JPH03278403A - Voltage-dependent non-linear resistor - Google Patents
Voltage-dependent non-linear resistorInfo
- Publication number
- JPH03278403A JPH03278403A JP2076777A JP7677790A JPH03278403A JP H03278403 A JPH03278403 A JP H03278403A JP 2076777 A JP2076777 A JP 2076777A JP 7677790 A JP7677790 A JP 7677790A JP H03278403 A JPH03278403 A JP H03278403A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- oxides
- mol
- total amount
- varistor voltage
- 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
- 230000001419 dependent effect Effects 0.000 title claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 titanate metal oxide Chemical class 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 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１
本発明は、チタン酸ストロンチウム
（ＳｒＴｉＯ３）を主成分とする電圧依存非直線抵抗体
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a voltage-dependent nonlinear resistor containing strontium titanate (SrTiO3) as a main component.
し従来の技術］
電圧依存非直線抵抗体、いわゆるバリスタは、非直線的
な電圧−電流特性を有することから、各種電気機器や電
子機器における異常高電圧（サージ）の吸収、雑音の除
去、火花消去等のために使用されてきた。[Prior art] Voltage-dependent nonlinear resistors, so-called varistors, have nonlinear voltage-current characteristics, so they are useful for absorbing abnormal high voltages (surges), removing noise, and sparks in various electrical and electronic devices. It has been used for purposes such as erasure.
この電圧依存非直線抵抗体の電圧−電流特性は、近似的
に次式のように表わすことができる。The voltage-current characteristic of this voltage-dependent nonlinear resistor can be approximately expressed as shown below.
１＝ （Ｖ／Ｃ）
ここで、■は電流、■は電圧、Ｃは電圧依存非直線抵抗
体固有の定数、αは非直線係数である。1=(V/C) Here, ■ is a current, ■ is a voltage, C is a constant specific to a voltage-dependent nonlinear resistor, and α is a nonlinear coefficient.
電圧依存非直線抵抗体の一般特性はαの大きさで表わす
ことができ、α値が大きいほど電圧非直線特性がよいこ
とになる。また、Ｃは電圧依存非直線抵抗体の材料や製
法等により定まる定数であるが、通常は電流Ｉが１ ｍ
Ａのときの電圧Ｅ、の値が用いられる。The general characteristics of a voltage-dependent nonlinear resistor can be expressed by the magnitude of α, and the larger the α value, the better the voltage nonlinear characteristics. In addition, C is a constant determined by the material and manufacturing method of the voltage-dependent nonlinear resistor, but usually when the current I is 1 m
The value of voltage E when A is used.
従来、この種の電圧依存非直線抵抗体としては、チタン
酸ストロンチウム（ＳｒＴｉＯ，）を主成分とする組成
物からなるものが知られており、非直線係数ａの値が３
．５〜８．０と比較的大きいことが特徴であった。Conventionally, as this type of voltage-dependent nonlinear resistor, one made of a composition containing strontium titanate (SrTiO,) as a main component is known, and the value of the nonlinear coefficient a is 3.
．． It was characterized by a relatively large value of 5 to 8.0.
このようなチタン酸ストロンチウムを主成分とする電圧
依存非直線抵抗体の製造方法の一例を示すと、まず５ｒ
ＴｉＯｘを主成分とするチタン酸金属酸化物粉末の混合
物に、酢酸ビニル系バインダーを添加、混合してこれを
原料粉末とする。この原料粉末を高圧にて所定形体に成
型した後、還元的雰囲気下又は酸化的雰囲気下で熱処理
工程を数回繰返す。通常は８回ないし１０回以上繰返し
て焼結体を得る。この焼結体に電極を配して電圧依存非
直線抵抗体とするものである。An example of a method for manufacturing a voltage-dependent nonlinear resistor containing strontium titanate as a main component is as follows.
A vinyl acetate-based binder is added and mixed to a mixture of titanate metal oxide powder containing TiOx as a main component, and this is used as a raw material powder. After this raw material powder is molded into a predetermined shape under high pressure, a heat treatment step is repeated several times under a reducing atmosphere or an oxidizing atmosphere. Usually, the process is repeated 8 to 10 times or more to obtain a sintered body. Electrodes are arranged on this sintered body to form a voltage-dependent nonlinear resistor.
［発明が解決しようとする課題］
しかし、従来のチタン酸ストロンチウムを主成分とした
電圧依存非直線抵抗体は、バリスタ電圧が比較的低いも
のが主であった。[Problems to be Solved by the Invention] However, conventional voltage-dependent nonlinear resistors containing strontium titanate as a main component mainly have relatively low varistor voltages.
