JPS60170207A - Voltage nonlinear resistor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a voltage nonlinear resistor containing zinc oxide as a main component.

Conventional technology Voltage nonlinear resistor (ZnO) whose main component is zinc oxide (ZnO)
ZnO elements (hereinafter referred to as ``ZnO elements'') have excellent nonlinearity and are therefore used, for example, in semiconductor elements such as transistors and thyristors, or as strain absorbers in electrical equipment. This type of ZnO element is usually obtained by mixing ZnO as a main component with several types of additives including bismuth oxide (Bit's) as subcomponents, and molding and sintering the mixture. Here, since Bi, O, and ZnO have low melting points compared to ZnOi, ZnO is formed by liquid phase sintering.
It is added to promote crystal growth of particles. Conventionally, in order to fully demonstrate their functions, Bi and O were used in large amounts of 0.3 molar or more relative to the total components.

On the other hand, when manufacturing a ZnO element, a heat treatment step of 400 to 900° C. is required after sintering in order to improve the life characteristics of the ZnO element and to form an insulating coating on the outer periphery of the ZnO element. However, as a result of such heat treatment C2, the crystal structure of Bi and O changed, and the electrical characteristics of the ZnO element were greatly deteriorated. The degree of the decrease is greater as the heat treatment temperature is higher. Such conventional ZnO elements are limited to a certain current range (for example, 100 μA
~IA), α (nonlinear index) is 20 or more, which is satisfactory, but there is a drawback that α is extremely reduced outside the above range.

Moreover, as mentioned above, Bi, 0. is used in large quantities, but the Clark number of the binumutous element is 2.
X 10-', and Bi, O, and C2 are extremely scarce resources.

OBJECTS OF THE INVENTION The present invention has been made in view of the problems of the prior art, and provides a long-life voltage nonlinear resistor that can be manufactured without using resources (--poor B110) and has excellent electrical characteristics. The purpose is to provide the following.

Summary of the Invention In order to achieve the above object, the first invention provides 0.1 to 5 mol of manganese oxide (MnO,), 1 to 5 mol of antimony oxide (Sb2O2), and chromium oxide (Cr).
, O,) 0.1 to 5 molti, silicon oxide (Sin,)
0.1-5 mol, cobalt oxide (Cot's) o,
For the first component consisting of 1 to 5 molar residual ZnO, C
rt03.

Any one of ZnO, Co103 and Mn01
0.2 to 20% by weight of a second component formed by calcining a mixture of seeds and lead oxide (pbo) and sb, o, etc.
In addition, it is sintered to form a ZnO element.

The second invention is Mn0.0.1 to 5 mol%, sb, o
sO01-5 mol%, Cr20B 0.1-5 mol%, Sin.

0.1~5moh'4, Cotol o, 1~5
Mol! , aluminum oxide (Afi*Os) 0.2/
The second component is 0.2 to 20% by weight with respect to the first component consisting of 1000 to 20/1ooo morch and the balance ZnO.
In addition, it is sintered to form a ZnO element, which is an fC element.

The third invention is MnO, 0.1 to 5 mol%, sb, o.

0.1-5 mol%, Cr, 0.0.1-5 mol q6
．． Sho.

A first component consisting of 0.1 to 5 mol% of Co20B, 0.1 to 5 mol% of Co20B, and the balance ZnO, zinc borosilicate glass, and the second component, each component composition being 0.1 to 5 mol% of zinc borosilicate glass.
, 01-5% by weight, second component 0.2-20% by weight.

The remaining part is mixed to become the first component, and it is sintered to form Zn.
This is an O element.

The fourth invention is Mn0.0.1 to 5 mol%, sb, o
30.1-5 mol%, cr, o, 0.1-5 mol ulb, 5iO10,1-5 mol%, Cot's
o, 1-5 mol%, All, O.

0.2/1000 to 20/1000 molti, balance ZnO
a first component consisting of a zinc borosilicate glass, and a second component, each component having a composition of 0.01 to 5% by weight of the zinc borosilicate glass, 0.2 to 20% by weight of the second component, and the remainder being the first component. The components are mixed and sintered to form a ZnO element.

