JPH01230207A - Nonlinear voltage resistor - Google Patents
Nonlinear voltage resistorInfo
- Publication number
- JPH01230207A JPH01230207A JP63054749A JP5474988A JPH01230207A JP H01230207 A JPH01230207 A JP H01230207A JP 63054749 A JP63054749 A JP 63054749A JP 5474988 A JP5474988 A JP 5474988A JP H01230207 A JPH01230207 A JP H01230207A
- Authority
- JP
- Japan
- Prior art keywords
- crystal phase
- specified
- bi2o3
- bismuth
- zinc oxide
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 11
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 First Substances 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は酸化亜鉛を主成分とする電圧非直線抵抗体に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a voltage nonlinear resistor containing zinc oxide as a main component.
（従来の技術）
従来から酸化亜鉛を主成分としＢｉｚＯ：＋＋ ５ｂｚ
Ｏ＋＋５ｉＯｚ＋ ＣｏｚＯ＝、 Ｍｎ０ｚ等の少量の
添加物を含有した抵抗体は、優れた電圧非直線性を示す
ことが広く知られており、その性質を利用して避雷器等
に使用されている。(Conventional technology) BizO: ++ 5bz has traditionally been made mainly of zinc oxide.
It is widely known that resistors containing small amounts of additives such as O++5iOz+ CozO=, Mn0z, etc. exhibit excellent voltage nonlinearity, and are used in lightning arresters and the like by taking advantage of this property.
特に避雷器として使用した場合、落雷により過大な電流
が流れても、その電流を通常は絶縁体であり所定電圧よ
りも過大な電圧が印加されると導体となる電圧非直線抵
抗体により接地するため、落雷による事故を防止するこ
とができる。In particular, when used as a lightning arrester, even if an excessive current flows due to a lightning strike, the current is grounded by a voltage nonlinear resistor that is normally an insulator and becomes a conductor when a voltage higher than the specified voltage is applied. , accidents caused by lightning can be prevented.
（発明が解決しようとする課題）
この電圧非直線抵抗体の結晶相として、酸化亜鉛の結晶
相のばか各種添加物に基く結晶相が存在し、この各種添
加物に基く結晶相持にビスマスの添加に基く結晶相がサ
ージ耐量、課電寿命等のバリスタ特性に大きな影響を与
えることが最近の研究で明らかになってきたが、未だそ
の結晶相の最適な組合せは知られておらず、サージ耐量
、課電寿命の点で未だ不十分な抵抗体が作製されていた
。(Problem to be solved by the invention) As the crystalline phase of this voltage nonlinear resistor, there is a crystalline phase based on various additives other than the crystalline phase of zinc oxide, and bismuth is added to the crystalline phase based on the various additives. Recent research has revealed that the crystalline phase based on However, resistors have been manufactured that are still insufficient in terms of electrification life.
本発明の目的は上述した課題を解消して、抵抗体の結晶
相を特定することによりサージ耐量、課電寿命等の特性
が良好な電圧非直線抵抗体を提供しようとするものであ
る。An object of the present invention is to solve the above-mentioned problems and provide a voltage nonlinear resistor with good characteristics such as surge resistance and energized life by specifying the crystalline phase of the resistor.
（課題を解決するための手段）
本発明の電圧非直線抵抗体は、酸化亜鉛を土成分とし、
少なくともビスマス、ケイ素成分を含む電圧非直線性を
有する焼結体において、焼結体中にＢｉ＋□ＳｉＯ□。(Means for solving the problems) The voltage nonlinear resistor of the present invention has zinc oxide as a soil component,
In a sintered body having voltage nonlinearity containing at least bismuth and silicon components, Bi+□SiO□ is present in the sintered body.
結晶相と、α−ＢｉｚＯ３結晶相、β−Ｂｉ２０３結晶
相およびＴ−Ｂｉ２０．結晶相のうち少なくとも１種以
上とを含むことを特徴とするものである。crystal phase, α-BizO3 crystal phase, β-Bi203 crystal phase and T-Bi20. It is characterized by containing at least one type of crystalline phase.
（作 用）
上述した構成において、焼結体中のビスマスの添加に基
く結晶相をＢｉｌ□ＳｉＯ□。結晶相と、α−Ｂｉ、Ｏ
。(Function) In the above structure, the crystal phase based on the addition of bismuth in the sintered body is Bil□SiO□. Crystal phase and α-Bi, O
.