ここでバリスタ電圧とは、印加電圧を増加させていった
ときに電流が急激に流れ始める電圧、すなわち抵抗が急
激に減少し始める電圧を意味し、通常は電流■が］、
Ｏｍ Ａのときの電圧Ｅ ｌ（＋として把握される。こ
のバリスタ電圧の値より大きな電圧が印加されると、急
激に電圧依存非直線抵抗体の抵抗が減少し、電圧依存非
直線抵抗体はバイパスとして機能するようになり、サー
ジの吸収や雑音の除去等が行えるものである。従って、
用途によってバリスタ電圧Ｅ ＋ａの異なる電圧依存非
直線抵抗体が求められる。Here, the varistor voltage means the voltage at which current begins to flow rapidly when the applied voltage increases, that is, the voltage at which resistance begins to rapidly decrease.
The voltage E l (+) when Om A is applied. When a voltage larger than the value of this varistor voltage is applied, the resistance of the voltage-dependent non-linear resistor decreases rapidly, and the voltage-dependent non-linear resistor becomes It functions as a bypass, absorbing surges and removing noise.Therefore,
Depending on the application, voltage-dependent nonlinear resistors with different varistor voltages E+a are required.
しかし、従来のチタン酸ストロンチウムを主成分とした
電圧依存非直線抵抗体は、大きな非直線係数αを有する
ものの、バリスタ電圧Ｅ １０は２〜６０ｖ程度のもの
が主であり、あまり高くはなかった。高バリスタ電圧Ｅ
、。特性を得るためには、熱処理工程すなわち焼成を何
度も繰返せばよいが、焼成コストがかさむことから実用
的ではなかった。However, although the conventional voltage-dependent nonlinear resistor mainly composed of strontium titanate has a large nonlinear coefficient α, the varistor voltage E10 is mainly around 2 to 60 V, which is not very high. . High varistor voltage E
,. In order to obtain these properties, the heat treatment step, that is, firing, can be repeated many times, but this has not been practical due to the high cost of firing.
また、このようにして得られる電圧依存非直線抵抗体の
非直線係数αは３〜５と比較的小さ（、電子機器や部品
の異常なサージやノイズからの保護、あるいは回路電圧
の安定化という用途に用いるには、非直線係数ａの値が
十分でない。In addition, the nonlinear coefficient α of the voltage-dependent nonlinear resistor obtained in this way is relatively small at 3 to 5. The value of the nonlinear coefficient a is not sufficient for this purpose.
本発明は上記のような問題点に鑑みてなされたものであ
り、大きな非直線係数ａを有するとともにバリスタ電圧
Ｅ、。が十分に高いチタン酸ストロンチウム系の電圧依
存非直線抵抗体を提供することを目的とする。The present invention has been made in view of the above problems, and has a large nonlinear coefficient a and a varistor voltage E. An object of the present invention is to provide a strontium titanate-based voltage-dependent nonlinear resistor with sufficiently high resistance.
［課題を解決するための手段］
本発明は、前記目的を達成すべく、チタン酸ストロンチ
ウム（ＳｒＴｉＯａ）を主成分とする電圧依存比直線抵
抗体において、チタン酸カルシウム（ＣａＴ ｉ Ｏｓ
）を５−００〜２６．００モル％、ニオブ（Ｎｂ）、
ランタン（Ｌａ）及びタンタル（Ｔａ）の各元素の酸化
物からなるグループから選択した１種又は２種以上の酸
化物の総量を０．０５〜０．５０モル％、銅（Ｃｕ）
、モリブデン（Ｍｏ）、鉄（Ｆｅ）及びマンガン（Ｍｎ
）の各元素の酸化物からなるグループから選択した１種
又は２種以上の酸化物のａｔを０．０５〜０．５０モル
％、二酸化ケイ素（Ｓｉｎ、）を０．５０〜１．００モ
／１．％それぞれ添加したものである。[Means for Solving the Problems] In order to achieve the above object, the present invention provides a voltage-dependent ratio linear resistor containing strontium titanate (SrTiOa) as a main component.
