JPH0249526B2 - - Google Patents
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- Publication number
- JPH0249526B2 JPH0249526B2 JP59173031A JP17303184A JPH0249526B2 JP H0249526 B2 JPH0249526 B2 JP H0249526B2 JP 59173031 A JP59173031 A JP 59173031A JP 17303184 A JP17303184 A JP 17303184A JP H0249526 B2 JPH0249526 B2 JP H0249526B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- voltage
- constant
- varistor
- zno
- 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.)
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 105
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 61
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 37
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 32
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 24
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910011255 B2O3 Inorganic materials 0.000 claims 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 description 51
- 229910000428 cobalt oxide Inorganic materials 0.000 description 30
- 238000010586 diagram Methods 0.000 description 22
- 239000000292 calcium oxide Substances 0.000 description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- -1 Sb 2 O 3 Inorganic materials 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003107 Zn2SnO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 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
- 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
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal 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
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102220037054 rs587780188 Human genes 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 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
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電気回路における異常高電圧の吸収
等に使用される電圧非直線抵抗体（以下、バリス
タと呼ぶ）に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a voltage nonlinear resistor (hereinafter referred to as a varistor) used for absorbing abnormally high voltage in an electric circuit.
従来の技術
ZnOを主成分とした酸化物バリスタとして、
ZnOにBi2O3、CoO、MnO、Sb2O3、NiOおよび
SiO2を添加してなるバリスタが例えば特公昭53
−11076号公報で知られている。また、ZnOに
SrO、CoOを添加してなるバリスタ（特公昭48−
6754号公報）、ZnOにBaO、CoOを添加してなる
バリスタ（特公昭48−6755号公報）、ZnOに
BaO、MnO2を添加してなるバリスタ（特公昭48
−6756号公報）なども知られている。Conventional technology As an oxide varistor whose main component is ZnO,
ZnO with Bi 2 O 3 , CoO, MnO, Sb 2 O 3 , NiO and
For example, a varistor made by adding SiO 2 was developed in 1973.
It is known from the publication No.-11076. Also, ZnO
Varistors made by adding SrO and CoO
6754), varistors made by adding BaO and CoO to ZnO (Special Publication No. 6755), ZnO
Varistors made by adding BaO and MnO 2 (Special Publication 1973
-6756) are also known.
発明が解決しようとする問題点
しかし、前者のビスマスを使用するバリスタ
は、非直線指数αは非常に大きいという長所を有
しているが、焼成工程において、酸化ビスマスが
蒸発するため、焼成された素子が互いに付着した
り、焼成炉の耐火物に付着したり、また耐火物が
割れたりするために素子歩留りが悪いという欠点
を有している。一方、後者の３種類のバリスタ
は、非直線指数αが10〜20程度であり、非直線指
数αを30程度にするためには、ZnOにSrOあるい
はBaOを添加して焼成した焼結体にCoOあるい
はMnO2を塗布して再度焼成しなければならない
という欠点を有している。そこで、本発明の目的
は、実用上十分な電圧非直線性と安定性とを有
し、且つ製造が容易であるバリスタを提供するこ
とにある。Problems to be Solved by the Invention However, although the former varistor using bismuth has the advantage of having a very large nonlinear index α, the bismuth oxide evaporates during the firing process, so This method has the disadvantage that the yield of devices is poor because the devices stick to each other, stick to the refractories of the firing furnace, and crack the refractories. On the other hand, the latter three types of varistors have a non-linearity index α of about 10 to 20, and in order to make the non-linearity index α about 30, it is necessary to use a sintered body made by adding SrO or BaO to ZnO. It has the disadvantage of having to be coated with CoO or MnO 2 and fired again. Therefore, an object of the present invention is to provide a varistor that has practically sufficient voltage nonlinearity and stability and is easy to manufacture.
問題点を解決するための手段
上記目的を達成するための本発明のバリスタ
は、亜鉛（Zn）、バリウム（Ba）、ストロンチウ
ム（Sr）、カルシウム（Ca）、マグネシウム
（Mg）、チタン（Ti）、錫（Sn）、ジルコニウム
（Zr）、ケイ素（Si）、ゲルマニウム（Ge）、コバ
ルト（Co）、アンチモン（Sb）、ホウ素(B)、イツ
トリウム（Ｙ）、イツテルビウム（Yb）、エルビ
ウム（Er）、アルミニウム（Al）、リチウム
（Li）、カリウム(K)を、これ等の代表的酸化物であ
る酸化亜鉛（ZnO）、酸化バリウム（BaO）、酸
化ストロンチウム（SrO）、酸化カルシウム
（CaO）、酸化マグネシウム（MgO）、酸化チタン
（TiO2）、酸化錫（SnO2）、酸化ジルコニウム
（ZrO2）、酸化ケイ素（SiO2）、酸化ゲルマニウム
（GeO2）、酸化コバルト（CoO）、酸化アンチモン
（Sb2O3）、酸化ホウ素（B2O3）、酸化イツトリウ
ム（Y2O3）、酸化イツテルビウム（Yb2O3）、酸
化エルビウム（Er2O3）、酸化アルミニウム
（Al2O3）、酸化リチウム（Li2O）、酸化カリウム
