JP2000252105A - Ceramics element and formation of material layer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonlinear resistor which has superior resistance against discharge energy or thunder impulse. SOLUTION: In this nonlinear resistor, a side insulating layer 2 is formed on a side surface of a sintered compact 1 by a high-speed blowing of powder material. Subsequently, upper and lower surfaces of the sintered compact 1 provided with the side surface insulating layer 2 are polished, a guard mask is placed on the sintered compact 1, an electrode 3 is formed on each of the upper and lower polished surfaces by high-speed spraying of metal powder, thus completing a nonlinear resistor. Upon the formation of the electrodes and insulating layer, material or formation conditions, such as the powder materials of the electrodes and insulating layer, an average particle diameter, atmosphere and rate of the material upon spraying, or the presence or absence of preheating of the sintered compact are limited to control the characteristics and dimensional shape, including porousities of the electrodes and insulating layer, the weigh ratio of metallic oxide or nitride, a mean surface roughness, resistivity, a distance between the electrode end and sintered compact end, and roughness of the electrode end.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ceramic element provided with a pair of electrodes, that is, a resistor, a non-linear resistor, a semiconductor capacitor, an IC substrate, an ignition element, a piezoelectric filter, a surface acoustic wave device, and a piezoelectric transformer. The present invention relates to a piezoelectric vibrator, a thermistor, and a gas adsorption type semiconductor, and more particularly to a non-linear resistor having zinc oxide as a main component and having non-linear resistance characteristics, which is used for an arrester, a surge absorber and the like.

[0002]

2. Description of the Related Art Generally, in a power system, an overvoltage protection device such as a lightning arrester or a surge absorber is used in order to remove an overvoltage superimposed on a normal voltage and protect the power system and electric equipment. In such an overvoltage protection device, a non-linear resistor having a characteristic of substantially exhibiting an insulating property at a normal voltage and having a low resistance value when an overvoltage is applied is used.

In the production of this non-linear resistor, zinc oxide is the main component, and at least one or more metal oxides are added to obtain non-linear characteristics, followed by mixing, granulation, and the like.
It is molded and sintered to obtain a zinc oxide sintered body. The nonlinear resistor is manufactured by forming an insulating layer on the side surface of the zinc oxide sintered body and forming electrodes such as aluminum on both end surfaces thereof.

[0004] On the other hand, with the recent increase in power demand, the voltage of the power transmission system is increasing. Among them, the non-linear resistor is required to have improved discharge energy resistance and lightning impulse resistance. The reason is that if a large amount of discharge energy is applied to the nonlinear resistor, it will be destroyed mechanically or electrically, so the breakdown resistance is increased by increasing the discharge energy withstand or lightning impulse withstand before the nonlinear resistor is destroyed. It is necessary to prevent it.

[0005] One of the modes of destruction of the non-linear resistor at the time of discharge energy absorption is destruction caused by an electrode or a side insulating layer of the non-linear resistor. When non-linear resistors are stacked, discharge occurs between the stacked electrodes due to the uneven surface of the electrodes, leading to destruction, or discharge occurs in the gap due to the presence of a gap in the electrode. In some cases, the non-linear resistor is partially concentrated due to the shape of the end of the electrode or a gap inside the electrode, resulting in destruction. In addition, creeping along the surface may occur due to voids existing in the side surface insulating layer, which may cause breakage.

From the viewpoint of preventing such destruction, various techniques have been developed to improve the energy withstand characteristics of the nonlinear resistor. For example, a technique using aluminum containing any of Mg, Ca, and Ti as an electrode spray material is disclosed in Japanese Patent Publication No. 7-44087 by the present applicant. Further, Japanese Patent Application Laid-Open No. 3-125401 discloses a technique in which the difference between the maximum value and the minimum value of the distance between the end of the electrode and the outer peripheral edge, that is, the eccentricity of the disc-shaped electrode with respect to the sintered body including the insulating layer is 1 mm or less. It is disclosed in the gazette.

[0007]

However, the above-mentioned Japanese Patent Publication No. Hei 7-44087 and Japanese Patent Laid-Open Publication No. Hei 3-12540.
The prior art disclosed in Japanese Patent Application Laid-Open No. 1-2003 cannot sufficiently satisfy the energy withstand characteristics and lightning impulse withstand characteristics required for the nonlinear resistor.

[0008] The deterioration of the characteristics due to the uneven surface of the electrode and the presence of voids in the electrode is a problem that exists not only in a non-linear resistor but also in a ceramic element generally having a pair of electrodes. . Examples of such a ceramic element include a resistor, a semiconductor capacitor, an IC substrate, an ignition element, a piezoelectric filter, a surface acoustic wave device, a piezoelectric transformer, a piezoelectric vibrator, a thermistor, and a gas adsorption type semiconductor.

Therefore, a first object of the present invention is to solve the above-mentioned problems of the prior art and to provide a nonlinear resistor having excellent discharge energy withstand characteristics and lightning impulse withstand characteristics. A second object of the present invention is to
By forming an electrode with a flat surface and few voids,
An object of the present invention is to provide a ceramic element having excellent characteristics.

[0010]

In order to solve the above-mentioned problems, the present invention uses a high-speed spraying method as a method of forming an electrode or a side insulating layer on a ceramic element, particularly, a nonlinear resistor. By limiting the material and forming conditions, and controlling the characteristics and dimensions and shape, it prevents breakdown and creeping caused by the electrode when applying discharge energy, and has excellent discharge energy withstand characteristics and lightning impulse withstand characteristics. It is possible to provide a non-linear resistor.

According to a first aspect of the present invention, there is provided a method for forming at least one of an electrode and a side insulating layer on a surface of a ceramic element, wherein the material layer is formed by high-speed spraying of a powder material to the ceramic element. It is characterized by doing. By performing the high-speed spraying of the powder material, a uniform electrode and a side surface insulating layer with few voids can be formed. A non-linear resistor with high discharge energy resistance and high lightning impulse resistance because the uniform electrode and side insulating layer with few voids can prevent uneven current distribution in the element when absorbing discharge energy. Is obtained. Also, when applied to a ceramic element other than the non-linear resistor, a ceramic element having excellent characteristics can be obtained.

According to a second aspect of the present invention, in the method of the first aspect, the components of the powder material are limited. That is, when an electrode is formed, the powder material for forming the electrode includes at least one selected from the group consisting of aluminum, copper, zinc, nickel, silver, tungsten, and alloys thereof. In the case where the side surface insulating layer is formed, the powder material for forming the side surface insulating layer includes at least one selected from the group consisting of aluminum, silicon, boron, an alloy thereof, and a compound thereof.

According to a third aspect of the present invention, in the method according to the first aspect, the powder material has a powder particle size of 0.1 μm to 200 μm.
m.