結晶相、β−Ｂｉ２（ｈ結晶相および７−Ｂｉｚ０３結
晶相のうち少なくとも１種以上とを含む電圧非直線抵抗
体が、後述する実施例から明らかなように、サージ耐量
、課電寿命の点で他の結晶相を有するものより良好な特
性を示すことを新規に見出した。As is clear from the examples described later, a voltage nonlinear resistor containing a crystalline phase, β-Bi2 (and at least one of the h crystalline phase and the 7-Biz03 crystalline phase) has excellent surge resistance and energized life. It has been newly discovered that this material exhibits better properties than those having other crystalline phases.
なお、ケイ酸ビスマス（Ｂｉ、□ＳｉＯ□。）の量は、
０．５〜３ ｗＬ％であると好ましい。The amount of bismuth silicate (Bi, □SiO□.) is
It is preferably 0.5 to 3 wL%.
（実施例）
酸化亜鉛を主成分とする電圧非直線抵抗体を得るには、
まず所定の粒度に調整した酸化亜鉛原料と所定の粒度に
調整した酸化ビスマス、酸化コバルト、酸化マンガン、
酸化アンチモン、酸化クロム、酸化ケイ素、酸化ニッケ
ル、酸化ホウ素、酸化銀等よりなる添加物の所定量を混
合する。なお、この場合酸化銀、酸化ホウ素の代わりに
硝酸銀、ホウ酸を用いてもよい。好ましくは銀を含むホ
ウケイ酸ビスマスガラスを用いるとよい。この際、これ
らの原料粉末に対して所定量のポリビニルアルコール水
溶液等を加える。また好ましくは酸化アルミニウム源と
して硝酸アルミニウム溶液の所定量を添加する。この混
合操作は好ましくは乳化機を用いる。(Example) To obtain a voltage nonlinear resistor whose main component is zinc oxide,
First, zinc oxide raw material adjusted to a predetermined particle size, bismuth oxide, cobalt oxide, manganese oxide, adjusted to a predetermined particle size,
A predetermined amount of additives such as antimony oxide, chromium oxide, silicon oxide, nickel oxide, boron oxide, silver oxide, etc. are mixed. In this case, silver nitrate or boric acid may be used instead of silver oxide or boron oxide. Preferably, bismuth borosilicate glass containing silver is used. At this time, a predetermined amount of polyvinyl alcohol aqueous solution or the like is added to these raw material powders. Preferably, a predetermined amount of aluminum nitrate solution is added as a source of aluminum oxide. This mixing operation preferably uses an emulsifying machine.
次に好ましくは２００ ｍｍＨｇ以下の真空度で減圧脱
気を行い混合泥漿を得る。ここに混合泥漿の水分量は３
０〜３５−ｔ％程度に、またその混合泥漿の粘度は１０
０±５０ｃｐとするのが好ましい。次に得られた混合泥
漿を噴霧乾燥装置に供給して平均粒径５０〜１５０ ｕ
ｍ、好ましくは８０〜１２０ ａｍで、水分量が０．５
〜２．Ｏｗｔ％、より好ましくは０．９〜１．５ ｗｔ
％の造粒粉を造粒する。次に得られた造粒粉を、成形工
程において、成形圧力８００〜１０００ｋｇ／ｃｍ”の
下で所定の形状に成形する。そしてその成形体を昇降温
速度５０〜７０°Ｃ／ｈｒで８００〜１０００°Ｃ１保
持時間１〜５時間という条件で焼成する。なお、仮焼成
の前に成形体を昇降温速度１０〜１００°Ｃ／ｈｒで４
００〜６００°Ｃ１保持時間１〜１０時間で結合剤を飛
散除去することが好ましい。Next, deaeration is performed under reduced pressure, preferably at a vacuum level of 200 mmHg or less, to obtain a mixed slurry. Here, the water content of the mixed slurry is 3
0 to 35-t%, and the viscosity of the mixed slurry is 10
It is preferable to set it to 0±50 cp. Next, the obtained mixed slurry is fed to a spray dryer to obtain an average particle size of 50 to 150 u.
m, preferably from 80 to 120 am, and the moisture content is 0.5
~2. Owt%, more preferably 0.9-1.5 wt
% of granulated powder is granulated. Next, in a molding process, the obtained granulated powder is molded into a predetermined shape under a molding pressure of 800 to 1000 kg/cm. The molded body is fired at 1000°C for 1 to 5 hours for a holding time of 1 to 5 hours.Before pre-firing, the molded body is heated at a temperature increase/decrease rate of 10 to 100°C/hr for 4 hours.
