à la revendication 10, dans laquelle ladite phase alpha ne représente pas
moins de 50%.
13. Varistance conforme à la revendication 10, dans laquelle ladite phase alpha représente
sensiblement 100%.