（K2O）に換算した組成比で、ZnO（第１成分）
52.9〜99.5985モル％、BaO、SrO、CaOおよび
MgOの一種以上の酸化物（第２成分）0.1〜５モ
ル％、TiO2、SnO2、ZrO2、SiO2およびGeO2の
一種以上の酸化物（第３成分）0.1〜５モル％、
CoO（第４成分）0.1〜30モル％、Sb2O3、B2O3、
Y2O3、Yb2O3およびEr2O3の一種以上の酸化物
（第５成分）0.1〜５モル％、Al2O3（第６成分）
0.001〜１モル％、Li2OおよびK2Oの一種以上の
酸化物（第７成分）0.0005〜1.1モル％（但し、
第７成分／第６成分のモル比の範囲は0.5〜1.1）
となるように含む焼結体から成る。Means for Solving the Problems The varistor of the present invention for achieving the above object contains zinc (Zn), barium (Ba), strontium (Sr), calcium (Ca), magnesium (Mg), titanium (Ti). , tin (Sn), zirconium (Zr), silicon (Si), germanium (Ge), cobalt (Co), antimony (Sb), boron (B), yttrium (Y), ytterbium (Yb), erbium (Er) ), aluminum (Al), lithium (Li), potassium (K), and their typical oxides such as zinc oxide (ZnO), barium oxide (BaO), strontium oxide (SrO), and calcium oxide (CaO). , magnesium oxide (MgO), titanium oxide (TiO 2 ), tin oxide (SnO 2 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), germanium oxide (GeO 2 ), cobalt oxide (CoO), antimony oxide (Sb 2 O 3 ), boron oxide (B 2 O 3 ), yttrium oxide (Y 2 O 3 ), ytterbium oxide (Yb 2 O 3 ), erbium oxide (Er 2 O 3 ), aluminum oxide (Al 2 O 3 ), ZnO (first component), composition ratio converted to lithium oxide (Li 2 O) and potassium oxide (K 2 O)
52.9~99.5985 mol%, BaO, SrO, CaO and
0.1 to 5 mol % of one or more oxides of MgO (second component), 0.1 to 5 mol % of one or more oxides of TiO 2 , SnO 2 , ZrO 2 , SiO 2 and GeO 2 (third component),
CoO (fourth component) 0.1 to 30 mol%, Sb 2 O 3 , B 2 O 3 ,
0.1 to 5 mol% of one or more oxides of Y 2 O 3 , Yb 2 O 3 and Er 2 O 3 (fifth component), Al 2 O 3 (sixth component)
0.001 to 1 mol%, 0.0005 to 1.1 mol% of one or more oxides of Li 2 O and K 2 O (seventh component) (however,
The molar ratio of the seventh component/sixth component is in the range of 0.5 to 1.1)
It consists of a sintered body containing the following.
作 用
上記発明によれば、各成分の相乗効果により、
実用上十分な電圧非直線性及び安定性（耐サージ
性）を有するバリスタを提供することが出来る。
また、ビスマスを使用しないので、これによつて
生じた弊害を除去することが出来る。Effect According to the above invention, due to the synergistic effect of each component,
A varistor having practically sufficient voltage nonlinearity and stability (surge resistance) can be provided.
Furthermore, since bismuth is not used, the adverse effects caused by bismuth can be eliminated.
実施例
次に、図面を参照して本発明の実施例について
述べる。本発明の酸化物バリスタを製作するため
に、まず、ZnOが52.9〜99.5985モル％、BaO、
SrO、CaOおよびMgOの一種以上が0.1〜５モル
％、TiO2、SnO2、ZrO2、SiO2およびGeO2の一
種以上が0.1〜５モル％、CoOが0.1〜30モル％、
Sb2O3、B2O3、Y2O3、Yb2O3およびEr2O3の一種
以上が0.1〜５モル％、Al2O3が0.001〜１モル％、
Li2OおよびK2Oの一種以上が0.0005〜1.1モル％
であり、これ等の総和が100モル％になるように
各酸化物原料を計量し、これをボールミルなどに
よつて十分混合した後、ポリビニールアルコール
などの有機結合剤を用いて造粒した。なお、出発
原料としては酸化物の代りに水酸化物や炭酸塩あ
るいは二元金属酸化物などを用いることも可能で
ある。また、成形焼成後の寸法、特性のバラツキ
などに支障をきたすときは600〜1000℃の空気中
で１〜３時間仮焼し、これを微粉に粉砕してその
後に造粒してもよい。このようにして得られた
種々の組成の造粒粉を0.5〜2.0ton／cm2の圧力で
加圧成形し、直径15.0mm、厚さ2.0mmのデイスク
型に仕上げ、更に、この成形物を1000〜1400℃の
空気中で１〜３時間焼成し、最後に、この焼結体
の両面にAgペーストを焼付けることにより電極
を形成して種々の組成の酸化物バリスタの素子を
完成させた。Embodiments Next, embodiments of the present invention will be described with reference to the drawings. In order to manufacture the oxide varistor of the present invention, first, ZnO was 52.9 to 99.5985 mol%, BaO,
0.1 to 5 mol% of one or more of SrO, CaO and MgO , 0.1 to 5 mol% of one or more of TiO2, SnO2 , ZrO2 , SiO2 and GeO2 , 0.1 to 30 mol% of CoO,
0.1 to 5 mol% of one or more of Sb 2 O 3 , B 2 O 3 , Y 2 O 3 , Yb 2 O 3 and Er 2 O 3 , 0.001 to 1 mol % of Al 2 O 3 ,
0.0005 to 1.1 mol% of one or more of Li 2 O and K 2 O
Each oxide raw material was weighed so that the total amount was 100 mol%, and after thoroughly mixing with a ball mill or the like, it was granulated using an organic binder such as polyvinyl alcohol. In addition, as a starting material, it is also possible to use a hydroxide, a carbonate, a binary metal oxide, etc. instead of an oxide. In addition, if it causes problems such as variations in dimensions and properties after shaping and firing, it may be calcined in air at 600 to 1000°C for 1 to 3 hours, pulverized into fine powder, and then granulated. The granulated powders of various compositions obtained in this way are press-molded at a pressure of 0.5 to 2.0 ton/cm 2 and finished into a disc shape with a diameter of 15.0 mm and a thickness of 2.0 mm. The sintered body was fired for 1 to 3 hours in air at 1000 to 1400°C, and finally, Ag paste was baked on both sides of the sintered body to form electrodes, completing oxide varistor elements with various compositions. .