According to a fourth aspect of the present invention, in the method of the first aspect, the atmosphere for the high-speed spraying of the powder material is limited. That is, when forming an electrode, oxygen, nitrogen, air, hydrogen, argon, performed in an atmosphere containing at least one selected from the group consisting of helium,
When the side surface insulating layer is formed, it is performed in an atmosphere containing at least one selected from the group consisting of oxygen and nitrogen.

According to a fifth aspect of the present invention, in the method of the first aspect, the high-speed spraying treatment of the powder material is performed with a grain speed of 10%.
It is characterized in that it is performed within the range of 0 m / s to 1000 m / s.

According to a sixth aspect of the present invention, in the method of the first aspect, prior to the high-speed spraying of the powder material,
At least the surface of the ceramic element is heated from 50 ° C. to 350
It is characterized by performing a pre-heat treatment of pre-heating within the range of ° C.

According to a seventh aspect of the present invention, in the method according to the first aspect, the conditions for forming the material layer in the high-speed spraying of the powder material are set so that the formed material layer satisfies certain characteristic conditions. It is characterized by: That is, the conditions for forming the material layer in the high-speed spraying process of the powder material are as follows: a) The porosity contained in the material component of the material layer is 5% or less; b) The metal contained in the material component of the material layer The weight ratio of the oxide and the metal nitride to the metal is 25% or less for the electrode, and 75% or less for the side insulating layer.
%) C) The average surface roughness of the material layer is 2.0 μm or less. D) The resistivity of the material layer is 15 μΩ ·
cm or less, and 10 ¹¹ Ω · cm in the case of a side insulating layer.
The above conditions are set so as to satisfy at least one of the four characteristic conditions a to d.

According to an eighth aspect of the present invention, in the method according to the first aspect, when forming the electrode, the electrode forming condition is set so that the formed material layer satisfies a certain dimensional condition. It is characterized by. That is, e) the distance between the electrode end and the ceramic element end is set to 0.0.
F) The irregularity in the main surface direction at the end of the electrode is ± 0.5 mm.
It is set so as to satisfy at least one or more of the following two dimensional conditions e and f:

According to the material layer forming method according to any one of claims 2 to 8 having the above-described structure, the material and the forming conditions when forming the electrode or the side surface insulating layer are limited, and the characteristics and the dimensional shape are controlled. By doing so, it is possible to form more uniform electrodes and side-surface insulating layers with fewer voids. Therefore, the unevenness of the current distribution in the element when the discharge energy is absorbed can be more effectively prevented, so that the discharge energy resistance and lightning impulse resistance of the nonlinear resistor can be further improved. Also, when applied to ceramic elements other than non-linear resistors,
A ceramic element having more excellent characteristics can be obtained.

According to a ninth aspect of the present invention, there is provided a ceramic element having at least one material layer of an electrode and a side surface insulating layer formed on a surface thereof, wherein the material layer is formed of any one of the first to eighth aspects.
The material layer is formed by a method selected from the material layer forming methods described in (1). Such a ceramic element is provided with a uniform electrode having small voids and a side insulating layer obtained by an excellent forming method, as described above with reference to claims 1 to 8. Therefore, the non-uniformity of the current distribution in the element when the discharge energy is absorbed can be effectively prevented, so that a non-linear resistor having a high discharge energy resistance and a high lightning impulse resistance can be obtained. Also, when applied to a ceramic element other than the non-linear resistor, a ceramic element having excellent characteristics can be obtained.

[0021]

The method for forming a material layer according to the present invention is described below.
An example in which the present invention is applied to the formation of an electrode of a non-linear resistor and a side surface insulating layer will be specifically described with reference to the drawings.

[1. Manufacturing Process of Nonlinear Resistor] FIG.
FIG. 4 is a cross-sectional view showing a non-linear resistor made according to the present invention. This non-linear resistor is basically manufactured by a series of steps as follows.

First, manganese dioxide and cobalt oxide are added to zinc oxide at 0.5 mol% each, and bismuth oxide, antimony oxide and nickel oxide are added at 1 mol% each. Next, the raw materials are mixed with water, an organic dispersant, and binders, and the mixture is spray-granulated by a spray drier. These granulated powders are put into a mold and pressurized to form a disk having a diameter of 100 mm and a thickness of 30 mm, and then fired at 1200 ° C. to obtain a sintered body 1.

Next, as shown in FIG. 1, a side surface insulating layer 2 is formed on the side surface of the sintered body 1 by a high-speed spraying method of a powder material (high-speed spraying process). Subsequently, after polishing the upper and lower surfaces of the sintered body 1 provided with the side surface insulating layers 2, the sintered body 1 is covered with a guard mask, and the upper and lower polished surfaces are sprayed with a metal powder at a high speed (high-speed spraying process). The electrode 3 is formed to complete the non-linear resistor.

[2. Outline of Comparative Test] And, in order to show the specific forming conditions and the working effects of the material layer forming method according to the present invention, for each of a plurality of condition objects assumed to affect the discharge energy resistance and the lightning impulse resistance,
By changing the forming method and the forming conditions of the electrode 3 or the side insulating layer 2 as described above, a plurality of types of non-linear resistors are manufactured,
The comparative test was performed.

Here, as a comparative test, three prepared non-linear resistors were laminated, and a discharge energy withstand test or a lightning impulse withstand test was performed under certain conditions. In addition,
The specific test conditions for each test are as follows.

[2-1. Discharge Energy Withstand Test] As the discharge energy withstand test, a rectangular wave discharge energy of 2 ms was applied to a three-layer nonlinear resistor by 200 J.
A destruction test was performed until the non-linear resistor was electrically destroyed by increasing the discharge energy from 20 / cc to 20 J / cc at intervals of 5 minutes. At this time, the discharge energy amount of the maximum value absorbed before breaking was defined as discharge energy resistance (J / cc). Further, with respect to each electrode forming condition and the electrode-shaped non-linear resistor, a discharge energy withstand test was performed on each of ten sets of non-linear resistors.

[2-2. Lightning impulse withstand test] As a lightning impulse withstand test, a 10 μs rectangular wave discharge current is sequentially increased from 100 kA for three stacked non-linear resistors until the non-linear resistors are creepage-enclosed. Was carried out. At this time, the current value until the creepage occurred was defined as the current withstand (kA). In addition, each electrode forming condition,
With respect to the non-linear resistors having the electrode shape, a lightning impulse withstand test was performed on each of ten sets of non-linear resistors.

[3. Details of Comparative Test] Hereinafter, individual comparative tests performed on each of a plurality of condition objects assumed to affect the discharge energy resistance and the lightning impulse resistance will be sequentially described. In addition, a plurality of condition objects are “formation method”, “powder material and its average particle size”, “atmosphere at spraying, speed, presence or absence of preheating”, “porosity”, “metal oxide, metal nitride”. Weight ratio "," average surface roughness "," resistivity "," distance between electrode end and sintered body end, irregularity of electrode end ", and various conditions other than the condition target are the same.
In each of the comparative tests of the condition objects other than the “forming method”, the electrode or the side surface insulating layer is formed by using the high-speed spraying method of the powder material according to the present invention as described above.

