JPH03112101A - Manufacture of varistor - Google Patents
Manufacture of varistorInfo
- Publication number
- JPH03112101A JPH03112101A JP1249036A JP24903689A JPH03112101A JP H03112101 A JPH03112101 A JP H03112101A JP 1249036 A JP1249036 A JP 1249036A JP 24903689 A JP24903689 A JP 24903689A JP H03112101 A JPH03112101 A JP H03112101A
- Authority
- JP
- Japan
- Prior art keywords
- predetermined
- mixture
- mixed
- oxide
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 8
- 239000011230 binding agent Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000000314 lubricant Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000001419 dependent effect Effects 0.000 abstract 1
- -1 dispersive Substances 0.000 abstract 1
- 238000010285 flame spraying Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、酸化亜鉛を主成分とする非直線抵抗体の製造
方法に係り、特に、キ４料混合工程に改良を施した非直
線抵抗体の製造方法に関するものである。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a method for manufacturing a non-linear resistor whose main component is zinc oxide, and in particular improves the key material mixing step. The present invention relates to a method for manufacturing a non-linear resistor.
（従来の技術）
酸化亜鉛を主成分とする非直線抵抗体は、酸化亜鉛粒子
とその周囲を取りまく添加物より形成される粒界層から
成り、優れた非直線抵抗特性は酸化亜鉛粒子と粒界層と
の界面に起因すると考えられている。(Prior art) A nonlinear resistor whose main component is zinc oxide consists of a grain boundary layer formed by zinc oxide particles and additives surrounding them. It is thought that this is caused by the interface with the boundary layer.
この様な酸化亜鉛を主成分とする非直線抵抗体の工業的
な製造方法としては、以下に述べるような方法が用いら
れている。即ち、原料である酸化物粉末を所定量秤量の
上、水と共に混合機に投入し、所定時間、粉砕メディア
により粉砕しながら混合する。粉砕メディアによる汚染
を避けるため、粉砕メディアを用いない間隙通過型の乳
化機を用いる場合もある。また、次の造粒工程のために
バインダ（例えば、ポリビニールアルコール）を加える
場合もある。また、混合を十分に行うために、長時間混
合する方法、液体に対する固形分量を小さくして混合す
る方法、添加物成分を予め混合してから主成分と混合す
る方法、添加物成分を予め仮焼結して微粉砕し、その後
、主成分と混合する方法等が試みられている。As an industrial method for manufacturing such a non-linear resistor containing zinc oxide as a main component, the following method is used. That is, a predetermined amount of oxide powder as a raw material is weighed, put into a mixer together with water, and mixed while being pulverized by a pulverizing media for a predetermined period of time. In order to avoid contamination by grinding media, a gap-passing type emulsifier that does not use grinding media may be used. A binder (eg, polyvinyl alcohol) may also be added for the next granulation step. In addition, in order to achieve sufficient mixing, methods include mixing for a long time, mixing with a small amount of solids relative to the liquid, mixing the additive components in advance and then mixing them with the main component, and pre-mixing the additive components in advance. Attempts have been made to sinter it, pulverize it, and then mix it with the main component.
（発明が解決しようとする課題）
しかしながら、上記の様な非直線抵抗体の製造方法にお
いては、以下に述べる様な解決すべき課題があった。(Problems to be Solved by the Invention) However, in the method for manufacturing a non-linear resistor as described above, there are problems to be solved as described below.
即ち、主成分である酸化亜鉛に添加され、粒界層を形成
するビスマス、アンチモン、コバルト、マンガン、クロ
ム等の酸化物の量が極めて少量であるため（添加物全体
でも１０％以下、成分によっては０．５％以下）、主成
分と添加物とを均一に混合することが非常に難しいこと
である。このことは、混合物スラリー中の成分分布や焼
結体の微細構造観察、元素分布等から確かめられている
。In other words, the amount of oxides such as bismuth, antimony, cobalt, manganese, and chromium that are added to the main component zinc oxide and form grain boundary layers is extremely small (less than 10% of all additives, depending on the component). (0.5% or less), it is very difficult to uniformly mix the main components and additives. This has been confirmed from the component distribution in the mixture slurry, observation of the fine structure of the sintered body, element distribution, etc.