MSCD invention is MnO,o, 1-5-E: k'
16, 5b2030.1-5 moh%, Cr20H
0.1-5 mol%, 5i020, 1-5 mol/L, %
, Co, 0. o, 1~5 mol%, niakel oxide (NiO) 0.1~5-fnyl%, At1tO
sO, 2/1000 to 20/1000 mol, balance Zn
a first component consisting of O; a zinc borosilicate glass; and the second component.
The composition of each component is borosilicate zinc glass 0.01 to 5.
% by weight, the second component is 0.2 to 20% by weight, and the remainder is the first component, and the mixture is sintered to form a ZnO element.

EXAMPLES Below, each of the first to fifth examples of the present invention will be described in detail.

1) An embodiment of the first invention First, a predetermined amount of PbO, Cr2O, Sb, and O powders were weighed in a molar ratio of 4:1:1 and thoroughly mixed in a centrifugal ball mill. It was made into a mixed powder.

Then, this mixed powder was placed in an aluminum crucible at a firing temperature of 1
The calcined body was calcined at 000° C. for 4 hours, and the calcined body was ground in a centrifugal ball mill to obtain a reaction product as a second component.

On the other hand, the first component contained 97.5 moles of ZnO.

MnO, 0.5 mol%, sb, o, 0.5 mol%
, Cr, 030.5 mol%, Si 0,0.5 mol%
, Co, and OB in an amount of 0.5 mol were added to the reaction product in an amount of 2% by weight, and then thoroughly mixed in a rotary ball mill and formed into a disk shape.

Next, this molded body was fired in air at a firing temperature of 1100°C for 6 hours, and both end faces of the obtained sintered body were polished, silver (Ag) electrodes were applied to both end faces, and the temperature was 590°C. A heat treatment was performed for 1 hour to obtain a voltage nonlinear resistor (ZnO element).

Here, PbO, Cr, 03. When X-ray diffraction was performed on the reaction product obtained by calcining the mixed powder of Sb and O, the X-ray diffraction pattern was as shown in FIG. As a result of assigning the signals in FIG. 1, it was found that the reaction product contained pyrochlore crystals py as a main component.

FIG. 2 is a graph showing the voltage-current characteristics of the ZnO element of this example, with the horizontal axis representing the current and the vertical axis representing the voltage. In FIG. 2, the solid line 1 shows the characteristics of the ZnO element of this example, and the solid line 2 shows the characteristics of the ZnO element of this example.

The graph shows the characteristics of a conventional ZnO element containing additives as the main component, and the slope of solid line 1 is smaller than the slope of solid line 2 in the microcurrent region and large current region. Here, C2, α is larger as the slope of the solid line in the second @ is smaller, so it can be seen that the ZnO element of this example has better nonlinear characteristics than the conventional ZnO element.

In addition, FIG. 3 shows each heating section gi1 when the temperature of the heat treatment, which is the final stage in the ZnO element manufacturing process, is varied.
A graph showing the relationship between the temperature and the rate of change in V + mA/m * Yori α before and after heat treatment.
Each rate of change is plotted on the vertical axis.

Note that the heat treatment time was 1 hour at each temperature.

Here, Vi mA/' is the voltage across both ends when a current of ITrLA is passed through the ZnO element, and α is z! If a voltage of V (V) is generated when a current of 1 (A) is passed through a 10-unit, the index is expressed by (2)=(-M-)a.

K is a nonlinear resistance. Further, this α is a current value of 1: Although it varies depending on the current value, in general, a value when a current in the range of 0.1 mA to 1 mA is applied is often used, and the value in this range will be adopted below.

In FIG. 3, solid lines a3 and 4 show the α and v1mA//, Io) characteristics of the ZnO device of this example, respectively, and solid lines 5 and 6 show the conventional ZnO with Bi 103 as the main component, respectively. α and Vsmi/
In the conventional ZnO element, the heat treatment temperature for both α, V, and rnVIII+ is higher than about 500°C (when the temperature rises, the characteristics rapidly decrease. On the other hand, it can be seen that in the ZnO element of this example, the characteristics of both α and V1mA/m hardly change due to heat treatment.

Furthermore, FIG. 4 shows that v
This is a graph showing the rate of increase in leakage current when a DC voltage of 85% of 1U/.