第１図は上述のごとき方法で製作した酸化物バ
リスタの断面図である。この酸化物バリスタのバ
リスタ作用は導電性微結晶１とこれを包囲する高
抵抗層２によつて生じるものと考えられる。従つ
て、材料組成や焼成条件を変えることにより、バ
リスタ電圧や非直線指数を制御することができ
る。以上のようにバリスタ作用は焼結体内部で生
じるので、電極３の材料や、形成方法には特に限
定はなく、Ag、In、Al、Snなどの蒸着による電
極あるいはNiメツキによる電極なども同様の結
果を得る。 FIG. 1 is a cross-sectional view of an oxide varistor manufactured by the method described above. It is considered that the varistor action of this oxide varistor is caused by the conductive microcrystal 1 and the high resistance layer 2 surrounding it. Therefore, by changing the material composition and firing conditions, the varistor voltage and nonlinear index can be controlled. As mentioned above, the varistor action occurs inside the sintered body, so there are no particular limitations on the material or formation method of the electrode 3, and electrodes formed by vapor deposition of Ag, In, Al, Sn, etc., or electrodes formed by Ni plating are also applicable. get the result.
上述の如き方法で製作した種々のバリスタのバ
リスタ電圧V1と、電圧非直線性を示す電圧比Ｒ
と、耐サージ性を示す電圧変化率△V1とを測定
したところ、第２図〜第２３図に示す結果が得ら
れた。なお、第２図〜第２３図のグラフにおい
て、代表的な組成のV1、Ｒ、△V1には点印、丸
印、三角印が付けられている。また、各図面に
は、比較のために、本発明の範囲外の組成のバリ
スタの特性も比較例として表示されている。ま
た、第２図〜第２０図の横軸の各成分の量（モル
％）は対数目盛で示されている。また、バリスタ
電圧V1は第１図の構造のバリスタに1.0ｍＡを流
した時の端子電圧を測定することにより求めた。
電圧比Ｒはバリスタ電流1.0ｍＡと25Aとにおけ
るバリスタの端子電圧V1とV25Aとを測定し、
V25A／V1を計算することにより求めた。従つて、
電圧比Ｒが小さいほど電圧非直線性が優れ、非直
線指数αが大きい。電圧変化率△V1は、８×
20μsの波形で1000Aのサージ電流をバリスタに２
回流し、この電流を流す前と後の逆方向のバリス
タ電圧V1を測定し、その変化分を計算すること
によつて求めた。従つて、電圧変化率△V1（絶対
値）が小さいほど耐サージ性が優れ、負荷に対す
る安定性が優れている。 Varistor voltage V 1 of various varistors manufactured by the method described above and voltage ratio R showing voltage nonlinearity
When the voltage change rate ΔV 1 indicating surge resistance was measured, the results shown in FIGS. 2 to 23 were obtained. In the graphs of FIGS. 2 to 23, typical compositions V 1 , R, and ΔV 1 are marked with dots, circles, and triangles. Further, in each drawing, for comparison, characteristics of varistors having compositions outside the scope of the present invention are also shown as comparative examples. Further, the amount (mol %) of each component on the horizontal axis of FIGS. 2 to 20 is shown on a logarithmic scale. Further, the varistor voltage V1 was determined by measuring the terminal voltage when 1.0 mA was applied to the varistor having the structure shown in FIG.
The voltage ratio R is determined by measuring the varistor terminal voltages V1 and V25A at varistor currents of 1.0mA and 25A,
It was determined by calculating V 25A /V 1 . Therefore,
The smaller the voltage ratio R, the better the voltage nonlinearity, and the larger the nonlinearity index α. The voltage change rate △V 1 is 8×
A surge current of 1000A is applied to the varistor with a waveform of 20μs.
The varistor voltage V 1 in the opposite direction was measured before and after the current was passed, and the change was calculated. Therefore, the smaller the voltage change rate ΔV 1 (absolute value), the better the surge resistance and the better the stability against load.
次に、第２図〜第２３図を更に詳しく説明す
る。 Next, FIGS. 2 to 23 will be explained in more detail.
第２図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 2 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
BaO 0.05〜10モル％
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第２図はBaOの量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。なお、
第２図〜第２３図においてZnOの量は、各図の横
軸の成分のモル％が決まれば、必然的に決まる。ZnO 73.31-83.26 mol% BaO 0.05-10 mol% TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 2 shows the amount of BaO (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown. In addition,
In FIGS. 2 to 23, the amount of ZnO is naturally determined once the mole % of the component on the horizontal axis in each figure is determined.
第３図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 3 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
SrO 0.05〜10モル％
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第３図はSrOの量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31-83.26 mol% SrO 0.05-10 mol% TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 3 shows the amount of SrO (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第４図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 4 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
CaO 0.05〜10モル％
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第４図はCaOの量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31-83.26 mol% CaO 0.05-10 mol% TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 4 shows the amount of CaO (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第５図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 5 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
MgO 0.05〜10モル％
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第５図はMgOの量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31-83.26 mol% MgO 0.05-10 mol% TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 5 shows the amount of MgO (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第６図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 6 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
BaO＋CaO 0.05〜10モル％
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第６図はBaO＋CaO（等モル混合物）の
量（モル％）及び合計100モル％となるように
ZnOの量を変化させた種々のバリスタのV1、Ｒ、
△V1を示す。ZnO 73.31 to 83.26 mol% BaO + CaO 0.05 to 10 mol% TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 6 shows the amount (mol%) of BaO + CaO (equimolar mixture) and the amount (mol%) of BaO + CaO (equimolar mixture) so that the total is 100 mol%.
V 1 , R, of various varistors with varying amounts of ZnO,
Indicates △V 1 .
第７図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 7 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
TiO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第７図はTiO2の量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31 to 83.26 mol% TiO 2 0.05 to 10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 7 shows the amount of TiO 2 (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第８図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 8 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
SnO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第８図はSnO2の量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31 to 83.26 mol% SnO 2 0.05 to 10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 8 shows the amount of SnO 2 (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第９図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 9 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
ZrO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第９図はZrO2の量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31-83.26 mol% ZrO 2 0.05-10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 9 shows the amount of ZrO 2 (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第１０図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 10 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
SiO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１０図はSiO2の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31 to 83.26 mol% SiO 2 0.05 to 10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 10 shows V 1 , R, and ΔV 1 of various varistors in which the amount of SiO 2 (mol %) and the amount of ZnO were varied so that the total amount was 100 mol %.