また、その結果として、非直線抵抗特性の低下や、その
特性上のバラツキばかりでなく、課電寿命、放電耐量等
の他の性能の低下やバラツキ等が生じるといった欠点が
あった。さらに、粉砕メディアによる不純物の混入が避
けられず、電気的特性が低下し、また、製造工程が複雑
になるといった欠点もあった。Further, as a result, there are drawbacks such as not only a decrease in non-linear resistance characteristics and variations in the characteristics, but also a decrease in and variations in other performances such as charging life and discharge withstand capacity. Furthermore, there are also drawbacks such as unavoidable contamination of impurities by the grinding media, deterioration of electrical characteristics, and complication of the manufacturing process.
本発明は、以上の欠点を解消するために提案されたもの
で、その目的は、材料混合工程における非直線抵抗体の
特性低下やバラツキを小さくし、放電耐量を向」ニさせ
ることのできる非直線抵抗体の製造方法を提供すること
にある。The present invention was proposed in order to eliminate the above-mentioned drawbacks, and its purpose is to reduce the deterioration and variation in the characteristics of non-linear resistors during the material mixing process, and to improve the discharge withstand capacity. An object of the present invention is to provide a method for manufacturing a linear resistor.
［発明の構成］
（課題を解決するだめの手段）
本発明の非直線抵抗体の製造方法は、酸化亜鉛を主成分
とした粉末に、電圧非直線性を生じさせるための添加物
を加えて水と共に混合する工程に、ポリアクリレートの
アンモニウム塩を分散剤として加えることを特徴とする
ものである。[Structure of the Invention] (Means for Solving the Problems) The method for manufacturing a non-linear resistor of the present invention involves adding an additive to produce voltage non-linearity to powder containing zinc oxide as a main component. This method is characterized by adding an ammonium salt of polyacrylate as a dispersant to the mixing step with water.
（作用）
本発明の非直線抵抗体の製造方法によれば、主成分と添
加物は、凝集した粒子が一次粒子にまで分散するため、
均一に混合でき、非直線抵抗特性が良好で、バラツキの
少ない放電耐量の大きな非直線抵抗体を得ることができ
る。(Function) According to the method for manufacturing a non-linear resistor of the present invention, since the main component and additives are aggregated and dispersed into primary particles,
It is possible to obtain a nonlinear resistor that can be mixed uniformly, has good nonlinear resistance characteristics, and has a large discharge withstand capacity with little variation.
（実施例） 以下、本発明の一実施例を詳細に説明する。(Example) Hereinafter, one embodiment of the present invention will be described in detail.
本実施例においては、酸化亜鉛（Ｚ ｎ Ｏ）と酸化ビ
スマス（ＢｆｚＯ９）の粉末を９７．５モル％と酸化コ
バルト（Ｃｏｄ）、酸化マンガン（Ｍｎｏ）、酸化アン
チモン（Ｓｂ２０３）、酸化クロム（ＣｒｚＯ３）の粉
末を各々０．５モル％ずつ秤量する。これを固形分濃度
が３０％になるように水と共にボールミルの中へ投入し
、さらに、ポリアクリレートのアンモニウム塩を固形分
で主成分原料の固形分に対し０，２ｗｔ％になるように
水溶液として添加し、さらにバインダと潤滑剤とを加え
２４時間混合する。この混合スラリーをスプレードライ
ヤで乾燥造粒し、直径８０ｍｍ。In this example, 97.5 mol% of powders of zinc oxide (ZnO) and bismuth oxide (BfzO9) were combined with cobalt oxide (Cod), manganese oxide (Mno), antimony oxide (Sb203), and chromium oxide (CrzO3). 0.5 mol % of each powder is weighed out. This was put into a ball mill with water so that the solid content concentration was 30%, and then the ammonium salt of polyacrylate was made into an aqueous solution so that the solid content was 0.2 wt% based on the solid content of the main component raw material. Add binder and lubricant and mix for 24 hours. This mixed slurry was dried and granulated with a spray dryer to a diameter of 80 mm.