In FIG. 4, the solid line 7 shows the characteristics of the ZnO element of this example, and the solid line 8 shows the characteristics of the conventional ZnO element whose main ingredients are Bi and O.
It can be seen that the nO element has a smaller rate of increase in leakage current and has better life characteristics than the conventional ZnO element.

FIG. 5 is a graph showing how α changes when the content ratio of 5i01 is changed, and the horizontal axis shows StO,
The content ratio of , α is plotted on the vertical axis.

In FIG. 5, a solid line 8 indicates the characteristic of α, which is Sin.

Regarding components other than MnO2, 5b101, C
r1O3°Co10B was fixed at 0.5 mol each, and was increased or decreased in accordance with the ZnO content, so that the content of the reaction product was fixed at 2% by weight. As can be seen from Figure 5, in order to obtain good characteristics,
It is necessary that sio be contained in the first component in a range of 0.1 to 5 mol.

In addition, as mentioned above, in the same way as confirming the effective content ratio of SiO, other additive components, namely MnO,
, 5b101 , Cr! Experiments on the Hibain ρ 5 product revealed that in order to obtain good properties, MnO!
Kao 0.1-5 mol%, sb, o, Kao, 1-
5 moles 96.

Cr, 01 is 0.1 to 5 mol (16, Co10@0.
1 to 5 mol of reaction product to 0.2 to 2 mol of the first component
It was necessary that each content be within the range of 0% by weight.

11) An example of the second invention First, a reaction product as the second component was obtained in the same manner as in the example of the first invention.

On the other hand, as the first component, Zn097.497 mol.

Mn 0.0.5 mol%, Sb 0.0.5 mol%,
Cr, 01 o, 5molti, sio, o, smolti,
Co20g 0.5 mole.

A predetermined amount of Affi, 0.3/1000 moles, was weighed.

Then, 2% by weight of the above reaction product was added to this first component, and then thoroughly mixed in a rotary ball mill and formed into a disk shape.

Next (2) In the same manner as in the example of the first invention, this molded body was fired, Ag electrodes were applied to both end faces, and heat treatment was performed to obtain a ZnO element.

FIG. 6 is a graph showing the voltage-current characteristics of the ZnO element of this example, with the horizontal axis representing the current and the vertical axis representing the voltage. In FIG. 6, the solid line 10 represents the ZnO of this example.
The solid line 2 shows the characteristics of a conventional ZnO device containing Bi, 03 as the main additive, and in the micro current region and large current region, the slope of solid line 10 is the slope of solid line 2. It is smaller than Z in this example.
It can be seen that the nO element has better nonlinear characteristics than the conventional product. In particular, An, 0. Since α is contained in the large current region, α becomes large.

In addition, Fig. 7 shows v1 in a constant temperature bath at a temperature of 130°C.
This is a graph showing the rate of increase in leakage current when a DC voltage of 85 volts of WLA/ is applied, with the horizontal axis (second charge time) and the rate of increase in leakage current on the vertical axis.

In FIG. 7, a solid line 11 shows the characteristics of the ZnO element of this example, a solid line 8 shows the characteristics of a conventional product whose main additive is Bi2O, and a solid line 12 shows the characteristics of the ZnO element of this example. This shows the characteristics of the ZnO element when the content ratio of ρ, 0.0 is set to 20/1000 molar ratio. It can be seen that the leakage current increase rate is small and the life characteristics are good.

Furthermore, FIG. 8 shows sto, or Co! This is a graph showing how α changes when each content ratio of OIL is changed, with the content ratio of each component on the horizontal axis and α on the vertical axis. In FIG. 8, the solid line 13 is 5 int.
By changing the content ratio of MnO□.

Sb, 03. Cr2O, , Co2O3, A4203
The characteristics of α are shown when the content ratio of ZnO is made the same as in the example, the content ratio of ZnO is increased or decreased corresponding to Sin, and the content ratio of the reaction product is fixed at 2% by weight. In addition, the solid line 14 shows that the content ratio of Co20B is changed and the content of MnO
,.

sb, o, Cr20B, 5i02. Afi, 0
．． The characteristics of α are shown when the content ratio of 1 is the same as in the example, the content ratio of ZnO is increased or decreased corresponding to Co2O3, and the content ratio of the reaction product is fixed at 2% by weight.

As shown in Figure 8, in order to obtain good characteristics, S
It is necessary that joy be contained in the first component in a range of 0.1 to 5 mol. Also, Co, O.