[3-1. FIG. 2 shows the results of a discharge energy withstand test of a non-linear resistor when a plurality of types of non-linear resistors are produced by changing the method of forming the non-linear resistor electrodes. It is a graph. In FIG. 2, Comparative Example 1 is a non-linear resistor in which electrodes are formed by arc spraying of aluminum in the air, and Comparative Example 2 is a non-linear resistor in which electrodes are formed by high-speed gas flame spraying of aluminum in the air. Reference numeral 1 denotes a non-linear resistor in which an electrode is formed using aluminum powder by a high-speed spraying method of metal powder according to the present invention.

As is clear from the test results shown in FIG.
The non-linear resistor of Example 1 in which the electrodes were formed by the high-speed spraying method of the metal powder was significantly superior to the non-linear resistors of Comparative Examples 1 and 2 in which the electrodes were formed by other methods. Is shown. This result can be interpreted as follows.

First, the non-linear resistor of Example 1 in which an electrode was formed by a high-speed spraying method of metal powder, had a smooth electrode surface, had few pores, oxides and nitrides in the electrode, and had a predetermined resistance. A shaped electrode is obtained. And since such a high quality electrode is formed favorably, excellent discharge energy withstand characteristics are obtained.

On the other hand, the non-linear resistor of Comparative Example 1 in which the electrode was formed by arc spraying had large sprayed particles to be melted and sprayed, so the surface of the electrode was not smooth, and the electrode had pores and pores. It is easy to contain many oxides. And, since the electrodes are not of high quality, excellent discharge energy withstand characteristics are not obtained.

Further, in the non-linear resistor of Comparative Example 2 in which the electrodes are formed by high-speed gas flame spraying, since the spray pressure at the time of spraying is high, the guard mask is easily deformed by spraying, and an electrode having a predetermined shape is formed. Can not. And, since the electrodes are not of high quality, excellent discharge energy withstand characteristics are not obtained.

FIG. 3 is a graph showing the results of a lightning impulse withstand test of a non-linear resistor when a plurality of types of non-linear resistors are produced by changing the method of forming the side surface insulating layer of the non-linear resistor. It is. In FIG. 3, Comparative Example 3 is a non-linear resistor in which an alumina-based inorganic insulator is applied and then baked to form a side surface insulating layer, and Example 2 is an aluminum resistor formed by a high-speed spraying method of a powder material according to the present invention. 3 illustrates a non-linear resistor in which a side surface insulating layer is formed using powder.

As is clear from the test results shown in FIG.
The non-linear resistor of Example 2 in which the side insulating layer was formed by the high-speed spraying method of the powder material was significantly superior to the non-linear resistor of Comparative Example 3 in which the side insulating layer was formed by another method. It shows the tolerance characteristics. This result can be interpreted as follows.

First, the non-linear resistor of Example 2 in which the side insulating layer was formed by high-speed spraying of the material powder had a smooth surface of the side insulating layer, few pores in the side insulating layer,
In addition, the adhesion strength of the side insulating layer is high, and the side insulating layer having a predetermined shape can be easily obtained. In addition, since the high-quality side insulating layer is formed favorably, excellent lightning impulse withstand voltage characteristics are obtained.

On the other hand, the non-linear resistor of Comparative Example 3 obtained by applying an alumina-based inorganic insulator and firing it is porous, so that the surface of the side insulating layer is not smooth, and There are many pores inside and the adhesion strength is low. Since the side insulating layer is not of high quality, excellent lightning impulse withstand characteristics are not obtained.

As described above, according to the present invention, by forming the electrode or the side insulating layer of the non-linear resistor by the high-speed spraying method, the non-linear resistor having excellent discharge energy withstanding characteristics or lightning impulse withstanding characteristics can be obtained. A resistor can be provided.

[3-2. FIG. 4 is a graph showing the relationship between the average particle size (μm) of the electrode material of the non-linear resistor and the metal raw material powder thereof and the discharge energy resistance (J / cc). It is. That is, FIG. 4 specifically shows a case where two kinds of powder materials, aluminum and carbon steel, are used as powder materials for the electrodes used in the high-speed spraying method, and the particle size of each material is changed. 9 shows the results of a discharge energy resistance test of a nonlinear resistor when various kinds of nonlinear resistors are manufactured. In FIG. 4, Example 3 shows a non-linear resistor formed with electrodes using aluminum, and Comparative Example 4 shows a non-linear resistor formed with electrodes using carbon steel. The average particle size in the figure is a 50% particle size obtained by a laser diffraction method of the powder.

As is clear from the test results shown in FIG.
The non-linear resistor of Example 3 in which the electrodes were formed using aluminum had an excellent discharge energy resistance of 500 J / cc or more on average over a wide range in which the average particle size of the raw material powder was 0.1 to 200 μm. Is shown. However, even when the electrode material is aluminum, when the average particle size of the raw material powder is smaller than 0.1 μm or when the average particle size exceeds 200 μm, the discharge energy resistance is low. Further, the non-linear resistor of Comparative Example 4 in which the electrode was formed using carbon steel had a low discharge energy resistance regardless of the average particle diameter of the powder. This result can be interpreted as follows.

First, the non-linear resistor of Comparative Example 4, in which the electrode was formed using carbon steel, had a low conductivity of the electrode and a low adhesive force between the sintered body and the electrode. Has a low discharge energy resistance. On the other hand, the nonlinear resistor of the third embodiment in which the electrode is formed using aluminum is
Since the conductivity of the electrode is high and the adhesion between the sintered body and the electrode is high, the discharge energy resistance of the non-linear resistor increases.

However, even in the case of a non-linear resistor having an electrode formed of aluminum, if the average particle size of the raw material powder for the electrode is smaller than 0.1 μm, the powder particle size is too small. Since the electrode layer formed at the time of spraying becomes thin and the current distribution in the non-linear resistor becomes uneven, the amount of discharge energy is reduced. Conversely, if the average particle size of the raw material powder for the electrode exceeds 200 μm, the raw material powder is too large, so that the surface of the sintered body undergoes erosion wear and a region where no electrode is formed occurs. , The discharge energy resistance is reduced.

FIG. 4 shows the results when aluminum was used as the electrode material. However, aluminum alloys, copper, zinc, nickel, silver, tungsten,
Alternatively, it has been confirmed that the use of these alloys also has an effect of obtaining a high discharge energy resistance.

As described above, when an electrode of a non-linear resistor is formed by a high-speed spraying method according to the present invention, aluminum, copper, zinc, nickel, silver,
By using tungsten or an alloy thereof as a raw material powder having an average particle size of 0.1 μm to 200 μm and forming an electrode by a high-speed spraying method, a nonlinear resistor having excellent discharge energy withstanding characteristics can be obtained. Can be provided.