厚さ３０ｍｍに圧縮成形する。添加した分散剤、バイン
ダ、潤滑剤を予め除くため、空気中で５００℃で焼成す
る。さらに、１０５０℃で予備焼成し、高抵抗形成物を
塗布後、空気中で１２００℃で焼結させて得られた焼結
体の両手面を研磨し、５００℃で再加熱し、この両手面
に例えばアルミニウムをメタリコンして電極を形成し、
非直線抵抗体を完成させる。Compression mold to a thickness of 30 mm. In order to remove the added dispersant, binder, and lubricant in advance, it is fired in air at 500°C. Furthermore, both hands of the sintered body were pre-fired at 1050°C, coated with a high-resistance material, and then sintered in air at 1200°C, and then reheated at 500°C. For example, metallized aluminum is used to form electrodes.
Complete the nonlinear resistor.
（以下余白）
第
表
第
表
第１表は本実施例により得られた混合スラリーを従来の
場合と比較したものである。表から明らかな様に、本実
施例においては、混合スラリーの粘性は著しく低下し、
ＰＨは大きく変化し、その効果の相違は明白である。ま
た、混合物スラリーの成分分布を調べた結果、従来例よ
りも均一に分布しており、また、水に分散した粒子の大
きさを調べた結果、本実施例ではほぼ一次粒子にまで分
散しており、一方、従来例では分散が不１−分で、主成
分、添加物共に凝集したままの状態で、偏在が認められ
た。(The following is a margin) Table 1 Table 1 compares the mixed slurry obtained in this example with the conventional case. As is clear from the table, in this example, the viscosity of the mixed slurry decreased significantly,
The PH varies greatly and the difference in effectiveness is obvious. In addition, as a result of examining the component distribution of the mixture slurry, it was found that the distribution was more uniform than in the conventional example, and as a result of examining the size of the particles dispersed in water, it was found that in this example, they were dispersed to almost primary particles. On the other hand, in the conventional example, the dispersion was insufficient, and both the main component and the additive remained aggregated, and uneven distribution was observed.
第２表は、−に連の様にして得られた非直線抵抗体の電
気緒特性を示したものである。この表において、Ｖ（１
ｍＡ）は、１ｍＡの交流抵抗分電流を流した時の電圧で
ある。また、Ｖ（１０ｋＡ）／Ｖ （１ｍＡ） 、Ｖ
（１ｍＡ）／Ｖ （０，１ｍＡ）、Ｖ （０，１ｍＡ）
／Ｖ （０，０１ｍＡ）は同様に、それぞれの電流を流
した時の電圧の比であり、表示電流値の範囲における非
直線抵抗特性を表すもので、値の小さいものほど良い性
能を示している。ａ （Ｖ （１ｍＡ）ｌ は、製造し
た１０００個に対するＶ（１ｍＡ）のバラツキを表わす
。また、εは交流５ Ｑ Ｈｚにおける誘電率を表わす
。さらに、放電耐量は２ｍｓの矩形波電流を５回流し、
破壊した電流値における消費エネルギーを単位体積当た
りに換算したものである。また、課電寿命試験は、周囲
温度１００℃でＶ （１ｍＡ）の８５％の交流電圧（最
大値）を２０００時間印加した場合の交流抵抗分電流の
変化率を表わしたものであり、変化率の小さいものが性
能の優れていることを表わしている。なお、第２表から
明らかな様に、」１記の各項目において、本発明に係る
実施例がいずれも優れた結果となった。Table 2 shows the electrical characteristics of the nonlinear resistors obtained in the same manner. In this table, V(1
mA) is the voltage when a current corresponding to an AC resistance of 1 mA flows. Also, V (10kA)/V (1mA), V
(1mA)/V (0,1mA), V (0,1mA)
Similarly, /V (0,01mA) is the ratio of the voltages when each current is passed, and it represents the nonlinear resistance characteristic in the range of displayed current values, and the smaller the value, the better the performance. There is. a (V (1 mA)l represents the variation in V (1 mA) for 1000 manufactured pieces. Also, ε represents the dielectric constant at AC 5 Q Hz. Furthermore, the discharge withstand capacity is determined by applying a 2 ms square wave current 5 times. sink,
The energy consumption at the current value of destruction is calculated per unit volume. In addition, the energization life test expresses the rate of change in the AC resistance current when an AC voltage (maximum value) of 85% of V (1 mA) is applied for 2000 hours at an ambient temperature of 100°C. A smaller value indicates better performance. As is clear from Table 2, all of the Examples according to the present invention achieved excellent results in each of the items listed in item 1.