It is also necessary that the first component contains 0.1 to 5 mol of mol.

In addition, as mentioned above, in the same way as confirming the effective content ratio of sio, etc., other additive components, namely MnO,
, Sb, 0. , Cr, O8, 12,0,, in order to obtain good characteristics (the second is MnO2, Sb20g, Cr, OB are 0, respectively).
．． 1 to 5 mol AQ, 03 is 0.2/1000 to 2
It is necessary that the reaction product is contained in the first component within the range of 0/1000 mole, and the reaction product is
．． It was necessary that the content be in the range of 2 to 20% by weight to 31%.

111) An example of the third invention First, a reaction product as the second component was obtained in the same manner as in the example of the first invention.

On the other hand, the first component contained 97.5 moles of ZnO.

MnO! 0.5 mol%, Sb, 0.0.5 mol%,
Cr@0B 0.5 mol%, 5i010.5 mol%
A predetermined amount of 0.5 mol of Co20B was weighed. Thereafter, the first component was weighed to be 97.8% by weight, the reaction product was weighed to be 2% by weight, and the zinc borosilicate glass was weighed to be 0.2% by weight, and these were thoroughly mixed in a rotating ball mill. It was formed into a disk shape.

Next, in the same manner as in the first embodiment of the invention, this molded body was fired, Ag electrodes were coated on both end faces, and heat treatment was performed to obtain a ZnO element.

FIG. 9 is a graph showing the voltage-current characteristics of the ZnO element of this example, with voltage plotted on the 11th axis. 9th
In the figure, real i! i15 shows the characteristics of the ZnO element of this example, and solid line 2 shows the characteristics of the conventional ZnO element containing Bi20B as the main component of the additive.In the micro current region and large current region, the slope of solid line 15 is is solid line 2
It can be seen that the ZnO element of this example has better nonlinear characteristics than the conventional product.

In addition, Fig. 10 shows the v
l, TLA/1. This is a graph showing the rate of increase in leakage current when a DC voltage of 85 inches is applied, with the horizontal axis representing the voltage application time and the vertical axis representing the rate of increase in leakage current.

In FIG. 10, the solid line 16 shows the characteristics of the ZnO element of this example, and the solid line 8 shows the characteristics of the conventional product whose main additives are Bi and O. It can be seen that the rate of increase in leakage current is smaller than that of conventional products, and the life characteristics are good.

Furthermore, FIGS. 11 and 12 show SiO□Coco
.

Or, it is a graph showing how α changes when each content ratio of zinc borosilicate glass is changed, and the content ratio of each component is shown on the horizontal axis.

The vertical axis (2α is taken. Figures 11 and 12)
In the figure, solid lines 11 and 19 are respectively 5i02
The characteristics of α are shown when the content ratios of Co2O3 and Co2O3 are changed, the content ratios of other additive components are the same as in the examples, and the content ratio of ZnO is increased or decreased in correspondence with 5i02 or Co203C. Moreover, the solid line 18 shows that the content ratio of the zinc borosilicate glass as a whole is changed, the content ratio of the reaction product is fixed at double i%, and each component in the first component is changed as in the example. The characteristics of α are shown when the content ratio of one component as a whole is increased or decreased in accordance with the zinc borosilicate glass.

As can be seen from FIGS. 11 and 12, in order to obtain good characteristics, it is necessary that each of Sin and Co2O3 be contained in the first component in a range of 0.1 to 5 mol. Yes, zinc borosilicate glass has a total of 0
It is necessary that the content be in the range of 0.01 to 5% by weight.

In addition, as mentioned above, in the same way that the effective content ratio of 5102 etc. was confirmed, other additive components, namely, Mn0
t, Sb, 01, Cr, 0. , reaction products
2Q, C2 is contained in the first component in the range of 0.1 to 5 mol, respectively, and the reaction product is 0, 2 to 2 in the whole.
It was necessary that the content be within the range of 0 weight it%.

Iv) An example of the fourth invention First, a reaction product as the second component was obtained in the same manner as in the example of the first invention.

On the other hand, as the first component, Zn097.497 mol%.