FIG. 5 shows the average particle size (μm) of the side insulating material of the non-linear resistor and its raw material powder, and the current withstand capability (k).
6 is a graph showing the relationship with A). That is, FIG.
Specifically, two types of powder materials, aluminum and carbon steel, are used as powder materials for the side insulating layer used in the high-speed spraying method, and the particle size of each material is changed to obtain a plurality of non-type materials. 9 shows the results of a lightning impulse withstand test of a non-linear resistor when a linear resistor is manufactured. In FIG. 5, Example 4 is a non-linear resistor having a side surface insulating layer formed of aluminum, and Comparative Example 5
Is a non-linear resistor with a side insulating layer formed using carbon steel,
Are respectively shown. The average particle size in the figure is a 50% particle size obtained by a laser diffraction method of the powder.

As is clear from the test results shown in FIG.
The nonlinear resistor of Example 4 in which the side surface insulating layer was formed using aluminum had an average particle diameter of the raw material powder of 0.1 μm to 2 μm.
It shows excellent current withstand capability of 200 kA or more on average over a wide range of 00 μm. However, even when the side surface insulating material is aluminum, when the average particle size of the raw material powder is smaller than 0.1 μm, or when the average particle size exceeds 200 μm, the current withstand capability is low. Further, the non-linear resistor of Comparative Example 5, in which the side surface insulating layer was formed using carbon steel, had a low withstand current regardless of the average particle size of the powder. This result can be interpreted as follows.

First, in the non-linear resistor of Comparative Example 5 in which the side insulating layer was formed using carbon steel, the conductivity of the side insulating layer was high, and the adhesion between the sintered body and the side insulating layer was low. For,
The current resistance of the non-linear resistor decreases. On the other hand, in the nonlinear resistor of Example 4 in which the side surface insulating layer was formed using aluminum, the conductivity of the side surface insulating layer was low, and the adhesion between the sintered body and the side surface insulating layer was low. In addition, the current resistance of the nonlinear resistor increases.

However, even in the case of a non-linear resistor having a side surface insulating layer formed of aluminum, if the average particle size of the raw material powder for the side surface insulating layer is smaller than 0.1 μm, the powder particle size is small. Too much, the side insulating layer formed at the time of spraying becomes thin, and the current distribution in the non-linear resistor becomes non-uniform. Conversely, when the average particle size of the raw material powder for the side surface insulating layer exceeds 200 μm, the raw material powder is too large, so that the surface of the sintered body undergoes erosion wear and a region where the side surface insulating layer is not formed. , The current withstand capability is reduced.

FIG. 5 shows the results when aluminum was used as a raw material of the side surface insulating layer. However, the same applies when aluminum alloy, silicon, boron, or a compound thereof is used. It has been confirmed that a high current withstand capability can be obtained.

As described above, according to the present invention, when forming the side insulating layer of the non-linear resistor by the high-speed spraying method, aluminum, silicon, boron, or an alloy or compound thereof is used as the material of the side insulating layer. By using the raw material powder having an average particle diameter of 0.1 μm to 200 μm to form a side insulating layer by a high-speed spraying method, it is possible to provide a nonlinear resistor having excellent lightning impulse withstand voltage characteristics.

[3-3. Comparative Test Regarding Atmosphere, Speed, Presence or Absence of Spraying] FIG. 6 shows the spraying speed of the metal raw material powder at the time of high-speed spraying when forming the electrode of the non-linear resistor, the presence or absence of preheating of the sintered body, It is a graph which shows the relationship with discharge energy tolerance (J / cc). That is, FIG. 6 specifically shows that, when electrodes are formed by a high-speed spraying method, a plurality of types of metal raw material powders are sprayed on the preheated sintered body and the non-preheated sintered body by changing the spraying speed. 4 shows the results of a discharge energy withstand test of the nonlinear resistor when the nonlinear resistor was manufactured.
In FIG. 6, Example 5 is a non-linear resistor in which electrodes are formed by spraying metal raw material powder in a state where at least the surface layer of the sintered body is preheated to 300 ° C., and Example 6 is to preheat the sintered body. , Respectively, shows non-linear resistors formed by spraying metal raw material powder to form electrodes.

As is clear from the test results shown in FIG.
The non-linear resistor of Example 6 in which the electrode was formed by spraying the metal raw material powder without preheating the sintered body had a spraying speed of 10
In the range of 0 m / s to 1000 m / s, 5
It shows a high discharge energy resistance of at least 00 J / cc. However, when the blowing speed is lower than 100 m / s or conversely, when the blowing speed is higher than 1000 m / s, the discharge energy resistance is low. Further, the non-linear resistor of Example 5 in which the electrode was formed by spraying the metal raw material powder in a state where the sintered body was heated in advance, had a spraying speed of 100 m.
/ S to 1000 m / s in an average of 600
It shows a high discharge energy resistance of J / cc or more.
This result can be interpreted as follows.

That is, in the non-linear resistor in which the electrodes are formed at a spraying speed of 100 m / s or less, since the spraying speed is too slow, the metal raw material powder does not melt on the surface of the sintered body and the electrodes are formed. In the non-linear region, the current distribution in the sintered body of the non-linear resistor becomes non-uniform, so that the discharge energy resistance decreases. Conversely, 100
In a non-linear resistor in which electrodes are formed at a spraying speed exceeding 0 m / s, the surface of the sintered body undergoes erosion wear, and it is difficult to obtain an electrode having a predetermined shape, and the spraying speed is too high. Residual stress in the film increases, peeling is likely to occur at the end of the electrode, and discharge energy resistance decreases.

On the other hand, 100 m / s to 1000 m
In the non-linear resistor having the electrode formed at a spraying speed of / s, an electrode having a predetermined shape is easily obtained, and since the residual stress in the electrode film is low, an electrode having high adhesion is obtained, and the discharge energy is reduced. The withstand capacity increases.

Further, in a non-linear resistor in which an electrode is formed by spraying a metal raw material powder in a state in which the sintered body is heated in advance, an electrode having a predetermined shape is easily obtained, and the residual stress in the electrode film is low. Therefore, an electrode with high adhesion can be obtained,
The discharge energy resistance increases. However, the properties of a sintered body containing ZnO as a main component deteriorate when heated to 420 ° C. or higher. Therefore, the preheating temperature is preferably set to 50 ° C. to 350 ° C.

As described above, according to the present invention, by setting the spraying speed of the metal raw material powder in forming the electrode of the non-linear resistor to 100 m / s to 1000 m / s,
It is possible to provide a non-linear resistor having excellent discharge energy withstand characteristics. In addition, by spraying the raw material powder in a state where the sintered body is heated in advance, it is possible to provide a non-linear resistor having more excellent discharge energy withstanding characteristics.

