U.S. patent number 3,764,566 [Application Number 05/237,675] was granted by the patent office on 1973-10-09 for voltage nonlinear resistors.
This patent grant is currently assigned to Matsushita Electric Industrial Co., Ltd.. Invention is credited to Yoshio Iida, Takeshi Masuyama, Michio Matsuoka.
United States Patent |
3,764,566 |
Matsuoka , et al. |
October 9, 1973 |
VOLTAGE NONLINEAR RESISTORS
Abstract
A voltage dependent resistor in a bulk type comprising a
sintered body consisting essentially of, as a major part, zinc
oxide (ZnO) and as an additive, 0.05 to 20.0 mole percent of
silicon dioxide (SiO.sub.2) and 0.05 to 10.0 mole percent, in
total, of at least one member selected from the group consisting of
bismuth oxide (Bi.sub.2 O.sub.3), cobalt oxide (CoO), manganese
oxide (MnO), barium oxide (BaO), strontium oxide (SrO), and lead
oxide (PbO), and electrodes in contact with the body.
Inventors: |
Matsuoka; Michio (Osaka,
JA), Masuyama; Takeshi (Osaka, JA), Iida;
Yoshio (Osaka, JA) |
Assignee: |
Matsushita Electric Industrial Co.,
Ltd. (Osaka, JA)
|
Family
ID: |
22894701 |
Appl.
No.: |
05/237,675 |
Filed: |
March 24, 1972 |
Current U.S.
Class: |
252/521.3;
338/21 |
Current CPC
Class: |
H01C
7/112 (20130101) |
Current International
Class: |
H01C
7/105 (20060101); H01C 7/112 (20060101); H01c
007/12 () |
Field of
Search: |
;338/21
;252/518,520 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chemical Abstracts, Vol. 52, Col. 16890 g.
|
Primary Examiner: Welsh; John D.
Claims
What we claim is:
1. A voltage dependent resistor of the bulk type comprising a
sintered body consisting essentially of, as a major part, zinc
oxide (ZnO) and as an additive, 0.05 to 20.0 mole percent of
silicon dioxide (SiO.sub.2) and 0.05 to 10.0 mole percent, in
total, of at least one member selected from the group consisting of
bismuth oxide (Bi.sub.2 O.sub.3), cobalt oxide (CoO), manganese
oxide (MnO), barium oxide (BaO), strontium oxide (SrO), and lead
oxide (PbO), and electrodes in contact with said body.
2. A voltage dependent resistor according to claim 1, wherein said
additive consists essentially of 0.1 to 10.0 mole percent of
silicon dioxide (SiO.sub.2) and 0.1 to 3.0 mole percent, in total,
of at least one member selected from the group consisting of
bismuth oxide (Bi.sub.2 O.sub.3), cobalt oxide (CoO), manganese
oxide (MnO), barium oxide (BaO), strontium oxide (SrO) and lead
oxide (PbO).
3. A voltage dependent resistor according to claim 1 wherein said
additive consists essentially of 0.1 to 10.0 mole percent of
silicon dioxide (SiO.sub.2), 0.1 to 3.0 mole percent of bismuth
oxide (Bi.sub.2 O.sub.3), and further contains 0.1 to 3.0 mole
percent of at least one member selected from the group consisting
of antimony oxide (Sb.sub.2 O.sub.3), chromium oxide (Cr.sub.2
O.sub.3) and nickel oxide (NiO).
4. A voltage dependent resistor according to claim 1, wherein said
additive consists essentially of 0.1 to 10.0 mole percent of
silicon dioxide (SiO.sub.2), 0.1 to 3.0 mole percent of bismuth
oxide (Bi.sub.2 O.sub.3), and 0.1 to 3.0 mole percent of cobalt
oxide (CoO) and further contains 0.1 to 3.0 mole percent of at
least one member selected from the group consisting of antimony
oxide (Sb.sub.2 O.sub.3), chromium oxide (Cr.sub.2 O.sub.3) and
nickel oxide (NiO).
5. A voltage dependent resistor according to claim 1 wherein said
additive consists essentially of 0.1 to 10.0 mole percent of
silicon dioxide (SiO.sub.2), 0.1 to 3.0 mole percent of bismuth
oxide (Bi.sub.2 O.sub.3) and 0.1 to 3.0 mole percent of manganese
oxide (MnO), and further contains 0.1 to 3.0 mole percent of at
least one member selected from the group consisting of antimony
oxide (Sb.sub.2 O.sub.3), chromium oxide (Cr.sub.2 O.sub.3) and
nickel oxide (NiO).
6. A voltage dependent resistor according to claim 1 wherein said
additive consists essentially of 0.1 to 10.0 mole percent of
silicon dioxide (SiO.sub.2), 0.1 to 3.0 mole percent of bismuth
oxide (Bi.sub.2 O.sub.3), 0.1 to 3.0 mole percent of cobalt oxide
(CoO) and 0.1 to 3.0 mole percent of manganese oxide (MnO), and
further contains 0.1 to 3.0 mole percent of at least one member
selected from the group consisting of antimony oxide (Sb.sub.2
O.sub.3), chromium oxide (Cr.sub.2 O.sub.3) and nickel oxide (NiO).