It is preferable to scatter and remove the binder at 00 to 600° C. for a holding time of 1 to 10 hours.
次に、仮焼成した仮焼体の側面に絶縁被覆層を形成する
。本願発明では、ＢＩＺＯ３１５ｂｚ０３＋ ＺｎＯ。Next, an insulating coating layer is formed on the side surface of the calcined body. In the present invention, BIZO315bz03+ ZnO.
ＳｉＯ□等の所定量に有機結合剤としてエチルセルロー
ス、ブチルカルピトール、酢酸ｎブチル等を加えた酸化
物ペーストを、６０〜３００μｍの厚さに仮焼体の側面
に塗布する。次に、これを昇降温速度２０〜６０°Ｃ／
ｈｒ 、１０００〜１３００°Ｃ好ましくは１１００〜
１２５０℃、３〜７時間という条件で本焼成する。なお
、ガラス粉末に有機結合剤としてエチルセルロース、ブ
チルカルピトール、酢酸ｎブチル等を加えたガラスペー
ストを前記の絶縁被覆層上に１００〜３００μｍの厚さ
に塗布し、空気中で昇降温速度５０〜２００”Ｃ／ｈｒ
、４００〜９００℃保持時間０．５〜２時間という条
件で熱処理することによりガラス層を形成すると好まし
い。An oxide paste prepared by adding organic binders such as ethyl cellulose, butyl calpitol, n-butyl acetate, etc. to a predetermined amount of SiO□ is applied to the side surface of the calcined body to a thickness of 60 to 300 μm. Next, this is heated at a rate of 20 to 60°C/
hr, 1000~1300°C, preferably 1100~
Main firing is performed at 1250° C. for 3 to 7 hours. A glass paste prepared by adding ethyl cellulose, butyl calpitol, n-butyl acetate, etc. as an organic binder to glass powder is applied to a thickness of 100 to 300 μm on the above-mentioned insulating coating layer, and the temperature is raised and cooled in air at a rate of 50 to 300 μm. 200”C/hr
It is preferable to form the glass layer by heat treatment under conditions of 400 to 900°C for 0.5 to 2 hours.
その後、得られた電圧非直線抵抗体の両端面をＳｉＣ，
Ａｊ２ｚ０３＋ダイヤモンド等の＃４００〜２０００相
当の研暦剤により水好ましくは油を研磨液として使用し
て研磨する。次に、研磨面を洗浄後、研磨した両端面全
面に例えばアルミニウムメタ、リコン等によってメタリ
コン電極を例えば溶射により設けて電圧非直線抵抗体を
得ている。After that, both end faces of the obtained voltage nonlinear resistor were bonded to SiC,
Polishing is performed using a polishing agent equivalent to #400 to 2000, such as Aj2z03+diamond, using water, preferably oil, as the polishing liquid. Next, after cleaning the polished surfaces, metallicon electrodes made of aluminum metal, silicone, etc., are provided on the entire surface of both polished end surfaces by, for example, thermal spraying to obtain a voltage nonlinear resistor.
上述した装造方法において、原料の種類及び添加量、本
焼成条件、本焼成冷却速度、本焼成後における熱処理条
件等を種々組合わせることにより、焼結体中にＢｊ＋ｚ
ＳｉＯｚ。結晶相と、α−Ｂｉ２０１結晶相、β−Ｂｉ
２０３結晶相およびγ−Ｂｉｚ（ｈ結晶相のうち少なく
とも１種以上とを含む本発明の電圧非直線抵抗体が装造
でき、目的とするサージ耐量、課電寿命等の良好な電圧
非直線抵抗体が得られるものである。In the above-mentioned mounting method, Bj+z is added to the sintered body by various combinations of the type and amount of raw materials, main firing conditions, main firing cooling rate, heat treatment conditions after main firing, etc.