FIG. 7 is a graph showing the relationship among the atmosphere at the time of high-speed spraying, the blowing speed of the raw material powder, and the current capacity (kA) when forming the side surface insulating layer of the nonlinear resistor. More specifically, FIG. 7 shows that, when the side surface insulating layer is formed by the high-speed spraying method, a plurality of types of non-linear resistances are formed by changing the blowing speed of the raw material powder in an oxidizing atmosphere and an inert atmosphere. 9 shows the results of a lightning impulse withstand test of a non-linear resistor when a body is manufactured. In FIG. 7, Example 7 shows a non-linear resistor formed with a side insulating layer in an oxidizing atmosphere, and Comparative Example 6 shows a non-linear resistor formed with a side insulating layer in an inert atmosphere. .

As is clear from the test results shown in FIG.
The non-linear resistor of Example 7, in which the side surface insulating layer was formed in an oxidizing atmosphere, had a spraying speed of 100 m / s to 1000 m / s.
In the range of s, a high current withstand capacity of 200 kA or more is shown on average. However, even in an oxidizing atmosphere, when the spraying speed is lower than 100 m / s or conversely, when the blowing speed is higher than 1000 m / s, the current withstand capability is low. The non-linear resistor of Comparative Example 6, in which the side surface insulating layer was formed in an inert atmosphere, had a low current withstand capability regardless of the blowing speed. This result can be interpreted as follows.

First, in an inert atmosphere, a metal oxide layer such as alumina cannot be formed as a side insulating layer, and a metal layer such as aluminum is formed, and the current resistance of the nonlinear resistor is low. Become. On the other hand, in an oxidizing atmosphere, a metal oxide layer such as alumina can be formed as a side surface insulating layer, so that the current resistance of the nonlinear resistor increases.

However, even with a non-linear resistor having a side insulating layer formed in an oxidizing atmosphere, if the side insulating layer is formed at a blowing speed of 100 m / s or less, the blowing speed is too slow. The metal raw material powder does not melt on the surface of the sintered body, and there is a region where the side surface insulating layer is not formed, resulting in low current withstand capability. Conversely, in the case of a non-linear resistor having a side insulating layer formed at a speed exceeding 1000 m / s, erosion wear occurs on the surface of the sintered body and a good side insulating layer cannot be formed. Too much, the residual stress in the side surface insulating layer increases, and peeling is likely to occur at the end of the side surface insulating layer, resulting in low current withstand capability.

On the other hand, in an oxidizing atmosphere, 100 m
In a non-linear resistor in which a side insulating layer is formed at a spraying speed of / m to 1000 m / s, a metal oxide layer such as alumina is uniformly formed, so that a side insulating layer having a predetermined shape is easily obtained. In addition, since the residual stress in the film is low, an insulating layer having high adhesion can be obtained, and the withstand current can be increased.

FIG. 7 shows the results when the side insulating layer is formed in an oxidizing atmosphere. However, similarly, when the side insulating layer is formed in a nitriding atmosphere, a high withstand current can be obtained. The effect has been confirmed. Further, similarly to the case of forming the electrode, when the side surface insulating layer is formed in a state where the sintered body is preheated at 50 ° C. to 350 ° C., an effect that a higher current withstand capacity can be obtained than when no preheating is performed has been confirmed. I have.

As described above, when forming the side surface insulating layer of the non-linear resistor according to the present invention, the raw material powder is reduced from 100 m / s to 1 m in an atmosphere in which oxides and nitrides can be formed.
By blowing at a blowing speed of 000 m / s,
A nonlinear resistor having excellent lightning impulse withstand characteristics can be provided. In addition, by spraying the raw material powder in a state where the sintered body is heated in advance, it is possible to provide a non-linear resistor having more excellent lightning impulse withstand voltage characteristics.

[3-4. Comparative test on porosity] FIG.
FIG. 9 shows the relationship between the porosity (%) of the electrode and the discharge energy resistance (J / cc) in the nonlinear resistor. FIG. 9 shows the porosity (%) and the current resistance (k) of the side surface insulating layer in the nonlinear resistor.
6A and 6B are graphs respectively showing the relationship with A). That is, FIGS. 8 and 9 specifically show a case where the porosity in the electrode or the side insulating layer is changed by changing the forming conditions when forming the electrode or the side insulating layer by the high-speed spraying method. The results of the discharge energy withstand test and the lightning impulse withstand test of the non-linear resistor in the case of producing various types of non-linear resistors are shown. The porosity in FIG. 8 and FIG.
It was determined by taking out a test piece having only the electrode and only the side insulating layer, and performing a mercury intrusion test on the test piece.

As is clear from the test results shown in FIGS. 8 and 9, a non-linear resistor having an electrode porosity of 15% or less has a high discharge energy resistance of 500 J / cc on average. A non-linear resistor having a porosity of 15% or less in the side surface insulating layer shows a high withstand current of 200 kA on average. In particular, a non-linear resistor having an electrode porosity of 5% or less stably exhibits a high discharge energy resistance of 600 J / cc, and a non-linear resistor having a side insulating layer having a porosity of 5% or less. Is 300
A high current withstand capability of kA is stably shown. This result can be interpreted as follows.

That is, when the porosity in the electrode exceeds 15%, when the non-linear resistor absorbs the discharge energy, the non-linear resistance is increased by the pores at the interface between the sintered body of the non-linear resistor and the electrode. The current distribution of the resistor becomes non-uniform, and the discharge energy resistance decreases. On the other hand, when the porosity in the electrode is 5% or less, the uneven distribution of current in the non-linear resistor due to pores at the interface between the sintered body of the non-linear resistor and the electrode is completely prevented. Therefore, particularly excellent discharge energy resistance can be obtained.

Similarly, when the porosity in the insulating layer exceeds 15%, the pores at the interface between the sintered body of the non-linear resistor and the insulating layer when the non-linear resistor absorbs the discharge energy. Thus, the probability of occurrence of creeping grounding increases, and the current withstand capability decreases. On the other hand, the porosity in the electrode is 5%.
In the following cases, creeping of the surface of the non-linear resistor due to pores at the interface between the sintered body of the non-linear resistor and the electrode can be completely prevented.

As described above, according to the present invention, the porosity of the electrode and the insulating layer of the non-linear resistor is set to 15% or less, especially 5%.
% Or less, it is possible to provide a non-linear resistor having excellent discharge energy withstand characteristics and lightning impulse withstand characteristics.

[3-5. Comparative Test Regarding Weight Ratio of Metal Oxide and Metal Nitride] FIG. 10 shows the relationship between the weight ratio (%) of the metal oxide in the electrode and the discharge energy resistance (J / cc) in the nonlinear resistor, FIG. 4 is a graph showing a relationship between a weight ratio (%) of a metal oxide in a side surface insulating layer and a current withstand capacity (kA) in a nonlinear resistor. That is, FIGS. 10 and 11 specifically show that the weight ratio of the metal oxide in the electrode or the side insulating layer is changed by changing the forming conditions when forming the electrode or the side insulating layer by the high-speed spraying method. The results of the discharge energy tolerance test and the results of the lightning impulse test of the non-linear resistor in the case where a plurality of types of non-linear resistors are produced by changing the resistance are shown. The weight ratio of the metal oxide in FIGS. 10 and 11 is determined by taking out a test piece of only the electrode and only the insulating layer from the non-linear resistor and obtaining the oxygen content in the test piece by the combustion method. The weight ratio as a product is calculated.

