JPS62237706A - Manufacture of voltage nonlinear resistance element - 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 3. Scope of Claims (Field of Industrial Application) The present invention relates to a method for manufacturing a voltage nonlinear resistor, and more specifically, it is suitable for a lightning arrester element with less variation in electrical characteristics. The present invention relates to a method for manufacturing a voltage nonlinear resistor.

(Prior art) - Conventionally, when manufacturing a voltage non-linear resistor, Bi 2031 was added and mixed with zinc oxide to ensure uniformity of the element.
Co 203. MnO2,5b203°Cr 203.
Si02, Ni○, AJ2203. Various additives such as bismuth borosilicate glass were wet mixed and dried, then calcined and further pulverized to produce additive powder.

(Problems to be Solved by the Invention) However, as described above, if all the additives are mixed wet, dried, calcined, and pulverized to obtain a powder, the process, especially the drying process and the calcining process, Among the additives, boron in the bismuth borosilicate glass was easily scattered, making it difficult to maintain a constant composition of the additive powder. Also, Al2O
Since the amount of ω added in No. 2 is very small, there is a reason to add it as an aluminum nitrate solution in order to disperse it uniformly, but when it is added in the above step, the dispersion of the AJ2203 component tends to become non-uniform. As a result, the electrical characteristics of the obtained voltage nonlinear resistor, such as voltage nonlinearity, energized life, and lightning surge resistance, deteriorate or vary widely.

The purpose of the present invention is to solve the above-mentioned problems and to provide a voltage non-linear resistor that has good electrical characteristics such as voltage non-linearity, energized life, and lightning surge resistance, and can obtain constant quality with little variation. This is part 1b which attempts to provide a manufacturing method.

(Means for Solving the Problems) The method for manufacturing a voltage nonlinear resistor of the present invention involves forming a grain boundary phase in a raw material containing zinc oxide as a main component. cto
z○3. Mnoz, 5bz03°Cr2Q3. NiO
, SiC2, bismuth borosilicate glass, aluminum nitrate solution, etc., in a method for manufacturing a voltage nonlinear resistor in which a sintered body is obtained. After pulverization and calcining, a predetermined amount of bismuth borosilicate glass and aluminum nitrate solution are added to the resulting calcined additive, which is further finely pulverized, and zinc oxide is mixed into the pulverized additive. The method is characterized in that a voltage nonlinear resistor is obtained by re-granulating, molding, and firing.

(Function) In the above configuration, additives other than bismuth borosilicate glass and aluminum nitrate solution are first mixed and ground in a wet process, dried, crushed and calcined, and then the borosilicate glass and aluminum nitrate solution are mixed and ground. In addition, since the glass is mixed and pulverized, scattering of boron in the bismuth borosilicate glass and non-uniform dispersion of the AJ2203 components during the drying and calcination steps do not occur at all. As a result, it is possible to obtain an additive raw material powder with a constant composition of each component, and the voltage nonlinear resistor produced from the additive raw material powder has good various characteristics and exhibits consistent performance with little variation. I can do it.

In order to make the various characteristics of the voltage nonlinear resistor roughly constant, the amount of bismuth borosilicate glass mixed after calcination of the additive should be 0.05 to 1.0% by weight. Preferably, the amount of aluminum nitrate added is preferably 0.001 to 0.05% by weight in terms of AJ220g.

Further, it is preferable to pulverize the mixture of the additive, bismuth borosilicate glass, and aluminum nitrate solution until the average particle size is 2.5 μm or less, since the mixture with ZnO becomes uniform.

To obtain a voltage nonlinear resistor whose main component is zinc oxide,
First, for example, 8i2030, 1 to 2.0% in mol%, C
o 203 0.1-2.0%, Mn 02 0.1
~2.0%, 5b2030.1~2.0%, Cr203
01-2.0%, N i Q O, 1-2.0%,
A mixture of bismuth borosilicate glass such as Si 021.0 to 11.0% and additives other than aluminum nitrate solution is preferably finely ground to 2 μm or less using a wet ball mill, dried and crushed, and then heated at 750 to 850°C for 50 minutes. Calculate for about 7 hours. Next, the calcined product is coarsely pulverized using a roll crusher or the like, and the obtained pulverized product is preferably placed in a wet pot mill, and further 71<0.
A predetermined amount of 0.05 to 1.0 wt. Then, zinc oxide is added and mixed into the pulverized additive using a disper mill or the like. At this time, a predetermined amount of a polyvinyl alcohol aqueous solution is added as a binder. This mixing operation preferably uses a disper mill. After degassing the slurry under reduced pressure and granulating it into fine particles, preferably using a spray dryer, the granules are heated under a molding pressure of 800 to 100.
It is compression molded into a predetermined shape under 0 kg/c. For example, the molded body is heated to 800 to
The binder is scattered and removed by calcining at 1000° C. for 1 to 5 hours. Next, an insulating coating layer is formed on the side surface of the calcined body. This insulating coating layer is made of Bi 2
03. It is an oxide paste made by adding ethyl cellulose, butyl calpitol, and acid 11Qn butyl as organic binders to Sb 203゜Si 02, etc.
Coat the side surface of the calcined body to a thickness of 00 μm. Next, raise and lower the temperature at a rate of 40-60℃/hr, 1000-130℃.
Main firing is carried out at 0°C, preferably at 1200°C for 3 to 7 hours.