第１１図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 11 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
GeO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１１図はGeO2の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.31-83.26 mol% GeO 2 0.05-10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 11 shows V 1 , R, and ΔV 1 of various varistors in which the amount of GeO 2 (mol %) and the amount of ZnO were varied so that the total amount was 100 mol %.
第１２図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 12 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.31〜83.26モル％
TiO2＋GeO2 0.05〜10モル％
BaO 0.5モル％一定
CoO 15モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１２図はTiO2＋GeO2（等モル混合）
の量（モル％）及び合計100モル％となるように
ZnOの量を変化させた種々のバリスタのV1、Ｒ、
△V1を示す。ZnO 73.31 to 83.26 mol% TiO 2 +GeO 2 0.05 to 10 mol% BaO 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol% In other words, Figure 12 shows TiO 2 +GeO 2 (equimolar mixture)
amount (mol%) and total 100 mol%
V 1 , R, of various varistors with varying amounts of ZnO,
Indicates △V 1 .
第１３図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 13 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 47.81〜97.76モル％
CoO 0.05〜50モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
Sb2O3 １モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１３図はCoOの量（モル％）及び合計
100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 47.81 to 97.76 mol% CoO 0.05 to 50 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant Sb 2 O 3 1 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, Figure 13 shows the amount of CoO (mol%) and the total
V 1 , R, and ΔV 1 of various varistors in which the amount of ZnO was changed to 100 mol % are shown.
第１４図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 14 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
Sb2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO3 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１４図はSb2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.81 to 83.76 mol% Sb 2 O 3 0.05 to 10 mol% BaO 0.5 mol% constant TiO 3 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 14 shows V 1 , R, and ΔV 1 of various varistors in which the amount of Sb 2 O 3 (mol %) and the amount of ZnO were changed so that the total amount was 100 mol %.
第１５図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 15 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
B2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１５図はB2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.81 to 83.76 mol% B 2 O 3 0.05 to 10 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 15 shows V 1 , R, and ΔV 1 of various varistors in which the amount of B 2 O 3 (mol %) and the amount of ZnO were changed so that the total amount was 100 mol %.
第１６図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 16 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
Y2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１６図はY2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.81-83.76 mol% Y 2 O 3 0.05-10 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 16 shows V 1 , R, and ΔV 1 of various varistors in which the amount of Y 2 O 3 (mol %) and the amount of ZnO were changed so that the total amount was 100 mol %.
第１７図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 17 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
Yb2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１７図はYb2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.81 to 83.76 mol% Yb 2 O 3 0.05 to 10 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 17 shows V 1 , R, and ΔV 1 of various varistors in which the amount of Yb 2 O 3 (mol %) and the amount of ZnO were changed so that the total amount was 100 mol %.
第１８図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 18 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
Er2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１８図はEr2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させた
種々のバリスタのV1、Ｒ、△V1を示す。ZnO 73.81 to 83.76 mol% Er 2 O 3 0.05 to 10 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol % That is, FIG. 18 shows V 1 , R, and ΔV 1 of various varistors in which the amount of Er 2 O 3 (mol %) and the amount of ZnO were changed so that the total amount was 100 mol %.
第１９図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 19 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 73.81〜83.76モル％
Sb2O3＋B2O3 0.05〜10モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Al2O3 0.1モル％一定
Li2O 0.09モル％一定
合 計 100モル％
即ち、第１９図はSb2O3＋B2O3（等モル混合）
の量（モル％）及び合計100モル％となるように
ZnOの量を変化させた種々のバリスタのV1、Ｒ、
△V1を示す。ZnO 73.81 to 83.76 mol% Sb 2 O 3 + B 2 O 3 0.05 to 10 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Al 2 O 3 0.1 mol% constant Li 2 O 0.09 mol% constant Total 100 mol% In other words, Figure 19 shows Sb 2 O 3 + B 2 O 3 (equimolar mixture)
amount (mol%) and total 100 mol%
V 1 , R, of various varistors with varying amounts of ZnO,
Indicates △V 1 .
第２０図は次の組成のバリスタのバリスタ電圧
V1と電圧比Ｒと電圧変化率△V1とを示す。 Figure 20 shows the varistor voltage of a varistor with the following composition.
V 1 , voltage ratio R, and voltage change rate ΔV 1 are shown.
ZnO 77.3〜82.99905モル％
Al2O3 0.0005〜３モル％
BaO 0.5モル％一定
TiO2 0.5モル％一定
CoO 15モル％一定
Sb2O3 0.1モル％一定
Li2O 0.00045〜2.7モル％
合 計 100モル％
即ち、第２０図はAl2O3の量（モル％）及び合
計100モル％となるようにZnOの量を変化させ且
つLi2O／Al2O3のモル比が第２図〜第１９図の場
合と同様に0.9に保たれるようにLi2Oの量を変化
させた種々のバリスタのV1、Ｒ、△V1を示す。ZnO 77.3 to 82.99905 mol% Al 2 O 3 0.0005 to 3 mol% BaO 0.5 mol% constant TiO 2 0.5 mol% constant CoO 15 mol% constant Sb 2 O 3 0.1 mol% constant Li 2 O 0.00045 to 2.7 mol% Total 100 In other words, Fig. 20 shows the amount of Al 2 O 3 (mol %) and the amount of ZnO changed so that the total becomes 100 mol %, and the molar ratio of Li 2 O / Al 2 O 3 in Fig. 2 ~ The V 1 , R, and ΔV 1 of various varistors are shown in which the amount of Li 2 O is varied so as to be kept at 0.9 as in the case of FIG. 19.