また、調査の結果、焼結体のどの部分においても、その
微細構造が均一になっていることが明らかとなった。即
ち、混合物スラリー中の成分分布が均一になり、且つ、
主成分も一次粒子にまで十分に分散した結果、焼結体に
おいて、非直線抵抗特性が生ずる原因となる微細構造が
、焼結体のどの部分においても均一になったため、上記
の諸特性が改善されたと考えられる。Furthermore, the results of the investigation revealed that the microstructure was uniform in all parts of the sintered body. That is, the component distribution in the mixture slurry becomes uniform, and
As the main components were sufficiently dispersed down to the primary particles, the microstructure that causes non-linear resistance characteristics in the sintered body became uniform in all parts of the sintered body, and the above characteristics were improved. It is thought that it was done.
さらに、第１図は、原料固形分濃度を６０％とし、バイ
ンダ・潤滑剤を加えた場合のポリアクリレートのアンモ
ニウム塩の添加量の分散効果を表わす混合スラリーの粘
度を示す図である。図から明らかな様に、その効果は、
ポリアクリレートのアンモニウム塩の添加量が０．１〜
１．０ｗｔ％の際に良好であることがわかる。Furthermore, FIG. 1 is a diagram showing the viscosity of a mixed slurry representing the dispersion effect of the amount of ammonium salt of polyacrylate added when the raw material solid content concentration is 60% and a binder/lubricant is added. As is clear from the figure, the effect is
Addition amount of ammonium salt of polyacrylate is 0.1~
It can be seen that the content is good when the content is 1.0 wt%.
また、第２図は、混合時間とＶ （１ｍＡ）のバラツキ
の関係を示す図で、この図からも明らかな様に、混合時
間は本実施例の２４時間でなくても、その１／４の６時
間まで短縮することができるといえる。Moreover, FIG. 2 is a diagram showing the relationship between the mixing time and the variation in V (1 mA). As is clear from this diagram, even if the mixing time is not 24 hours as in this example, it is 1/4 of that. It can be said that the time can be shortened to 6 hours.
この様に、本実施例によれば、酸化亜鉛を主体とする非
直線抵抗体を製造する際に、原料粉末を水と混合する時
に、ポリアクリレートのアンモニウム塩を添加すること
により、主体成分と添加成分が均一に混合でき、その結
果、焼結体中の微細構造が均一になり、非直線抵抗特性
をはじめ、放電耐Ｊ″ｎその他の諸特性が著しく改善さ
れる。また、この様にして得られた非直線抵抗体は、電
力用機器を保護するために高い信頼性が要求される電力
用避雷器の素子等の用途には特に適している。さらに、
固形分濃度を著しく高くできること、混合時間を著しく
短縮できること等、工業的価値も大きい。As described above, according to this example, when manufacturing a non-linear resistor mainly composed of zinc oxide, by adding ammonium salt of polyacrylate when mixing raw material powder with water, the main component can be mixed with water. The additive components can be mixed uniformly, and as a result, the fine structure in the sintered body becomes uniform, and nonlinear resistance characteristics, discharge resistance J″n, and other various characteristics are significantly improved. The obtained nonlinear resistor is particularly suitable for applications such as elements of power surge arresters that require high reliability to protect power equipment.Furthermore,
It also has great industrial value, such as being able to significantly increase the solid content concentration and significantly shortening the mixing time.