Then, a glass paste prepared by adding ethyl cellulose, butyl calpitol, butyl vinegar, etc. as an organic binder to glass powder is applied to the insulating coating layer to a thickness of 100 to 200 μm.
coating to a thickness of 100 to 200℃ in air
/hr, it is preferable to form the glass layer by heat treatment under the conditions of 400 to 600°C for 0.5 to 2 hours. Finally, both end faces of the voltage nonlinear resistor are polished smooth, and aluminum electrodes are provided by thermal spraying to obtain a voltage nonlinear resistor.

Example 1 Additives other than bismuth borosilicate glass and aluminum nitrate were wet-pulverized, dried,
Comparison of samples No. 1 to 6 within the scope of the present invention, which were further finely pulverized by adding bismuth borosilicate glass and aluminum nitrate after crushing and calcining, and samples Nos. 1 to 6, which were calcined and finely pulverized with all additives added at the same time. Example No. 011 was prepared. In addition, in this example other than the comparative example, the addition balance of the aluminum nitrate solution was kept constant at 0.0025% by weight in terms of AA203, and the addition m of the bismuth borosilicate glass was as shown in Table 1. The effect was also evaluated by changing the The evaluation was carried out by determining the average and standard deviation of each of the electrical characteristics such as the voltage nonlinearity index, the ratio of lightning surge attack to A V + TlN, and the leakage current. The results are shown in Table 1. In Table 1, voltage non-linearity 7FaTiαGt I = K
It is calculated from 1iff of V+Tn8 and V+ooμA based on the formula of Vct (1: Tsm, V:?l<pressure, K: proportionality constant). Also, AV+i△ of lightning surge attack is 4×
It shows the rate of decrease in V + m^ when a current of 40 KA is repeatedly applied 10 times with a current waveform of 10 μs. Zarani,'i! The ratio of i11 leakage current is
Charge at a charging rate of 95%, and charge 100% immediately after charging.
The current ratio after time FfA was determined from I + oo time / I 0 time.

As is clear from Table 1, sample N0 is a voltage nonlinear resistor obtained using the raw material powder produced by the method of the present invention
11 to 6 have higher nonlinearity than the comparative example, section? 2 lifespan,
It was found that it has lightning surge and needle resistance properties and that there is little variation in each property.

Furthermore, among the samples obtained by the method of the present invention, the amount of bismuth borosilicate glass added was 0.05 to 1.0% by weight.
It was found that it is even more preferable.

Example 2 A diameter of 47vn and a thickness of 2O produced in the same manner as described above.
n voltage nonlinear resistors, samples N051 to 5 obtained by the manufacturing method of the present invention and samples of comparative examples similar to Example 1 were prepared, and voltages were applied to these samples in the same manner as in Example 1. The average and standard deviation of each of the electrical secret characteristics such as the nonlinear index, ΔV + v^ after lightning surge, and the ratio of leakage current were determined. In addition, in this example other than the comparative example, the amount of bismuth borosilicate glass added was kept constant at 0.5% by weight on the outside, and A1. Attachment 7J11 m converted to zOs was varied as shown in Table 2 to evaluate its influence.

Table 2 As is clear from Table 2, sample No. 2 is a voltage nonlinear resistor obtained using the raw material powder produced by the method of the present invention.
, 1 to 5 have higher nonlinearity and charge life than the comparative example,
It was found that it has lightning surge resistance characteristics and that there is little variation in each characteristic.

Furthermore, among the samples obtained by the method of the present invention, the amount of aluminum nitrate solution added in terms of AJ2203 was o,
It has been found that 9% by weight of ooi~0.05 is roughly preferred.

(Effects of the Invention) As is clear from the above detailed explanation, according to the method for manufacturing a voltage nonlinear resistor of the present invention, the addition and pulverization of bismuth borosilicate glass and aluminum nitrate solution are replaced by the addition and grinding of bismuth borosilicate glass and aluminum nitrate solution. By adding and mixing them after calcination, it is possible to create an excellent voltage non-linearity with good electrical characteristics such as voltage non-linearity, energized life, and lightning surge resistance, with little variation and whose characteristics do not change even when produced with large scratches. A linear resistor can be obtained.

Claims (1)

[Claims] 1. Bi_2O_3, Co_2, MnO_2, and Sb_2O_ that form grain boundary phases in a raw material containing zinc oxide as a main component.
3. In the method for manufacturing a voltage nonlinear resistor in which a sintered body is obtained by mixing additives such as Cr_2O_3, NiO, SiO_2, bismuth borosilicate glass, and aluminum nitrate solution, additives other than bismuth borosilicate glass and aluminum nitrate solution are used. After finely pulverizing the mixture and calcining it, a predetermined amount of bismuth borosilicate glass and aluminum nitrate solution is added to the resulting calcined additive mixture and further finely pulverizing it to obtain a finely pulverized mixture of all additives. A method for manufacturing a voltage non-linear resistor, which comprises mixing zinc oxide with the liquid, followed by granulation, molding, and firing to obtain a voltage non-linear resistor. 2. The amount of added bismuth borosilicate glass is 0 on the outside.
．． The method for manufacturing a voltage nonlinear resistor according to claim 1, wherein the amount is 05 to 1.0% by weight. 3. The amount of aluminum nitrate added is 0.001 to 0.05 in terms of Al_2O_3.
% by weight. A method for manufacturing a voltage nonlinear resistor according to claim 1. 4. The method for manufacturing a voltage nonlinear resistor according to claim 1, wherein the mixture of calcined additives is finely pulverized using a wet ball mill until the average particle size of the additives becomes 2.5 μm or less.