As is clear from the test results shown in FIG. 10, the non-linear resistor having a metal oxide weight ratio of 25% or less in the electrode exhibits a high discharge energy resistance of 500 J / cc or more on average. On the other hand, in a non-linear resistor in which the weight ratio of the metal oxide in the electrode exceeds 25%, the discharge energy resistance is low. This result can be interpreted as follows.

That is, when the weight ratio of the metal oxide in the electrode exceeds 25%, when the nonlinear resistor absorbs the discharge energy, the metal at the interface between the sintered body of the nonlinear resistor and the electrode. When an oxide is present, the current distribution of the non-linear resistor becomes non-uniform, and the discharge energy resistance is reduced. On the other hand, the weight ratio of the metal oxide in the electrode was 25%.
% Or less, it is possible to prevent non-uniform current distribution in the non-linear resistor due to the metal oxide at the interface between the sintered body of the non-linear resistor and the electrode, so that an excellent discharge energy resistance is obtained. .

Further, as is apparent from the test results shown in FIG. 11, the weight ratio of the metal oxide in the side insulating layer was 75%.
% Or more, 150 kA on average
While the above high current withstand capability is shown, the current withstand capability is low in the non-linear resistor in which the weight ratio of the metal oxide in the side surface insulating layer is less than 75%. This result can be interpreted as follows.

That is, when the weight ratio of the metal oxide in the side insulating layer is less than 75%, when the non-linear resistor absorbs discharge energy, the sintered body of the non-linear resistor and the side insulating layer If the metal is present at an interface of 25% or more, creeping along the surface is likely to occur, and the current resistance is reduced. On the other hand, the weight ratio of the metal oxide in the electrode is 75%.
% Or more, it is possible to prevent creeping of the non-linear resistor in the non-linear resistor at the interface between the sintered body of the non-linear resistor and the side surface insulating layer.

FIGS. 10 and 11 show the results when the weight ratio of the metal oxide in the electrode or the side insulating layer is changed. However, the weight of the metal nitride in the electrode or the side insulating layer is shown. Even when the ratio is changed, by setting the weight ratio of the metal nitride in the electrode to 25% or less,
Similarly, it has been confirmed that a high discharge withstand capability can be obtained, and that a high current withstand capability can be obtained by setting the weight ratio of the metal nitride in the insulating layer to 75% or more.

As described above, according to the present invention, the weight ratio of the metal oxide or metal nitride in the electrode in the non-linear resistor is reduced to 25% or less, or By setting the weight ratio of the metal oxide or metal nitride to 75% or more, it is possible to provide a non-linear resistor having excellent discharge energy withstand characteristics or excellent lightning impulse withstand characteristics.

[3-6. Comparison Test Regarding Average Surface Roughness] FIG. 12 shows the relationship between the average surface roughness (μm) of the electrode and the discharge energy resistance (J / cc) in the nonlinear resistor, and FIG. 13 shows the side insulation in the nonlinear resistor. It is a graph which shows the relationship between the average surface roughness (micrometer) of a layer, and current withstand (kA), respectively. 12 and 13
Specifically, by changing the forming conditions when forming the electrode or the side surface insulating layer by a high-speed spraying method, the average surface roughness of the electrode or the side surface insulating layer is changed, and a plurality of types of non-linear resistors are formed. 5 shows the results of the discharge energy withstand test and the lightning impulse withstand test of the non-linear resistor in the case of manufacturing a non-linear resistor.

As is apparent from the test results shown in FIGS. 12 and 13, the non-linear resistor having an average surface roughness of the electrode of 8 μm or less has a high discharge energy resistance of 500 J / cc on average. On the other hand, a non-linear resistor having an average surface roughness of 8 μm or less of the side insulating layer has a high current withstand capability of 200 kA on average. In particular, in a non-linear resistor having an average electrode surface roughness of 2 μm or less,
A high discharge energy resistance of 600 J / cc is stably exhibited, and a non-linear resistor having an average surface roughness of the side surface insulating layer of 2 μm or less stably exhibits a high current resistance of 300 kA. This result can be interpreted as follows.

That is, when the porosity in the electrode exceeds 8 μm, when the non-linear resistor absorbs the discharge energy, the discharge easily occurs in the voids of the laminated non-linear resistor, and the discharge energy resistance is low. Lower. On the other hand, when the average surface roughness of the electrode is 2 μm or less,
Since discharge caused by voids between the laminated non-linear resistors can be almost completely prevented, particularly excellent discharge energy resistance can be obtained.

Similarly, the average surface roughness of the side insulating layer is 8 μm.
When the distance exceeds m, the probability that creepage entanglement occurs due to the gap between the sintered body of the non-linear resistor and the side insulating layer increases when the non-linear resistor absorbs discharge energy, and the current withstand capability is increased. Lower. On the other hand, when the average surface roughness of the side insulating layer is 2 μm or less, the creepage of the surface of the non-linear resistor due to the void at the interface between the sintered body of the non-linear resistor and the side insulating layer is completely eliminated. As a result, particularly excellent current withstand capability can be obtained.

As described above, according to the present invention, by setting the average surface roughness of the electrode and the insulating layer of the non-linear resistor to 2 μm or less, a non-linear resistor having excellent discharge energy withstand characteristics and excellent lightning impulse withstand characteristics can be obtained. A linear resistor can be provided.

[3-7. Comparative test on resistivity] FIG.
4 is the resistivity (μΩ · c) of the electrode in the non-linear resistor.
m) and discharge energy resistance (J / cc), FIG.
5 is the resistivity (Ω ·
7 is a graph showing the relationship between the current withstand capability (cm) and the withstand current (kA). That is, FIGS. 14 and 15 specifically show that a plurality of types of electrodes or side insulating layers are formed by changing the forming conditions when forming the electrodes or the side insulating layers by a high-speed spraying method. 3 shows the results of the discharge energy resistance test and the lightning impulse resistance test of the non-linear resistor when the non-linear resistor was manufactured. The resistivity in FIG. 14 and FIG. 15 is obtained by taking out a test piece of only an electrode and only an insulating layer from a non-linear resistor and obtaining the resistance value of the test piece by a DC four-terminal method. This is calculated based on the shape of the piece.

As is clear from the test results shown in FIG. 14, the non-linear resistor having an electrode resistivity of 15 μΩ · cm or less has a high discharge energy resistance of 500 J / cc or more on average. On the other hand, a non-linear resistor having a porosity of more than 15 μΩ · cm in the electrode has a low discharge energy resistance. This result can be interpreted as follows.