SiOz. Crystal phase, α-Bi201 crystal phase, β-Bi
The voltage nonlinear resistor of the present invention containing at least one type of 203 crystal phase and γ-Biz (h crystal phase) can be installed, and has a good voltage nonlinear resistance such as desired surge resistance and energized life. It's what the body gets.
以下、実際に本発明の範囲内および範囲外の電圧非直線
抵抗体において、各種特性を測定した結果について説明
する。Hereinafter, the results of actually measuring various characteristics of voltage nonlinear resistors within and outside the scope of the present invention will be described.
ス」１丸上
上述した方法に従って、ＢｉｚＯ３，Ｃｏｚ０３． Ｍ
ｎ０ｚ。According to the method described above, BizO3, Coz03. M
n0z.
５ｂ２０３． Ｃｒ２Ｃｈ＋ ＮｉＯを各々０．１〜２
．０モル％、Ａ ｆｆ （ＮＯ３） ・９８２０ ０
．００１〜０．０１モル％、ｉ艮を含むボウケイ酸ビス
マスガラス０４０１〜０．５モル％、ＳｉＯ□１．０〜
３．０モル％、残部ＺｎＯからなる原料から直径４７ｍ
ｍ、厚さ２０ｍｍの形状でバリスタ電圧（ＶｌｆｆｉＡ
）が１８０〜２２０ Ｖ／ｍｍの第１表に示す本発明試
料Ｎｏ、 １〜６と比較例試料Ｎｏ、 １の電圧非直線
抵抗体を準備した。5b203. Cr2Ch+ NiO 0.1-2 each
．． 0 mol%, A ff (NO3) ・9820 0
．． Bismuth borosilicate glass containing 0401-0.5 mol%, SiO□1.0-001-0.01 mol%
A diameter of 47 m from a raw material consisting of 3.0 mol% and the balance ZnO.
The varistor voltage (VlffiA
) of 180 to 220 V/mm, voltage nonlinear resistors of present invention samples No. 1 to 6 and comparative example sample No. 1 shown in Table 1 were prepared.
＄備した本発明および比較例の抵抗体に対して、雷サー
ジ耐量破壊率、開閉サージ耐量破壊率、雷サージ印加に
よるＶｌｆｆｉＡ低下率、漏洩電流の比を測定した。結
果を第１表に示す。ここで、雷サージ耐量破壊率は、１
００ＫＡおよび１２０ＫＡの電流を４７１０μｓの電流
波形で２回繰り返し印加した後に破壊したものの割合と
して求めた。開閉サージ耐量破壊率は、１００ＯＡおよ
び１２０ＯＡの電流を２１１１５の電流波形で２０回繰
り返し印加した後に破壊したものの割合として求めた。For the resistors of the present invention and comparative example, the lightning surge withstand breakdown rate, switching surge withstand breakdown rate, VlffiA reduction rate due to lightning surge application, and leakage current ratio were measured. The results are shown in Table 1. Here, the lightning surge resistance breakdown rate is 1
It was determined as the percentage of broken cells after 00 KA and 120 KA currents were repeatedly applied twice with a current waveform of 4710 μs. The switching surge withstand breakdown rate was determined as the percentage of breakdowns after 20 repeated applications of currents of 100OA and 120OA with a current waveform of 21115.
雷サージ印加によるＶＩｍＡ低下率は、４０ＫＡの電流
を４７１０μｓの電流波形で１０回印加した前後のＶＩ
ｆｆｉＡより求めた。漏洩電流の比は、素子を周囲温度
１３０°Ｃ課電率９５％で課電し、課電直後に対する課
電１００時間後の電流比１１０゜時間７１０時間から求
めた。また、Ｂｉ ＋ ｚｓｉｏｚ。の結晶相およびそ
の量比はＸ線回折による内部標準法により求めた。具体
的にはＢｉ１□Ｓｉｎｇ。の（１１１）ピークを用い、
ピーク分離等を行い定量した。The VImA reduction rate due to lightning surge application is the VImA decrease rate before and after applying a 40KA current 10 times with a 4710μs current waveform.
Obtained from ffiA. The leakage current ratio was determined from the current ratio of 110° hours and 710 hours after applying electricity for 100 hours to that immediately after applying electricity by applying electricity to the device at an ambient temperature of 130° C. and an application rate of 95%. Also, Bi + zsioz. The crystal phases and their quantitative ratios were determined by an internal standard method using X-ray diffraction. Specifically, Bi1□Sing. Using the (111) peak of
Quantification was performed by peak separation, etc.