第２１図は、BaOを0.5モル％、TiO2を0.5モル
％、CoOを15モル％、Sb2O3を１モル％、Al2O3
を0.1モル％にそれぞれ固定し、Li2O／Al2O3の
モル比を0.3〜1.3の範囲で変化させ、残部をZnO
として総和を100モル％としたもののV1、Ｒ、△
V1を示す。 Figure 21 shows 0.5 mol% BaO, 0.5 mol% TiO 2 , 15 mol% CoO, 1 mol% Sb 2 O 3 , Al 2 O 3
were each fixed at 0.1 mol%, the molar ratio of Li 2 O / Al 2 O 3 was varied in the range of 0.3 to 1.3, and the remainder was ZnO.
V 1 , R, △ with the total sum as 100 mol%
Indicates V 1 .
第２２図は、第２１図におけるLiO2の代りに
K2Oを使用した他は、第２１図と全く同一条件の
バリスタのV1、Ｒ、△V1を示す。 Figure 22 shows that LiO 2 in Figure 21 is replaced by
FIG. 21 shows V 1 , R, and ΔV 1 of the varistor under exactly the same conditions as in FIG. 21 except that K 2 O was used.
第２３図は、第２１図におけるLi2Oの代りに
Li2O＋K2O（等モル混合）を使用した他は、第２
１図と全く同一条件のバリスタのV1、Ｒ、△V1
を示す。 Figure 23 shows that Li 2 O in Figure 21 is replaced by
In addition to using Li 2 O + K 2 O (equimolar mixture), the second
V 1 , R, △V 1 of the varistor under exactly the same conditions as in Figure 1
shows.
次に、本発明の組成の限定理由を説明する。 Next, the reasons for limiting the composition of the present invention will be explained.
第２図、第３図、第４図、第５図および第６図
において、第２成分としてのBaO、SrO、CaO、
MgO、およびBaO＋CaOが５モル％を越えたも
のは電圧比Ｒが大きく、電圧変化率△V1の絶対
値も大きい。一方、この第２成分が0.1モル％よ
り少ないものも、電圧比Ｒおよび電圧変化率△
V1の絶対値が大きい。これに対して、第２成分
が0.1〜５モル％の範囲にあれば、電圧比Ｒが３
以下であり、且つ△V1の絶対値が10％以下であ
る。従つて、第２成分の好ましい範囲は0.1〜0.5
モル％である。また、第２成分のより好ましい範
囲は、Ｒが２以下、△V1の絶対値が５以下にな
る0.2〜２モル％である。 In FIGS. 2, 3, 4, 5, and 6, BaO, SrO, CaO,
Those in which MgO and BaO+CaO exceed 5 mol % have a large voltage ratio R and a large absolute value of the voltage change rate ΔV 1 . On the other hand, if the second component is less than 0.1 mol%, the voltage ratio R and voltage change rate △
The absolute value of V 1 is large. On the other hand, if the second component is in the range of 0.1 to 5 mol%, the voltage ratio R is 3.
and the absolute value of ΔV 1 is 10% or less. Therefore, the preferred range of the second component is 0.1 to 0.5
It is mole%. Further, a more preferable range of the second component is 0.2 to 2 mol % where R is 2 or less and the absolute value of ΔV 1 is 5 or less.
第７図、第８図、第９図、第１０図、第１１
図、および第１２図において、第３成分としての
TiO2、SnO2、ZrO2、SiO2、GeO2、TiO2＋GeO2
が５モル％を越えたものは、電圧比Ｒが大きく、
電圧変化率△V1も大きい。一方、この第３成分
が0.1モル％より少ないものも、Ｒおよび△V1が
大きい。これに対して、第３成分が0.1〜５モル
％の範囲にあれば、Ｒが３以下であり、且つ△
V1の絶対値が10以下である。従つて、第３成分
の好ましい範囲は0.1〜0.5モル％である。また、
第３成分のより好ましい範囲は、Ｒが2.1以下、
△V1の絶対値が７％以下になる0.2〜２モル％で
ある。 Figure 7, Figure 8, Figure 9, Figure 10, Figure 11
In the figure and Figure 12, as the third component
TiO 2 , SnO 2 , ZrO 2 , SiO 2 , GeO 2 , TiO 2 +GeO 2
If it exceeds 5 mol%, the voltage ratio R is large;
The voltage change rate △V 1 is also large. On the other hand, those containing less than 0.1 mol % of this third component also have large R and ΔV 1 . On the other hand, if the third component is in the range of 0.1 to 5 mol%, R is 3 or less and △
The absolute value of V 1 is 10 or less. Therefore, the preferred range of the third component is 0.1 to 0.5 mol%. Also,
A more preferable range of the third component is that R is 2.1 or less;
The content is 0.2 to 2 mol % at which the absolute value of ΔV 1 is 7% or less.
第１３図において、第４成分としてのCoOが30
モル％を越えたものは、Ｒが大きく、△V1も大
きい。一方、この第４成分が0.1モル％より少な
いものも、Ｒが大きく、△V1も大きい。これに
対して、この第４成分が0.1〜30モル％の範囲に
あれば、Ｒが３以下であり、且つ△V1の絶対値
が10％以下である。従つて、第４成分の好ましい
範囲は0.1〜30モル％である。また、第４成分の
より好ましい範囲は、Ｒが２以下になり、△V1
の絶対値が５％以下になる0.5〜15モル％である。 In Figure 13, CoO as the fourth component is 30
If it exceeds mol%, R is large and ΔV 1 is also large. On the other hand, those containing less than 0.1 mol% of this fourth component also have a large R and a large ΔV1 . On the other hand, if this fourth component is in the range of 0.1 to 30 mol %, R is 3 or less and the absolute value of ΔV 1 is 10% or less. Therefore, the preferred range of the fourth component is 0.1 to 30 mol%. Further, a more preferable range of the fourth component is that R is 2 or less, and ΔV 1
It is 0.5 to 15 mol% such that the absolute value of is 5% or less.