MnO, o, 5% le%, Sb, 010.5 mok
%, Cr1O,,0,5Mok'16,5i02
0.5mol, z%, Co, 0.0.5mol LAI2t0
1 a/1ooo mole was weighed out. Thereafter, this first component is 97.8% by weight, and the reaction product is double f.
Weigh each crab so that the zinc borosilicate glass is 0.2% by weight, mix them thoroughly in a rotating ball mill,
It was formed into a disk shape.

Next, in the same manner as in the first embodiment of the invention, this molded body was fired, Ag electrodes were applied to both end faces, and heat treatment was performed to obtain a ZnO element.

FIG. 13 is a graph showing the voltage-current characteristics of the ZnO element of this example, with the horizontal axis representing the current and the vertical axis representing the voltage. In FIG. 13, the actual @20 is Z of this example.
The characteristics of the nO element are shown, and the solid line 2 indicates Bi, 0. The graph shows the characteristics of a conventional ZnO element containing additives as the main component. It can be seen that the element has better nonlinear characteristics than the conventional product. In particular, since it contains AQtO,
α becomes large in the large current region.

In addition, Fig. 14 shows the v
l 711A/fllll! This is a graph showing the rate of increase in leakage current when a DC voltage of 85% of 1 is applied, with the horizontal axis representing the voltage application time and the vertical axis representing the rate of increase in leakage current.

In FIG. 14, a solid line 21 shows the characteristics of the ZnO element of this example, a solid line 8 shows the characteristics of a conventional product whose main additives are Bi and O, and a solid line 22 shows the characteristics of the ZnO element of this example. This shows the characteristics of the ZnO element when the content ratio of , O, is set to 20/1000 molar ratio, and both the ZnO element of this example and the other examples shown by the solid line 22 have an increase in leakage current compared to the conventional product. It can be seen that if the ratio is small, the life characteristics are good.

Furthermore, FIGS. 15 and 16 show that Sin.

A graph showing how α changes when the content ratio of Coco or zinc borosilicate glass is changed, with the content ratio of each component on the horizontal axis and α on the vertical axis. It is. In FIGS. 15 and 16, solid lines 23 and 25 represent Sin and C, respectively.
The content ratio of o10B was changed, the content ratio of other additive components was the same as in the example, and the content ratio of Sin or Co was changed.
The characteristics of α are shown when the content ratio of ZnO is increased or decreased corresponding to 20 g. Moreover, the solid line 24 shows that the content ratio of the zinc borosilicate glass as a whole is changed, the content ratio of the reaction product is fixed at 2% by weight, and each component in the first component is changed in the same way as in the example. The characteristics of α are shown when the content ratio of all the components is increased or decreased in accordance with the zinc borosilicate glass.

As can be seen from FIGS. 15 and 16, in order to obtain good characteristics, it is necessary that Si02 and Co20B be contained in the first component in a range of 0.1 to 5 mol, respectively; Zinc borosilicate glass has a total of 0
, it is necessary that the content be in the range of 01 to 5% by weight.

In addition, as mentioned above, in the same way as confirming the effective content ratio of Sin, etc., other additive components, namely, Mn0
t, 5JO3, Cr, 031 AflxOam
When conducting experiments on the reaction products, Mn01, S
b20g and CrzOB are each contained in the first component in a range of 0.1 to 5 mol, and AmO is 0.2
The reaction product was required to be contained in the first component in the range of 0.2 to 20% by weight based on the total weight.

'v) An example of the fifth invention First, a reaction product as the second component was obtained in the same manner as in the example of the first invention.

On the other hand, the first component contained 96,997 moles of ZnO.

MnO, 0.5 mol%, Sb, 0.0.5 mol%,
Cr, 0. o, 5 mol%, 5i020.5 mol, Co2O30,5 mol.

Predetermined amounts of 0.5 mol of Ni and 0.3/1000 mol of An were weighed. Then, this first component was 97.8% by weight.

The weight of the above reaction product is 2, and the zinc borosilicate glass is 0.2.
They were each weighed so as to have a weight of f#, thoroughly mixed in a rotary ball mill, and formed into a disk shape.

Next, in the same manner as in the first embodiment of the invention, this molded body was fired, Ag electrodes were applied to both end faces, and heat treatment was performed to obtain a ZnO element.