That is, the resistivity in the electrode is 15 μΩ · c
m, that is, when there is a high-resistance portion at the interface between the sintered body of the nonlinear resistor and the electrode, when the nonlinear resistor absorbs discharge energy, the burning of the nonlinear resistor occurs. Due to the high resistance portions of the union and the electrodes, the current distribution of the non-linear resistor becomes non-uniform, and the discharge energy resistance is reduced. On the other hand, when the resistivity in the electrode is 15 μΩ · cm or less, the non-uniform current distribution in the nonlinear resistor due to the high resistance portion at the interface between the sintered body of the nonlinear resistor and the electrode. Therefore, excellent discharge energy resistance can be obtained.

Further, as is apparent from the test results shown in FIG. 15, a non-linear resistor having a side surface insulating layer having a resistivity of 10 ¹¹ Ω · cm or more exhibits a high discharge energy resistance of 200 kA or more on average. On the other hand, in a non-linear resistor in which the resistivity of the side insulating layer is smaller than 10 ¹¹ Ω · cm, the current withstand capability is low. This result can be interpreted as follows.

That is, the resistivity in the side insulating layer is 10 ¹¹
If it is smaller than Ωcm, that is, if there is a low resistance part at the interface between the sintered body of the nonlinear resistor and the insulating layer,
When the nonlinear resistor absorbs the discharge energy, the sintered body of the nonlinear resistor and the low resistance part of the side insulating layer
Creepage is likely to occur, and the current withstand capability is reduced.
On the other hand, if the resistivity in the electrode is 10 ¹¹ Ω · cm or more, creeping at the interface between the sintered body of the non-linear resistor and the electrode can be prevented, so that excellent current withstand capability can be obtained.

As described above, according to the present invention, by setting the resistivity of the electrode of the nonlinear resistor to 15 μΩ · cm or less and the resistivity of the side insulating layer to 10 ¹¹ Ω · cm or more,
A non-linear resistor having excellent discharge energy withstand characteristics and excellent lightning impulse withstand characteristics can be provided.

[3-8. The distance between the electrode end and the sintered body end,
FIG. 16 shows a plurality of types of non-linear resistance elements formed by changing the conditions for forming an electrode of a non-linear resistor and thereby changing the dimensions of the electrode and the unevenness of the end of the electrode. It is a schematic diagram which expands and shows the electrode end part at the time of producing a linear resistor. In the figure, 11 is the end of the sintered body, 12 is the electrode, and 13 is the end of the electrode. Also,
In the figure, L ₁ is the distance between the line 14 indicating the average position of the electrode end 13 in the radial direction of the electrode 12 and the sintered body end 11, that is, the average distance between the electrode end 13 and the sintered body end 11. is there.
Further, in the figure, L ₂ indicates the maximum value of the unevenness in the main surface direction at the electrode end 13.

FIG. 17 shows the relationship between the distance L ₁ between the electrode end 13 and the sintered body end 11 in the nonlinear resistor and the discharge energy resistance (J / cc), and FIG. 18 shows the voltage of the nonlinear resistor. relationship of the maximum value of the main surface direction of the projections and depressions of the end portion 13 L ₂ and the discharge energy withstand (J / cc), is a graph showing respectively. That is, FIGS. 17 and 18 specifically show the electrode end 13 and the sintered body end 1 by changing the forming conditions when forming the electrode of the non-linear resistor.
In the case where a plurality of types of non-linear resistors were produced by changing the distance L _{1 of 1} or the maximum value L ₂ of the unevenness in the main surface direction at the electrode end 13, the results of the discharge energy resistance test of the non-linear resistors were respectively Is shown.

As is clear from the test results shown in FIG. 17, the distance between the end of the sintered body and the end of the electrode was 0.01 to 1.0 m.
m for a non-linear resistor within the range of m
It shows a high discharge energy resistance of J / cc or more.
On the other hand, the distance between the end of the sintered body and the end of the electrode was 0.01 m.
In a non-linear resistor shorter than m and a non-linear resistor in which the distance between the end of the sintered body and the end of the electrode exceeds 1.0 mm, the discharge energy resistance is low. This result can be interpreted as follows.

That is, when the distance between the electrode end of the non-linear resistor and the end of the sintered body is shorter than 0.01 mm, when the non-linear resistor absorbs discharge energy, Since dielectric breakdown easily occurs at the interface between the sintered body and the side insulating layer, or inside or on the side surface of the side insulating layer, the discharge energy resistance of the non-linear resistor decreases. Conversely, when the distance between the electrode end and the end of the sintered body is longer than 1.0 mm, when the non-linear resistor absorbs discharge energy, the current inside the non-linear resistor sintered body is reduced. Since the distribution becomes non-uniform, the discharge energy resistance of the non-linear resistor decreases.

On the other hand, when the distance between the end of the sintered body and the end of the electrode is in the range of 0.01 mm to 1.0 mm, the interface between the sintered body and the side insulating layer at the time of discharge energy absorption. Since it is possible to prevent dielectric breakdown inside the side surface insulating layer and on the side surface of the side surface insulating layer or to make the current distribution in the non-linear resistor non-uniform, an excellent discharge energy resistance can be obtained.

Further, as is clear from the test results shown in FIG. 18, in the non-linear resistor having the maximum value of the unevenness of the electrode end portion of ± 0.5 mm or less, the high discharge energy of 500 J / cc or more on average. While the resistance value is shown, the non-linear resistor having the maximum value of the unevenness of the electrode end portion larger than ± 0.5 mm has a low discharge energy resistance. This result can be interpreted as follows.

That is, when the maximum value of the unevenness in the main surface direction at the electrode end portion of the non-linear resistor is larger than ± 0.5 mm, when the non-linear resistor absorbs discharge energy, Since the current distribution inside the sintered body of the non-linear resistor becomes non-uniform at the tip of the convex portion at the electrode end, the discharge energy resistance of the non-linear resistor decreases. On the other hand, when the maximum value of the unevenness of the electrode end portion is ± 0.5 mm or less, it is possible to prevent the current distribution in the non-linear resistor from being uneven due to the tip of the convex portion of the electrode end portion. Excellent discharge energy resistance is obtained.

As described above, according to the present invention, the distance between the end of the sintered body of the non-linear resistor and the end of the electrode is 0.01 mm to
Providing a non-linear resistor having excellent discharge energy withstand characteristics by setting it within the range of 1.0 mm or by setting the maximum value of the unevenness of the electrode end portion in the non-linear resistor to ± 0.5 mm or less. can do.

[4. Other Embodiments] The present invention is not limited to the above-described manufacturing process, and various other manufacturing processes can be used to freely manufacture non-linear resistors having various materials and dimensions. Further, the present invention is most suitable as a method for forming an electrode or a side surface insulating layer in a non-linear resistor, but is not limited thereto, and can be similarly applied to various other ceramic elements, and similarly excellent material layers can be used. Can be formed.