第１４図、第１５図、第１６図、第１７図、第
１８図、第１９図において、第５成分としての
Sb2O3、B2O3、Y2O3、Yb2O3、Er2O3、Sb2O3＋
B2O3が、５モル％を越えたもの、および0.1モル
％より少ないものは、Ｒが大きく且つ△V1も大
きい。これに対して、第５成分が0.1〜５モル％
の範囲であれば、Ｒが３以下であり、△V1の絶
対値がほぼ10％以下である。従つて、第５成分の
好ましい範囲は0.1〜５モル％である。また、第
５成分のより好ましい範囲は、Ｒが2.5以下にな
り、△V1が８％以下になる0.2〜２モル％である。 In Fig. 14, Fig. 15, Fig. 16, Fig. 17, Fig. 18, and Fig. 19,
Sb 2 O 3 , B 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Er 2 O 3 , Sb 2 O 3 +
Those containing B 2 O 3 exceeding 5 mol % and those containing less than 0.1 mol % have a large R and a large ΔV 1 . In contrast, the fifth component is 0.1 to 5 mol%
In the range of , R is 3 or less and the absolute value of ΔV 1 is approximately 10% or less. Therefore, the preferred range of the fifth component is 0.1 to 5 mol%. Further, a more preferable range of the fifth component is 0.2 to 2 mol % so that R is 2.5 or less and ΔV 1 is 8% or less.
第２０図において、第６成分としてのAl2O3
が、１モル％を越えたものおよび0.001モル％よ
り少ないものは、Ｒが大きく且つ△V1も大きい。
これに対して、第６成分が0.001〜１モル％の範
囲であれば、Ｒが３以下であり、△V1の絶対値
が５％以下である。従つて、第６成分の好ましい
範囲は0.001〜１モル％である。また、第６成分
のより好ましい範囲は、Ｒが２以下になり、△
V1が３以下になる0.005〜0.5モル％である。 In FIG. 20, Al 2 O 3 as the sixth component
However, those exceeding 1 mol% and those less than 0.001 mol% have a large R and a large ΔV1 .
On the other hand, if the sixth component is in the range of 0.001 to 1 mol %, R is 3 or less and the absolute value of ΔV 1 is 5% or less. Therefore, the preferred range of the sixth component is 0.001 to 1 mol%. Further, a more preferable range of the sixth component is that R is 2 or less, and △
It is 0.005 to 0.5 mol % where V 1 is 3 or less.
第２１図、第２２図、第２３図において、第７
成分としてのLi2O、K2O、Li2O＋K2Oと第６成
分としてのAl2O3とのモル比が1.1を越えたもの、
および0.5よりも少ないものは、Ｒ及び△V1の絶
対値が大きい。これに対して、モル比が0.5〜1.1
の範囲にあれば、Ｒが３以下であり、△V1の絶
対値は10％以下である。第２１図〜第２２図では
Al2O3が0.1モル％とされているが、Al2O3を0.001
〜１モル％とした場合にも同様な傾向となる。従
つて、第７成分／第６成分（モル比）の好ましい
範囲は、0.5〜1.1であり、より好ましい範囲は0.7
〜1.0である。モル比の好ましい範囲が上述の如
く0.5〜1.1であれば、第７成分（Li2O、K2O）の
好ましい範囲は必然的に0.0005〜1.1モル％とな
る。 In Figures 21, 22, and 23, the 7th
Those in which the molar ratio of Li 2 O, K 2 O, Li 2 O + K 2 O as components and Al 2 O 3 as the sixth component exceeds 1.1,
and those less than 0.5 have large absolute values of R and ΔV 1 . In contrast, the molar ratio is 0.5 to 1.1
If it is within the range, R is 3 or less and the absolute value of ΔV 1 is 10% or less. In Figures 21-22
Al 2 O 3 is said to be 0.1 mol%, but Al 2 O 3 is 0.001 mol%.
A similar tendency occurs when the amount is set to 1 mol %. Therefore, the preferable range of the seventh component/sixth component (molar ratio) is 0.5 to 1.1, and the more preferable range is 0.7.
~1.0. If the preferable range of the molar ratio is 0.5 to 1.1 as described above, the preferable range of the seventh component (Li 2 O, K 2 O) is necessarily 0.0005 to 1.1 mol %.
上述の如く、ZnOを除く他の成分の範囲が決ま
れば、ZnOの量（モル％）は残部であるので、必
然的に52.9〜99.5985モル％である。なお、第２
図〜第２３図において、固定した部分の量（モル
％）を変えても同様な傾向が得られる。また、第
２、第３、第５成分中の酸化物の種類を変えて
も、同一群の酸化物はほぼ同一の働きをなすの
で、同様な傾向を示す。 As mentioned above, once the range of other components other than ZnO is determined, the amount (mol%) of ZnO is the remainder and is necessarily 52.9 to 99.5985 mol%. In addition, the second
Similar trends can be obtained even if the amount (mol %) of the fixed portion is changed in FIGS. Further, even if the types of oxides in the second, third, and fifth components are changed, oxides of the same group perform almost the same function, and therefore exhibit the same tendency.
以上、本発明の実施例及び比較例について述べ
たが、本発明はこれに限定されるものでなく、更
に変形可能なものである。例えば、各種の成分を
二元金属酸化物（BaSnO3、SrTiO3、MgZrO3、
Co2TiO4、Zn2SiO4、Zn2SnO4等）として添加し
てもよい。例えば、
BaO 0.5モル％
TiO2 0.5モル％
CoO 15モル％
Sb2O3 １モル％
Al2O3 0.1モル％
Li2O 0.09モル％
BaSnO3又はSrTiO3又はZn2SnO4 0.3モル％
ZnO 残 部
で100モル％となるバリスタを製作し、その特性
を調べたところ、一元金属酸化物を使用したもの
と比較し、V1とＲはほぼ同一であり、△V1は向
上した。また、本発明の目的を損なわない範囲で
希土類物質（La2O3、Pr2O3、Nd2O3など）や、
Nb2O5、Ta2O5、MnO、NiO、Cr2O3等の酸化物
等を添加してもよい。 Although Examples and Comparative Examples of the present invention have been described above, the present invention is not limited thereto and can be further modified. For example, various components can be mixed into binary metal oxides (BaSnO 3 , SrTiO 3 , MgZrO 3 ,
Co2TiO4 , Zn2SiO4 , Zn2SnO4 , etc. ) may be added. For example, BaO 0.5 mol% TiO 2 0.5 mol% CoO 15 mol% Sb 2 O 3 1 mol% Al 2 O 3 0.1 mol% Li 2 O 0.09 mol% BaSnO 3 or SrTiO 3 or Zn 2 SnO 4 0.3 mol% ZnO remaining When a varistor with a concentration of 100 mol % was manufactured and its characteristics were investigated, V 1 and R were almost the same, and ΔV 1 was improved compared to a varistor using a monometal oxide. Furthermore, rare earth substances (such as La 2 O 3 , Pr 2 O 3 , Nd 2 O 3 ), and
Oxides such as Nb 2 O 5 , Ta 2 O 5 , MnO, NiO, Cr 2 O 3 and the like may be added.