FIG. 17 is a graph showing the voltage-current characteristics of the ZnO element of this example, with the horizontal axis representing the current and the vertical axis representing the voltage. In FIG. 17, the solid line 26 indicates the Z
The solid line 2 shows the characteristics of a conventional ZnO element whose main additives are Bi, O, etc. In the micro current region and the large current region, the slope of the solid line 26 is the same as that of the solid line 2. It can be seen that the ZnO element of this example has better nonlinear characteristics than the conventional product. In particular, since Afi, O, is contained, α in the large current region becomes large.

In addition, Fig. 18 shows the v
This is a graph showing the rate of increase in leakage current when a DC voltage of 85 inches of xmh/y is applied, with the horizontal axis representing the charging time and the vertical axis representing the rate of increase in leakage current.

In FIG. 18, a solid line 27 shows the characteristics of the ZnO element of this example, a solid line 8 shows the characteristics of a conventional product whose main additives are Bi, O, and a solid line 28 shows the characteristics of the ZnO element of this example. , O, shows the characteristics of the ZnO element when the content ratio is 20/1000 molar ratio 1. It can be seen that both the ZnO elements of this example and the other examples shown in Example @2B have a smaller leakage current increase rate and better life characteristics than the conventional products.

Furthermore, Fig. 19 is a graph showing the rate of voltage change (Δv1U/v1□A) after applying an 8x20 μs pulse, with the pulse current value on the horizontal axis and the rate of voltage change after applying the pulse on the vertical axis. It is something. In FIG. 19, a solid line 29 shows the characteristics of the ZnO device of this example, and a solid line 30 shows the characteristics of the ZnO device when NiO is removed in the example and the content ratio of ZnO is increased accordingly. As can be seen from FIG. 19, the ZnO element that does not contain NiO (solid line 30) has a large decrease in voltage change rate with respect to the increase in pulse current, but the ZnO element of this example (solid line 29) has a large decrease in voltage change rate with respect to an increase in pulse current. The degree of reduction is smaller than that of a ZnO element that does not contain NiO. That is, by adding NiO, it is possible to suppress the degree of decrease in the voltage change rate with respect to an increase in pulse current.

Figures 20 and 21 show Sing, Nip, C
This is a graph showing how α changes when each content ratio of o2O3 or zinc borosilicate glass is changed, and the content ratio of each component is shown on the horizontal axis.

α is plotted on the vertical axis. In FIGS. 20 and 21, solid lines 31, 32, and 33 represent S
in, NiO and Co! α is shown when the content ratio of ZnO is varied by changing the content ratio of O1, the content ratio of other additive components is the same as in the example, and the content ratio of ZnO is increased or decreased by reacting with slQ, N10 or Coco. Also,
A solid line 34 indicates that the content ratio of the zinc borosilicate glass as a whole is changed, the content ratio of the reaction product is fixed at 21 parts, and each component in the first component is changed to the entire first component as in the example. The characteristics of α are shown when the content ratio of α is increased or decreased in accordance with the zinc borosilicate glass.

As can be seen from FIGS. 20 and 21, in order to obtain good characteristics, it is necessary that each of Sin, NiO, and Cocos be contained in the first component in a range of 0.1 to 5 mol. However, it is necessary that the zinc borosilicate glass be contained in the range of 0.01 to 5% by weight based on the total weight.

In addition, as mentioned above, in the same way as confirming the effective content ratio of Sin, etc., other additive components, namely, MnO
2,sb,o,, Cr2O4,Afi201+ reaction product was tested and found that MnO,,5b20B
, Cr, and 0° are each contained in the first component in a range of 0.1 to 5 molar proportions, and Afi20. is 0.2/10
It was necessary that the reaction product be contained in the first component in a range of 0.00 to 20/1000 molti, and that the reaction product be contained in a range of 0.2 to 20% by weight based on the total weight.

By the way, Zn in each example of the second to fifth inventions
Regarding the O element, we investigated the changes in v1□/ and α before and after the heat treatment when the temperature of the heat treatment, which is the final step in the ZnO element manufacturing process, was varied variously.
Similar to the ZnO element in the example of the invention, the properties hardly changed due to the heat treatment.

Note that the first to fifth aspects of the present invention are not limited to the above embodiments. f, that is, in each of the above embodiments,
The compounding ratio of the reaction products was pbo:5bto.