[0097]

As described above, according to the present invention, when forming a material layer of a ceramic element, in particular, an electrode or a side insulating layer in a non-linear resistor composed mainly of zinc oxide,
To provide a non-linear resistor with excellent discharge energy withstand characteristics and lightning impulse withstand characteristics by adopting a high-speed spraying method, limiting materials and forming conditions, and controlling characteristics and dimensions. Can be.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a non-linear resistor according to the present invention.

FIG. 2 is a graph showing a relationship between a method of forming a non-linear resistor electrode and a discharge energy resistance.

FIG. 3 is a graph showing a relationship between a forming method when forming a side surface insulating layer of a non-linear resistor and a lightning impulse resistance.

FIG. 4 shows the average particle size (μm) of the electrode material of the non-linear resistor and its metal raw material powder, and the discharge energy resistance (J / c).
It is a graph which shows the relationship with c).

FIG. 5 is a graph showing the relationship between the average particle size (μm) of the side surface insulating material of the non-linear resistor and its raw material powder and the current withstand capability (kA).

FIG. 6 is a graph showing the relationship between the spraying speed of metal raw material powder during high-speed spraying when forming a non-linear resistor electrode, the presence or absence of preheating of a sintered body, and the discharge energy resistance (J / cc). It is.

FIG. 7 is a graph showing the relationship among the atmosphere at the time of high-speed spraying, the spraying speed of the raw material powder, and the current resistance (kA) when forming the side surface insulating layer of the nonlinear resistor.

FIG. 8 is a graph showing the relationship between the porosity (%) of the electrode and the discharge energy resistance (J / cc) in the nonlinear resistor.

FIG. 9 is a graph showing the relationship between the porosity (%) of the side insulating layer and the current withstand capability (kA) in the nonlinear resistor.

FIG. 10 is a graph showing a relationship between a weight ratio (%) of a metal oxide in an electrode and a discharge energy resistance (J / cc) in a nonlinear resistor.

FIG. 11 is a graph showing the relationship between the weight ratio (%) of the metal oxide in the side surface insulating layer and the current withstand capability (kA) in the nonlinear resistor.

FIG. 12 is a graph showing a relationship between an average surface roughness (μm) of an electrode and a discharge energy resistance (J / cc) in a nonlinear resistor.

FIG. 13 is a graph showing the relationship between the average surface roughness (μm) of the side insulating layer and the current withstand capability (kA) in the nonlinear resistor.

FIG. 14 shows the resistivity of a non-linear resistor (μΩ ·
7 is a graph showing the relationship between the discharge energy (J / cc) and the discharge energy resistance (J / cc).

FIG. 15 is a graph showing the relationship between the resistivity (Ω · cm) of the side insulating layer and the current withstand capability (kA) in the non-linear resistor.

FIG. 16 is a schematic diagram showing an enlarged electrode end of a non-linear resistor.

FIG. 17 is a graph showing the relationship between the distance between the end of the electrode and the end of the sintered body and the discharge energy resistance (J / cc) in the non-linear resistor.

FIG. 18 is a graph showing the relationship between the maximum value of the unevenness in the main surface direction at the electrode end of the nonlinear resistor and the discharge energy resistance (J / cc).

[Explanation of symbols]

1 ... sinter 2 ... side insulating layer 3 ... electrode 11 ... sintered end 12 ... electrode 13 ... electrode end 14 ... line L ₁ ... electrode end that indicates the average position of the electrode end and the sintered body end Distance between parts L ₂ ... Maximum value of unevenness in the main surface direction at the electrode end

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideyasu Ando 2-1 Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Toshiba Hamakawasaki Plant (72) Inventor Yoshiyasu Ito 2, Ukishima-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 F-term in Toshiba Hamakawasaki Plant (reference) 5E034 CA09 CB01 CC02 DA03 DB13 DB17 DC03 DC05 EA07 EB04

Claims (9)

[Claims] 1. A method for forming at least one of an electrode and a side insulating layer on a surface of a ceramic element, wherein the material layer is formed by high-speed spraying of a powder material to the ceramic element. A method for forming a material layer of a ceramic element. 2. When forming the electrode, the powder material for forming the electrode is at least one selected from the group consisting of aluminum, copper, zinc, nickel, silver, tungsten, and alloys thereof. In the case where the side surface insulating layer is formed, the powder material for forming the side surface insulating layer includes aluminum, silicon, boron,
2. The method for forming a material layer of a ceramic element according to claim 1, comprising at least one selected from the group consisting of alloys and compounds thereof. 3. The powder material according to claim 1, wherein a particle size of the powder is in a range of 0.1 μm to 200 μm.
The method for forming a material layer of a ceramic element according to the above. 4. The high-speed spraying process of the powder material is performed in an atmosphere including at least one selected from the group consisting of oxygen, nitrogen, air, hydrogen, argon, and helium when forming the electrode. 2. The method according to claim 1, wherein the side insulating layer is formed in an atmosphere containing at least one selected from the group consisting of oxygen and nitrogen. 5. The method for forming a material layer of a ceramic element according to claim 1, wherein the high-speed spraying of the powder material is performed at a particle velocity in a range of 100 m / s to 1000 m / s. 6. The ceramic element according to claim 1, wherein prior to the high-speed spraying of the powder material, a pre-heat treatment for preheating at least the surface of the ceramic element within a range of 50 ° C. to 350 ° C. is performed. Material layer forming method. 7. The forming conditions of the material layer in the high-speed spraying treatment of the powder material are as follows: a) the porosity contained in the material component of the material layer is 5% or less; b) the material component of the material layer The weight ratio of the metal oxide and metal nitride contained in the metal to the metal is 25% or less in the case of the electrode, and 75% or less in the case of the side surface insulating layer.
%) The average surface roughness of the material layer is 2.0 μm or less. D) The resistivity of the material layer is 15 μΩ ·
cm or less, and 10 ¹¹ Ω · cm in the case of a side insulating layer.
2. The method for forming a material layer of a ceramic element according to claim 1, wherein the method is set so as to satisfy at least one of the four characteristic conditions a to d. 8. When forming the electrode, the electrode forming conditions in the high-speed spraying process of the powder material are as follows: e) The distance between the electrode end and the ceramic element end is 0.0
F) The irregularity in the main surface direction at the end of the electrode is ± 0.5 mm.
2. The method for forming a material layer of a ceramic element according to claim 1, wherein the material is set so as to satisfy at least one of the following two dimensional conditions e and f: 9. A ceramic element having at least one material layer of an electrode and a side surface insulating layer formed on a surface thereof, wherein the material layer is selected from the material layer forming method according to any one of claims 1 to 8. A ceramic element, characterized by being a material layer formed by a modified method.