なお、本発明は上述した実施例に限定されるものではな
（、酸化亜鉛に添加される添加物としては、酸化ビスマ
ス（Ｂｉ２０３）、酸化コバルト（ＣｏＯ）、酸化マン
ガン（ＭｎＯ）、酸化アンチモン（Ｓｂ２０３）、酸化
クロム（Ｃｒｚ０３）の他に、酸化鉛（ＰｂＯ）、酸化
バリウム（ＢａＯ）、酸化ニッケル（Ｎ ｉ Ｏ） 、
酸化第二錫（Ｓｎ０２）、二酸化ケイ素（ＳｉＯ７）、
酸化チタン（Ｔ ｉ ０２ ） 、酸化アルミニウム（
Ａｌ□０３）、酸化銀（Ａｇ２０） 、酸化ホウ素（Ｂ
２０３）、各種のホウケイ酸系ガラスフリット、ホウケ
イ酸鉛ガラスフリット系等、酸化亜鉛粒子の半導性を変
えるもの、酸化亜鉛粒子を取り囲む粒界層を構成する部
分の性質を変えるもの等、上記のすべての場合に、本発
明の有効性は何等損なわれることなく、同様の効果が得
られることが確かめられている。Note that the present invention is not limited to the above-mentioned examples (additives added to zinc oxide include bismuth oxide (Bi203), cobalt oxide (CoO), manganese oxide (MnO), antimony oxide ( Sb203), chromium oxide (Crz03), lead oxide (PbO), barium oxide (BaO), nickel oxide (N i O),
tin oxide (Sn02), silicon dioxide (SiO7),
Titanium oxide (T i 02 ), aluminum oxide (
Al□03), silver oxide (Ag20), boron oxide (B
203), various borosilicate glass frits, borosilicate lead glass frits, etc. that change the semiconductivity of zinc oxide particles, things that change the properties of the part that constitutes the grain boundary layer surrounding zinc oxide particles, etc. It has been confirmed that in all cases, the effectiveness of the present invention is not impaired in any way and similar effects can be obtained.
また、本発明ではボールミルによる粉砕メディアが用い
られているが、ボールミル以外の粉砕メディアを用いる
混合機、また、粉砕メディアを用いない間隙通過型の混
合機においても、本発明の有効性は何等損なわれること
がないことが確認されている。さらに、本発明によって
、粉砕メディアの摩耗による不純物の混入が増大して、
上記諸特性を損なうことがなかったことは、実施例の結
果からも明らかである。また、上記の実施例においては
、分散剤の他にバインダと潤滑剤を添加したが、これは
次工程のためであり、本発明の効果に何等影響のないこ
とはいうまでもない。In addition, although the present invention uses a grinding media produced by a ball mill, the effectiveness of the present invention is not impaired in any way in a mixer using grinding media other than a ball mill, or in a gap-passing mixer that does not use grinding media. It has been confirmed that there will be no Furthermore, according to the present invention, contamination of impurities due to abrasion of the grinding media is increased,
It is clear from the results of Examples that the above properties were not impaired. Further, in the above embodiments, a binder and a lubricant were added in addition to the dispersant, but this was for the next step, and it goes without saying that this has no effect on the effects of the present invention.