: Cr20s=4:1:1, but the present invention is not limited to this example. In other words, it is sufficient that the blending ratio is such that pyrochlore crystals are generated after calcination. Also, regarding the components, PbO, Sb, 03°C
Not limited to the combination of r, OB, Cr2O,, ZnO
.

Pyrochlore crystals can also be produced using any combination of any one or more of Co2O3 and MnO with PbO and sb, o, and similar effects can be obtained. Furthermore, the calcination temperature and time in the calcination step to obtain the reaction product are 800 to 1100' respectively.
C and a range of 1 to 10 hours is preferred. When the calcination temperature is less than 800°C, the reaction is slow and the temperature is 1100°C.
If the temperature exceeds ℃, a large amount of PT
This is because if the time exceeds 10 hours, the degree of volatilization of PF)0 will increase.

On the other hand, the firing temperature and firing time in the firing step after mixing the first component and the second component (reaction product) are preferably in the range of 1000 to 1300°C and 1 to 20 hours, respectively. If the firing temperature is less than 1000°C, a dense sintered body cannot be obtained, and if it exceeds 1300°C, the nonlinear characteristics will deteriorate due to the volatilization of PbO, and the firing time will be 1 hour. If the time is less than 20 hours, a uniform sintered body cannot be obtained, and if the time exceeds 20 hours, PbO near the surface will volatilize, resulting in poor nonlinear characteristics.

In addition, the heat treatment temperature of the sintered body is 500 to 850℃---
--- It is preferable that it is in the range. When the heat treatment temperature is less than 500°C, the life characteristics of the obtained ZnO cords are poor;
This is because if the value exceeds , the nonlinear characteristics will deteriorate.

``Oh, in each of the above examples, a centrifugal ball mill, an aluminum crucible, etc. were used to manufacture the ZnO element.
The types of these instruments may be of any type as long as they meet the purpose, and are not limited to the instruments used in each of the above embodiments.

Effects of the Invention As described above, according to the fifth invention from 8g1, since B110B, which has conventionally been used in large amounts as an additive, is not used at all, the nonlinear characteristics do not deteriorate due to heat treatment. The non-linear index in the micro-current region and the large-current region is larger than that of the conventional one, and the non-linear index in the micro-current region is especially large, so that the leakage current during energization is small. Furthermore, since the increase in leakage current due to long-term energization is small, a surge absorbing element with a long life can be obtained. Further (2, Clark number is 2×1
In place of B110B+2, which is poor in terms of resources at 0-5, PbO or the like having a Clark number of 1.5×10'' is used, so it is advantageous in terms of resources.

[Brief explanation of drawings]

Figure 1 shows the reaction product X used in an example of invention I.
Line diffraction diagram, FIG. 2 is an example 1 of the first invention: Zn
Voltage-current characteristic diagram of the O element. Figure 3 is a graph showing changes in 1,71A/ and α with respect to the heat treatment temperature of the ZnO element. Figure 4 shows the leakage current increase rate with respect to the energization time of the ZnO element. The graph, FIG. 5, is 5 in the first invention C.
A graph showing α when the content ratio of i04 is changed,
Fig. 6 is a voltage-current characteristic diagram of a ZnO element according to an embodiment of the f42 invention, Fig. 7 is a graph showing the rate of increase in leakage current with respect to energization time of the ZnO element, and Fig. 8 is a graph showing the leakage current increase rate with respect to the energization time of the ZnO element. 9 is a graph showing α when each content ratio of Co2O3 is changed. FIG. 9 is a voltage-current characteristic diagram of a ZnO element according to an embodiment of the third invention. FIG. Graphs showing the leakage current increase rate, FIGS. 11 and 12, are respectively 5i02. in the third invention. A graph showing α when the content ratio of zinc borosilicate glass or Co, O, is changed, FIG. 13 is a voltage-current characteristic diagram of a ZnO element according to an embodiment of the fourth invention, and FIG. Graphs 15 and 16 showing the rate of increase in leakage current with respect to the energization time of the element are shown in the fourth invention C2, respectively, using Sin, zinc borosilicate glass, or Co! A graph showing α when the content ratio of 03 is changed, FIG. 17 is a graph showing α according to an embodiment of the fifth invention
The voltage-current characteristic diagram of the nO element, FIG.
FIG. 9 is a graph showing the rate of voltage change after applying an 8×10 μs pulse to a ZnO element, and FIGS. Nip, Co
201 or a graph showing α when the content ratio of zinc borosilicate glass is changed. Fig. 2 Electric current (A) PL reason L (°C) Fig. 4 ↑ Fig. 5 5iOz 4AIiJna (tub °t.) Fig. 9 Metamorphosis (A) Fig. 10 Takume time Empty (hr) Fig. 11 Fig. 12 CO2O3@V'l+call\(f-le 0m) Fig. 13 @Y (A) Mineden Ginkai (hr) Fig. 15 5102 +A meeting f<cnyoto> No. Figure 16 CO2O3'11"Jite ← Jin a-01o)) Figure 17 Figure 18 Figure 19 Figure 20