発明の効果
上述から明らかな如く、本発明によれば、電圧
比Ｒが1.45〜2.5程度、電圧変化率△V1の絶対値
が10％以下、バリスタ電圧V1が380〜860V程度
のバリスタをビスマスを使用しないで得ることが
出来る。なお、本発明のバリスタは電圧比Ｒが小
さいので、非直線性に優れ、また電圧変化率△
V1が小さいので、耐サージ性に優れている。Effects of the Invention As is clear from the above, according to the present invention, a varistor with a voltage ratio R of about 1.45 to 2.5, an absolute value of the voltage change rate ΔV 1 of 10% or less, and a varistor voltage V 1 of about 380 to 860 V can be used. It can be obtained without using bismuth. In addition, since the varistor of the present invention has a small voltage ratio R, it has excellent nonlinearity, and the voltage change rate △
Since V 1 is small, it has excellent surge resistance.
第１図は本発明に係わる酸化物電圧非直線抵抗
体の焼結結晶粒子の配列を模型的に示す断面図、
第２図はBaOの変化に対するバリスタ電圧V1、
電圧比Ｒ、電圧変化率△V1の変化を示す特性曲
線図、第３図はSrOの変化に対するバリスタ電圧
V1、電圧比Ｒ、電圧変化率△V1の変化を示す特
性曲線図、第４図はCaOの変化に対するバリスタ
電圧V1、電圧比Ｒ、電圧変化率△V1の変化を示
す特性曲線図、第５図はMgOの変化に対するバ
リスタ電圧V1、電圧比Ｒ、電圧変化率△V1の変
化を示す特性曲線図、第６図はBaO、CaOの合
計の変化に対するバリスタ電圧V1、電圧比Ｒ、
電圧変化率△V1の変化を示す特性曲線図、第７
図はTiO2の変化に対するバリスタ電圧V1、電圧
比Ｒ、電圧変化率△V1の変化を示す特性曲線図、
第８図はSnO2の変化に対するバリスタ電圧V1、
電圧比Ｒ、電圧変化率△V1の変化を示す特性曲
線図、第９図はZrO2の変化に対するバリスタ電
圧V1、電圧比Ｒ、電圧変化率△V1の変化を示す
特性曲線図、第１０図はSiO2の変化に対するバ
リスタ電圧V1、電圧比Ｒ、電圧変化率△V1の変
化を示す特性曲線図、第１１図はGeO2の変化に
対するバリスタ電圧V1、電圧比Ｒ、電圧変化率
△V1の変化を示す特性曲線図、第１２図はTiO2、
GeO2の合計の変化に対するバリスタ電圧V1、電
圧比Ｒ、電圧変化率△V1の変化を示す特性曲線
図、第１３図はCoOの変化に対するバリスタ電圧
V1、電圧比Ｒ、電圧変化率△V1の変化を示す特
性曲線図、第１４図はSb2O3の変化に対するバリ
スタ電圧V1、電圧比Ｒ、電圧変化率△V1の変化
を示す特性曲線図、第１５図はB2O3の変化に対
するバリスタ電圧V1、電圧比Ｒ、電圧変化率△
V1の変化を示す特性曲線図、第１６図はY2O3の
変化に対するバリスタ電圧V1、電圧比Ｒ、電圧
変化率△V1の変化を示す特性曲線図、第１７図
はYb2O3の変化に対するバリスタ電圧V1、電圧
比Ｒ、電圧変化率△V1の変化を示す特性曲線図、
第１８図はEr2O3の変化に対するバリスタ電圧
V1、電圧比Ｒ、電圧変化率△V1の変化を示す特
性曲線図、第１９図はSb2O3、B2O3の合計の変化
に対するバリスタ電圧V1、電圧比Ｒ、電圧変化
率△V1の変化を示す特性曲線図、第２０図は
Al2O3の変化に対するバリスタ電圧V1、電圧比
Ｒ、電圧変化率△V1の変化を示す特性曲線図、
第２１図はLi2OとAl2O3のモル比の変化に対する
バリスタ電圧V1、電圧比Ｒ、電圧変化率△V1の
変化を示す特性曲線図、第２２図はK2OとAl2O3
のモル比の変化に対するバリスタ電圧V1、電圧
比Ｒ、電圧変化率△V1の変化を示す特性曲線図、
第２３図はLi2O、K2Oの合計とAl2O3のモル比の
変化に対するバリスタ電圧V1、電圧比Ｒ、電圧
変化率△V1の変化を示す特性曲線図である。
１……結晶、２……高抵抗層、３……電極。
FIG. 1 is a cross-sectional view schematically showing the arrangement of sintered crystal particles of an oxide voltage nonlinear resistor according to the present invention;
Figure 2 shows the varistor voltage V 1 with respect to changes in BaO,
Characteristic curve diagram showing changes in voltage ratio R and voltage change rate △V 1. Figure 3 shows varistor voltage with respect to changes in SrO.