（内部標準としてはＣａＣＯ３を使用）。(CaCO3 was used as the internal standard).
第１表の結果から、結晶相にＢｉ＋□５ｉＯｚ。と少な
くともα−Ｂｉｚ（ｈ結晶相とβ−Ｂｉｚ０３結晶相と
を含有する本発明試料Ｎｏ、 １〜６は、それらを含有
しない比較例試料Ｎαｌと比べて、サージ耐量、課電寿
命等のバリスタ特性が良好であることがわかる。From the results in Table 1, the crystal phase is Bi+□5iOz. Samples Nos. 1 to 6 of the present invention containing at least α-Biz (h crystal phase and β-Biz03 crystal phase) have improved varistor properties such as surge resistance and energized life compared to comparative sample Nαl which does not contain them. It can be seen that the characteristics are good.
ス新Ｉ生影
原料中のＳｉＯ□量を７〜１０モル％とした以外は実施
例１と同様の方法で、直径４７ｍｍ、厚さ２０ｍｍの形
状でＶＩ＋＋＋Ａが４００〜５００ Ｖ／ｍｍの第２表
に示す本発明試料Ｎａ ｌ〜５と比較例試料Ｎｏ、 １
の電圧非直線抵抗体を準備し、実施例１と同様の方法で
雷サージ耐量破壊率、開閉サージ耐量破壊率、雷サージ
印加によるＶＩ＋＊Ａ低下率、漏洩電流の比を測定した
。ただし、雷サージ耐量破壊率は７０ＫＡと８０ＫＡの
電流で、開閉サージ耐量破壊率は４００Ａと５００への
電流でそれぞれ測定した。結果を第２表に示す。A second film with a diameter of 47 mm and a thickness of 20 mm and a VI+++A of 400 to 500 V/mm was prepared in the same manner as in Example 1 except that the amount of SiO□ in the new I raw shadow material was 7 to 10 mol%. Invention samples Nal to 5 and comparative sample No. 1 shown in the table
A voltage nonlinear resistor was prepared, and the lightning surge withstand breakdown rate, switching surge withstand breakdown rate, VI+*A reduction rate due to lightning surge application, and leakage current ratio were measured in the same manner as in Example 1. However, the lightning surge withstand breakdown rate was measured at a current of 70 KA and 80 KA, and the switching surge breakdown rate was measured at a current of 400 A and 500 A, respectively. The results are shown in Table 2.
第２表の結果から、実施例１と同様に結晶相にＢｉ＋□
ＳｉＯ□０結晶相と少なくともα−８ｉ、０３結晶相と
７ Ｂｉ２Ｏ３結晶相とを含有する本発明試料Ｎａｌ
〜５は、それらを含有しない比較例試料Ｎａｌと比べて
、サージ耐量、課電寿命等のバリスタ特性が良好である
ことがわかる。From the results in Table 2, it can be seen that Bi+□ is present in the crystal phase as in Example 1.
Sample Nal of the present invention containing a SiO□0 crystal phase, at least an α-8i, 03 crystal phase, and a 7 Bi2O3 crystal phase
It can be seen that Samples No. 5 to No. 5 have better varistor characteristics such as surge resistance and energized lifespan than Comparative Example Sample Nal which does not contain them.
なお、実施例１の試料Ｎα４と実施例２の試料Ｎα３に
ついて、Ｘ線回折試験を行なった結果を第１図に示す。The results of an X-ray diffraction test performed on sample Nα4 of Example 1 and sample Nα3 of Example 2 are shown in FIG.
また、Ｂ１１ｚ ５ｉＯｚｏ結晶はＣｒ＋ Ｚｎ、 Ｓ
ｂ。In addition, the B11z 5iOzo crystal contains Cr+Zn, S
b.
Ｂ＋ Ｇｏ、 Ｍｎ等を固溶させることができ、その場
合には多少ピークがずれることがある。B+ Go, Mn, etc. can be dissolved in solid solution, and in that case, the peak may shift to some extent.