［発明の効果］
以上述べた様に、本発明によれば、主成分としての酸化
亜鉛に対して加えられる微量の各種添加物を、十分に均
一に混合させることができ、非直線抵抗特性や他の電気
的緒特性を向上させると共に、均質な特性を有する非直
線抵抗体の製造方法を提供することができる。[Effects of the Invention] As described above, according to the present invention, trace amounts of various additives added to zinc oxide as the main component can be mixed sufficiently uniformly, and non-linear resistance characteristics and It is possible to provide a method for manufacturing a nonlinear resistor that has uniform characteristics while improving other electrical characteristics.
第１図は本発明に係るポリアクリレートのアンモニウム
塩の添加量と粘度との関係を示す図、第２図は本発明に
係る混合スラリーの混合時間と特性上のバラツキの関係
を示す図である。FIG. 1 is a diagram showing the relationship between the amount of ammonium salt added and the viscosity of polyacrylate according to the present invention, and FIG. 2 is a diagram showing the relationship between the mixing time and the variation in characteristics of the mixed slurry according to the present invention. .
Claims (1)
せるための添加物を加えて水と共に混合する工程に、ア
クリル酸とアクリル酸エステル共重合体のアンモニウム
塩（以下、ポリアクリレートのアンモニウム塩と称す）
を分散剤として加えることを特徴とする非直線抵抗体の
製造方法。An ammonium salt of acrylic acid and acrylic acid ester copolymer (hereinafter referred to as ammonium salt of polyacrylate) is added to a powder mainly composed of zinc oxide, and mixed with water to create voltage nonlinearity. (referred to as salt)
A method for manufacturing a nonlinear resistor, characterized by adding as a dispersant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1249036A JPH03112101A (en) | 1989-09-27 | 1989-09-27 | Manufacture of varistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1249036A JPH03112101A (en) | 1989-09-27 | 1989-09-27 | Manufacture of varistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03112101A true JPH03112101A (en) | 1991-05-13 |
Family
ID=17187050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1249036A Pending JPH03112101A (en) | 1989-09-27 | 1989-09-27 | Manufacture of varistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03112101A (en) |
-
1989
- 1989-09-27 JP JP1249036A patent/JPH03112101A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH03112101A (en) | Manufacture of varistor | |
| JP2000232005A (en) | Nonlinear resistor | |
| KR920005155B1 (en) | Zno-varistor making method | |
| JPS6322602B2 (en) | ||
| JPS621202A (en) | Voltage non-linear resistor | |
| JPH02164006A (en) | Zinc oxide type varistor | |
| JPH05234716A (en) | Zinc oxide varistor | |
| WO2024056557A1 (en) | Ceramic materials including core-shell particles and varistors including the same | |
| JPS63132401A (en) | Manufacture of voltage nonlinear resistor | |
| JPS59189604A (en) | Method of producing nonlinear resistor | |
| JP2003007512A (en) | Nonlinear resistor element | |
| JPH0212901A (en) | Manufacture of zinc oxide varistor | |
| JPH0744088B2 (en) | Method for manufacturing voltage non-linear resistor | |
| JP2001052907A (en) | Ceramic element and manufacturing method | |
| JPH0510804B2 (en) | ||
| JP2563970B2 (en) | Oxide voltage nonlinear resistor manufacturing method | |
| JP5929152B2 (en) | Method for manufacturing non-linear resistor element | |
| JPH0528883B2 (en) | ||
| KR20040078915A (en) | Zinc Oxide Sintered Body, and Manufacturing Method thereof and Zinc Oxide Varistor | |
| JPS59108301A (en) | Method of producing nonlinear resistor | |
| JPS59103303A (en) | Method of producing nonlinear resistor | |
| JPS63132402A (en) | Manufacture of voltage nonlinear resistor | |
| JPS61139004A (en) | Non-linear resistor | |
| JP2003077707A (en) | Method for manufacturing non linear resistor | |
| JPH05275208A (en) | Manufacture of voltage nonlinear resistor |