A characteristic curve diagram showing changes in V 1 , voltage ratio R, and voltage change rate △V 1. Figure 4 is a characteristic curve showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in CaO. 5 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in MgO, and FIG. voltage ratio R,
Characteristic curve diagram showing changes in voltage change rate △V 1 , 7th
The figure is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in TiO 2 ,
Figure 8 shows the varistor voltage V 1 with respect to changes in SnO 2 ,
A characteristic curve diagram showing changes in voltage ratio R and voltage change rate ΔV 1 ; FIG. 9 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate ΔV 1 with respect to changes in ZrO 2 ; FIG. 10 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate ΔV 1 with respect to changes in SiO 2 , and FIG. 11 shows changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in GeO 2 . A characteristic curve diagram showing changes in voltage change rate △V 1 , Fig. 12 shows TiO 2 ,
Characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in total GeO 2 . Figure 13 shows varistor voltage with respect to changes in CoO
A characteristic curve diagram showing changes in V 1 , voltage ratio R, and voltage change rate △V 1. Figure 14 shows changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in Sb 2 O 3 . The characteristic curve diagram shown in Fig. 15 shows the varistor voltage V 1 , voltage ratio R, and voltage change rate △ with respect to changes in B 2 O 3
Figure 16 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in Y 2 O 3. Figure 17 is a characteristic curve diagram showing changes in Yb 2 A characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in O 3 ,
Figure 18 shows the varistor voltage with respect to changes in Er 2 O 3
A characteristic curve diagram showing changes in V 1 , voltage ratio R, and voltage change rate △V 1 . Figure 19 shows varistor voltage V 1 , voltage ratio R, and voltage change with respect to changes in the total of Sb 2 O 3 and B 2 O 3 Figure 20 is a characteristic curve diagram showing changes in the rate △V 1 .
Characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in Al 2 O 3 ,
Figure 21 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in the molar ratio of Li 2 O and Al 2 O 3 , and Figure 22 is a characteristic curve diagram showing changes in varistor voltage V 1, voltage ratio R, and voltage change rate △V 1 with respect to changes in the molar ratio of Li 2 O and Al 2 O 3. 2 o 3
A characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate △V 1 with respect to changes in molar ratio of
FIG. 23 is a characteristic curve diagram showing changes in varistor voltage V 1 , voltage ratio R, and voltage change rate ΔV 1 with respect to changes in the total of Li 2 O and K 2 O and the molar ratio of Al 2 O 3 . 1...Crystal, 2...High resistance layer, 3...Electrode.
Claims (1)
Ge、Co、Sb、Ｂ、Ｙ、Yb、Er、Al、Li、Ｋを、
これ等の代表的酸化物であるZnO、BaO、SrO、
CaO、MgO、TiO2、SnO2、ZrO2、SiO2、
GeO2、CoO、Sb2O3、B2O3、Y2O3、Yb2O3、
Er2O3、Al2O3、Li2O、K2Oに換算した組成で、 ZnO52.9〜99.5985モル％、 BaO、SrO、CaOおよびMgOの内の一種以上
の酸化物0.1〜５モル％、 TiO2、SnO2、ZrO2、SiO2およびGeO2の内の
一種以上の酸化物0.1〜５モル％、 CoO0.1〜30モル％、 Sb2O3、B2O3、Y2O3、Yb2O3およびEr2O3の内
の一種以上の酸化物0.1〜５モル％、 Al2O30.001〜１モル％、 Li2OおよびK2Oの内の一種以上の酸化物0.0005
〜1.1モル％（但し、Al2O3に対するLi2Oおよび
K2Oの内の一種以上の酸化物のモル比の範囲は
0.5〜1.1） となるように含む焼結体からなる酸化物電圧非直
線抵抗体。[Claims] 1 Zn, Ba, Sr, Ca, Mg, Ti, Sn, Zr, Si,
Ge, Co, Sb, B, Y, Yb, Er, Al, Li, K,
These representative oxides are ZnO, BaO, SrO,
CaO, MgO, TiO2 , SnO2 , ZrO2 , SiO2 ,
GeO2 , CoO, Sb2O3 , B2O3 , Y2O3 , Yb2O3 ,
Composition calculated as Er 2 O 3 , Al 2 O 3 , Li 2 O, K 2 O, 52.9 to 99.5985 mol% of ZnO, 0.1 to 5 mol of oxide of one or more of BaO, SrO, CaO and MgO %, 0.1 to 5 mol% of oxide of one or more of TiO 2 , SnO 2 , ZrO 2 , SiO 2 and GeO 2 , CoO 0.1 to 30 mol %, Sb 2 O 3 , B 2 O 3 , Y 2 0.1 to 5 mol% of oxide of one or more of O 3 , Yb 2 O 3 and Er 2 O 3 , 0.001 to 1 mol% of Al 2 O 3 , oxidation of one or more of Li 2 O and K 2 O thing 0.0005
~1.1 mol% (however, Li 2 O and
The range of molar ratio of one or more oxides in K 2 O is
0.5 to 1.1) An oxide voltage nonlinear resistor made of a sintered body containing 0.5 to 1.1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173031A JPS6150304A (en) | 1984-08-20 | 1984-08-20 | Oxide voltage nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59173031A JPS6150304A (en) | 1984-08-20 | 1984-08-20 | Oxide voltage nonlinear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6150304A JPS6150304A (en) | 1986-03-12 |
| JPH0249526B2 true JPH0249526B2 (en) | 1990-10-30 |
Family
ID=15952916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59173031A Granted JPS6150304A (en) | 1984-08-20 | 1984-08-20 | Oxide voltage nonlinear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6150304A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3212672B2 (en) * | 1992-03-12 | 2001-09-25 | 株式会社東芝 | Power resistor |
| DE69317407T2 (en) * | 1992-10-09 | 1998-08-06 | Tdk Corp | RESISTANCE ELEMENT WITH NON-LINEAR VOLTAGE DEPENDENCE AND MANUFACTURING METHOD |
| JP5674317B2 (en) * | 2010-01-13 | 2015-02-25 | コーア株式会社 | Zinc oxide varistor and method for producing the same |
| CN106316384B (en) * | 2016-08-29 | 2019-03-12 | 张颖 | A kind of piezoresistive material |
-
1984
- 1984-08-20 JP JP59173031A patent/JPS6150304A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6150304A (en) | 1986-03-12 |
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