（発明の効果）
以上詳細に説明したところから明らかなように、本発明
の電圧非直線抵抗体によれば、抵抗体中のビスマス添加
に基く結晶相を所定の結晶相とすることにより、サージ
耐量、課電寿命等のバリスタ特性が良好な電圧非直線抵
抗体を得ることができる。また、制限電圧比、雷サージ
印加後におけるバリスタ電圧の変化率等の特性も良好な
ことが確認された。(Effects of the Invention) As is clear from the detailed explanation above, according to the voltage nonlinear resistor of the present invention, by changing the crystal phase based on bismuth addition in the resistor to a predetermined crystal phase, surge A voltage nonlinear resistor having good varistor characteristics such as withstand capacity and energized life can be obtained. It was also confirmed that the characteristics such as the limiting voltage ratio and the rate of change in varistor voltage after lightning surge application were also good.
第１図は、本発明の電圧非直線抵抗体に対するＸ線回折
試験の結果を示すグラフである。
特許出願人 日本碍子株式会社FIG. 1 is a graph showing the results of an X-ray diffraction test on the voltage nonlinear resistor of the present invention. Patent applicant Nippon Insulator Co., Ltd.
Claims (1)
素成分を含む電圧非直線性を有する焼結体において、焼
結体中にＢｉ＿１＿２ＳｉＯ＿２＿０結晶相と、α−Ｂ
ｉ＿２Ｏ＿３結晶相、β−Ｂｉ＿２Ｏ＿３結晶相および
γ−Ｂｉ＿２Ｏ＿３結晶相のうち少なくとも１種以上と
を含むことを特徴とする電圧非直線抵抗体。1. In a sintered body containing zinc oxide as a main component and having voltage nonlinearity and containing at least bismuth and silicon components, the sintered body contains a Bi_1_2SiO_2_0 crystal phase and an α-B
A voltage nonlinear resistor comprising at least one of an i_2O_3 crystal phase, a β-Bi_2O_3 crystal phase, and a γ-Bi_2O_3 crystal phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63054749A JPH07105286B2 (en) | 1988-03-10 | 1988-03-10 | Voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63054749A JPH07105286B2 (en) | 1988-03-10 | 1988-03-10 | Voltage nonlinear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230207A true JPH01230207A (en) | 1989-09-13 |
| JPH07105286B2 JPH07105286B2 (en) | 1995-11-13 |
Family
ID=12979417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63054749A Expired - Lifetime JPH07105286B2 (en) | 1988-03-10 | 1988-03-10 | Voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07105286B2 (en) |
-
1988
- 1988-03-10 JP JP63054749A patent/JPH07105286B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07105286B2 (en) | 1995-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0812807B2 (en) | Voltage nonlinear resistor and method of manufacturing the same | |
| CA1100749A (en) | Pre-glassing method of producing homogeneous sintered zno non-linear resistors | |
| US5039971A (en) | Voltage non-linear type resistors | |
| US4906964A (en) | Voltage non-linear resistor | |
| JPH0670658B2 (en) | Voltage inspection method for voltage non-linear resistors | |
| JPH01230207A (en) | Nonlinear voltage resistor | |
| JP2942027B2 (en) | Method of manufacturing voltage non-linear resistor | |
| JPH01228105A (en) | Manufacture of non-linear voltage resistance | |
| JP2533597B2 (en) | Method of manufacturing voltage non-linear resistor | |
| JPH0247802A (en) | Voltage nonlinear resistor body | |
| JPH0379850B2 (en) | ||
| JPH0412007B2 (en) | ||
| JPH0555008A (en) | Voltage-dependent nonlinear resistor | |
| JPH0254501A (en) | Nonlinear-to-voltage resistor | |
| JPH0812806B2 (en) | Voltage nonlinear resistor | |
| JPH03142801A (en) | Manufacture of voltage-dependent nonlinear resistor | |
| JPH04257201A (en) | Voltage non-linear resistor | |
| JPH07109804B2 (en) | Method for manufacturing voltage non-linear resistor | |
| JPH03250605A (en) | Manufacture of voltage non-linearity resistor | |
| JPH03181102A (en) | Manufacture of nonlinearly voltage-dependent resistor | |
| JPH0547514A (en) | Manufacture of non-linearly voltage dependent resistor | |
| JPH0379851B2 (en) | ||
| JPH0429206B2 (en) | ||
| JPS62249401A (en) | Manufacture of voltage nonlinear resistance element | |
| JPH0379852B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 13 |