Description
This invention relates to voltage dependent resistors having
non-ohmic resistance due to the bulk thereof and more particularly
to varistors comprising zinc oxide and silicon dioxide.
Various voltage dependent resistors such as silicon carbide
varistors, selenium rectifiers and germanium or silicon p-n
junction diodes have been widely used for stabilization of voltage
or current of electrical circuits. The electrical characteristics
of such a voltage dependent resistor are expressed by the
relation:
I = (V/C).sup.n
Where V is the voltage across the resistor, I is the current
flowing through the resistor, C is a constant corresponding to the
voltage at a given current and exponent n is a numerical value
greater than 1. The value of n is calculated by the following
equation:
n = [log.sub.10 (I.sub.2 /I.sub.1)]/[log.sub.10 (V.sub.2
/V.sub.1)]
where V.sub.1 and V.sub.2 are the voltages at given currents
I.sub.1 and I.sub.2, respectively. The given currents of I.sub.1
and I.sub.2 are conveniently set up to 0.1mA and 1mA, respectively.
The desired value of C depends upon the kind of application to
which the resistor is to be put. It is ordinarily desirable that
the value of n be as large as possible since this exponent
determines the extent to which the resistors depart from ohmic
characteristics.
Voltage dependent resistors comprising sintered bodies of zinc
oxide with or without additives and silver paint electrodes applied
thereto, have previously been disclosed. The non-linearity of such
varistors is attributed to the interface between the sintered body
of zinc oxide with or without additives and the silver paint
electrode and is controlled mainly by changing the compositions of
said sintered body and silver paint electrode. Therefore, it is not
easy to control the C-value over a wide range after the sintered
body is prepared. Similarly, in varistors comprising germanium or
silicon p-n junction diodes, it is difficult to control the C-value
over a wide range because the non-linearity of these varistors is
not attributed to the bulk but to the p-n junction. On the other
hand, thd silicon carbide varistors have non-linearity due to the
contacts among the individual grains of silicon carbide bonded
together by a ceramic binding material, i.e. to the bulk, and the
C-value is controlled by changing a dimension in the direction in
which the current flows through the varistors. The silicon carbide
varistors, however, have a relatively low n-value ranging from 3 to
6.
An object of the present invention is to provide a voltage
dependent resistor having non-linearity due to the bulk thereof and
being characterized by a high C-value, high n-value and high
stability with respect to temperature, humidity and electric
load.
A further object of the present invention is to provide a voltage
dependent resistor characterized by a high resistance to surge
current.
The other objects of the invention will become apparent upon
consideration of the following description taken together with the
accompanying drawing in which the single FIGURE is a partly
cross-sectional view through a voltage dependent resistor in
accordance with the invention.
Before proceeding with a detailed description of the voltage
dependent resistors contemplated by the invention, their
construction will be described with reference to the aforesaid
figure of drawing wherein reference character 10 designates, as a
whole, a voltage dependent resistor comprising, as its active
element, a sintered body having a pair of electrodes 2 and 3
applied to opposite surfaces thereof. Said sintered body 1 is
prepared in a manner hereinafter set forth and is in any form such
as circular, square or rectangular plate form. Wire leads 5 and 6
are attached conductively to the electrodes 2 and 3, respectively,
by a connection means 4 such as solder or the like.
A voltage dependent resistor according to the invention comprises a
sintered body of a composition consisting essentially of, as a
major part, zinc oxide (ZnO) and, as an additive, 0.05 to 20.0 mole
percent of silicon dioxide (SiO.sub.2) and 0.05 to 10.0 mole
percent, in total, of at least one member selected from the group
consisting of bismuth oxide (Bi.sub.2 O.sub.3), cobalt oxide (CoO),
manganese oxide (MnO), barium oxide (BaO), strontium oxide (SrO)
and lead oxide (PbO) and electrodes in contact with said body.
The higher n-value can be obtained when said additive consists
essentially of 0.1 to 10 mole percent of silicon dioxide
(SiO.sub.2) and 0.1 to 3.0 mole percent, in total, of at least one
member selected from the group consisting of bismuth oxide
(Bi.sub.2 O.sub.3), cobalt oxide (CoO), manganese oxide (MnO),
barium oxide (BaO), strontium oxide (SrO) and lead oxide (PbO).
Table 1 shows the optimal compositions of said additive for
producing a voltage dependent resistor having high n-value, high
C-value, high stability with respect to temperature, humidity,
electric load and high resistance to surge current. The voltage
dependent resistor according to the present invention is
particularly characterized by a high resistance to surge current as
shown in the Table.