Claims (4)

[Claims] (1) 0.1 to 5 mol of manganese oxide, 0.1 to 5 mol of antimony oxide, 0.1 to 5 mol of chromium oxide, 0.1 to 5 mol of silicon oxide, 0.1 to 5 mol of carbon oxide A first component consisting of morch and the remainder zinc oxide is calcined with a mixture consisting of at least one of chromium oxide, zinc oxide, cobalt oxide and manganese oxide, and lead oxide and antimony oxide. A voltage nonlinear resistor characterized in that it is formed by adding 0.2 to 20 weight of a second component and sintering it. (2) Manganese oxide 0.1 to 5 mol%, antimony oxide α1 to 5 mol%, [chromium oxide α1 to α1-5 to 20/1000 mol%. The first part consists of the remainder being zinc oxide.
Ingredients include chromium oxide and zinc oxide. A second product obtained by calcining a mixture consisting of at least one of cobalt oxide and manganese oxide, and lead oxide and antimony oxide.
It is made by adding α2 to 20% by weight of the ingredients and sintering it.
Voltage non-linear resistor with characteristics. (3) Manganese oxide α1-r) Morti. Antimony oxide αl~6 mol%. II compound 01-6 molti. Silicon oxide u1-5molti. A first component consisting of cobalt #alpha to 5 molt, the balance being zinc oxide, zinc borosilicate glass,
Chromium oxide. Zinc oxide. i! A second component formed by calcining a mixture of at least one of cobalt IN oxide and manganese oxide, lead oxide and antimony oxide, and a zinc borosilicate glass having a composition of 0.01 to 5% by weight of each component. Section, second component 0
．． 2 to 20 parts by weight, the remainder being the first component,
A voltage nonlinear resistor characterized by being made by sintering. (4) Manganese oxide 0.1 to 5 mol, antimony oxide 0.1 to 5 mol, chromium oxide 0.1 to 5 mol, silicon oxide 0.1 to 5 mol, cobalt oxide 0.1 to 5 mol, oxidation Aluminum 0.2/1000~20/1000
A first component consisting of morch, the remainder being zinc oxide, and a second component formed by oxidizing and calcining zinc borosilicate glass and any one or more of chromium oxide, zinc oxide, cobalt oxide and manganese oxide, Each component composition is borosilicate zinc glass 0.
1. A voltage nonlinear resistor characterized in that the voltage nonlinear resistor is obtained by mixing and sintering the mixture so that 0.01 to 5 weight jl, a second component to 0.2 to 20% by weight, and the balance to the first component. +5) Manganese oxide 0.1-5 mol, antimony oxide 0.1-5 mol, chromium oxide 0.1-5 mol, silicon oxide 0.1-5 mol, cobalt oxide 0.1-5 mol, A first component consisting of 0.1 to 5 moles of nickel oxide, 0.2/1000 to 20/1000 moles of aluminum oxide, and the balance zinc oxide, zinc borosilicate glass, chromium oxide, zinc oxide, cobalt oxide, and manganese oxide. A second component formed by calcining a mixture consisting of one or more of the above and lead oxide and antimony oxide, each component having a composition of 0.01 to 5% by weight of zinc borosilicate glass, and a second component of 0.01 to 5% by weight of zinc borosilicate glass. ．．
1. A voltage nonlinear resistor, characterized in that the voltage nonlinear resistor is obtained by mixing 2 to 20% by weight and the remainder being a first component, and sintering the mixture.