The sintered body 1 can be prepared by a per se well known ceramic
technique. The starting materials in the compositions described in
the foregoing description are mixed in a wet mill so as to produce
a homogeneous mixture. The mixtures are dried and pressed in a mold
into the desired shape at a pressure from 100 kg/cm.sup.2 to 1,000
kg/cm.sup.2. The pressed bodies are sintered in air at
1,000.degree.C to 1,450.degree.C for 1 to 10 hours, and then
furnace- cooled to room temperature (about 15.degree. to about
30.degree.C).
The mixture can be preliminarily calcined at 700.degree. to
1,000.degree.C and pulverized for easy fabrication in the
subsequent pressing step. The mixture to be pressed can be admixed
with a suitable binder such as water, polyvinyl alcohol, etc.
It is advantageous that the sintered body be lapped at the opposite
surfaces by abrasive powder such as silicon carbide having a
particle size of 300 meshe to 1,500 meshe.
The sintered bodies are provided, at the opposite surfaces thereof,
with suitable electrodes by any available and suitable method, for
example, with a spray metallized film of aluminum and/or copper.
##SPC1##
Lead wires can be attached to the electrodes in a per se
conventional manner by using conventional solder having a low
melting point. It is convenient to employ a conductive adhesive
comprising silver powder and resin in an organic solvent in order
to connect the lead wires to the electrodes.
Voltage dependent resistors according to this invention have a high
stability with respect to temperature and in the load life test,
which is carried out at 70.degree.C at a rating power for 1,000
hours. The n-value and C-value do not change remarkably after
heating cycles and load life test. Similarly, voltage dependent
resistors according to this invention show a high surge resistance.
It is advantageous for achievement of a high stability with respect
to humidity that the resultant voltage dependent resistors be
embedded in a humidity proof resin such as epoxy resin and phenol
resin in a per se well known manner. The n-value is independent of
the thickness of the sintered body, while the C-value varies in
proportion to the thickness of the sintered body. The variation in
the C-value with thickness of the sintered body indicates that the
nonlinearity of voltage dependent resistor according to this
invention is attributable to the bulk of the sintered body itself,
not to the barrier between the electrodes and the sintered
body.
Presently preferred illustrative embodiments of the invention are
as follows:
Example 1
Starting materials listed in Table 2 are mixed in a wet mill for 5
hours. Each mixture is dried and pressed in a mold into a disc 13mm
in diameter and 2.5mm thick at a pressure of 340 kg/cm.sup.2.
##SPC2##
The pressed bodies are sintered in air for 1 hour at the
temperatures listed in Table 2, and then furnace-cooled to room
temperature (about 15.degree.C to about 30.degree.C). The sintered
discs are lapped to the thicknesses listed in Table 2 by lapping
opposite surfaces thereof with silicon carbide abrasive having a
particle size of 600 meshes. The opposite surfaces of the sintered
discs are provided with a spray metallized film of aluminum by a
per se well known technique. Lead wires are attached to the
aluminum electrodes by means of conductive silver paint. The
electric characteristics of the resultant resistors are shown in
Table 2. It will be readily understood that the C-value changes in
proportion to the thickness of the sintered body.
Example 2
Starting materials according to Table 3 are mixed and pressed in
the same manner as that described in Example 1.
Each pressed body is sintered in air at 1,250.degree.C for 1 hour
and then furnace-cooled to room temperature (about 15.degree. to
about 30.degree.C). The sintered disc is lapped by lapping the
opposite surfaces thereof with silicon carbide abrasive having a
particle size of 600 mesh. The resulting sintered disc is 10mm in
diameter; and 1.5mm in thick. The opposite surfaces of the sintered
disc are provided with a spray metallized film of aluminum by a per
se well known technique. Lead wires are attached to the aluminum
electrodes by means of conductive silver paint. The resultant
resistors are tested in accordance with a method widely used in
testing electronic components parts. The load life test is carried
out at 70.degree.C ambient temperature at 1.5 watt rating power for
1,000 hours. The heating cycle test is carried out by repeating 5
times a cycle in which said resistors are kept at 85.degree.C
ambient temperature for 30 minutes, cooled rapidly to -20.degree.C
and then kept at such temperature for 30 minutes. Further, the
impulse test is carried out by applying 100 times 8 .times. 20.mu.s
impulses of 1,500Ap. The electric characteristics of the resultant
resistor are shown in Table 3. It will be readily understood that
the high n-value, the high C-value at a given current of 1 mA and
the high stability are obtained by the addition of silicon
dioxide.
Example 3
Starting materials according to Table 4 are pressed, fired, lapped,
electrodes are attached and then the resistor tested in the same
manner as described in Example 2. The electric characteristics of
the resultant resistors are shown in Table 4. It can be easily
understood that the resistors having the compositions of Table 4
have higher n-value, high C-value and more excellent stability,
particularly with respect to the impulse test. ##SPC3##
* * * * *