) 5-00 to 26.00 mol%, niobium (Nb),
The total amount of one or more oxides selected from the group consisting of oxides of each element of lanthanum (La) and tantalum (Ta) is 0.05 to 0.50 mol%, copper (Cu)
, molybdenum (Mo), iron (Fe) and manganese (Mn
) of 0.05 to 0.50 mol % of one or more oxides selected from the group consisting of oxides of each element, and 0.50 to 1.00 mol % of silicon dioxide (Sin). /1. % respectively.
Ｃａ Ｔ ｊ、 ０ 、の添加量を１．５．０Ｏ−２６
，００モル％の範囲内とした理由は、添加量が１５．０
０モル％以下の場合、所望の高バリスタ電圧ＥＩＯを得
るために焼成を多数行わなければならず、また非直線係
数ａ値も低下し、さらにバリスタ電圧Ｅ １０の温度変
化率△Ｅ ｔｏも太き（なるという問題があるからであ
る。一方、添加量が２６．００モル％以上の場合、ａ値
が低下するとともにバリスタ電圧Ｅ、。The amount of Ca T j,0 added was 1.5.0O-26
,00 mol% is within the range of 15.0 mol%.
If it is less than 0 mol%, many firings must be performed to obtain the desired high varistor voltage EIO, the nonlinear coefficient a value also decreases, and the temperature change rate ΔE to of the varistor voltage E10 also increases. On the other hand, if the amount added is 26.00 mol% or more, the a value decreases and the varistor voltage E.
の温度変化率△Ｅ １０も大きくなるという問題がある
。There is a problem that the temperature change rate ΔE10 also increases.
また、Ｎｂ、Ｌａ、Ｔａの各元素の酸化物がら選択した
１種又は２種以上の酸化物の添加量の総量を０．０５〜
０．５０モル％の範囲内としたこと、Ｃｕ、ＭＯｌＦｅ
、Ｍｎの各元素の酸化物から選択した１種又は２種以上
の酸化物の添加量の総量を０．０５〜０．５０モル％の
範囲内としたこと、及びＳｉｎｇの添加量を０．５０〜
１．００モル％の範囲内としたことの理由は、いずれも
各範囲を外れる量の添加量では、非直線係数α値が低下
してしまうとともに、バリスタ電圧Ｅ ＩＱの温度変化
率ΔＥ１゜が大きくなってしまうという問題があるため
である。In addition, the total amount of one or more oxides selected from the oxides of each element of Nb, La, and Ta is 0.05~
Within the range of 0.50 mol%, Cu, MOLFe
, Mn, the total amount of one or more oxides selected from the oxides of each element was within the range of 0.05 to 0.50 mol %, and the amount of Sing was 0.05 to 0.50 mol %. 50~
The reason for setting it within the range of 1.00 mol% is that if the amount added is outside the respective ranges, the nonlinear coefficient α value will decrease, and the temperature change rate ΔE1° of the varistor voltage E IQ will decrease. This is because there is a problem in that it becomes large.
なお、バリスタ電圧Ｅ１゜の温度変化率△Ｅ ＩＱの値
は、バリスタ電圧が高い場合には０．１以下が望ましい
が、従来の電圧依存非直線抵抗体の温度変化率ΔＥ ｌ
（ｌの値は０．２〜０．３程度であった。しかし、上記
組成からなる本発明の電圧依存非直線抵抗体の温度変化
率ΔＥ ｔｏは十分低く、安定したバリスタ電圧Ｅ、。Note that the value of the temperature change rate ΔE IQ of the varistor voltage E1° is preferably 0.1 or less when the varistor voltage is high, but the temperature change rate ΔE l of a conventional voltage-dependent nonlinear resistor is
(The value of l was about 0.2 to 0.3. However, the temperature change rate ΔE to of the voltage-dependent nonlinear resistor of the present invention having the above composition is sufficiently low, and the varistor voltage E is stable.
が得られるものである。is obtained.
このように、上記本発明による組成からなる電圧依存非
直線抵抗体は、熱処理工程が大幅に短縮され、高い非直
線係数αが得られるとともに、バリスタ電圧Ｅ、。の温
度変化率△Ｅ、。も小さい安定した特性を得ることがで
きる。As described above, the voltage dependent nonlinear resistor having the composition according to the present invention can significantly shorten the heat treatment process, obtain a high nonlinear coefficient α, and have a high varistor voltage E. The temperature change rate △E,. It is also possible to obtain small and stable characteristics.
［実施例］
次に、本発明の実施例について、組成比の異なる電圧依
存非直線抵抗体の試料を作製し、その特性を評価しなが
ら説明する。[Example] Next, an example of the present invention will be described while producing samples of voltage-dependent nonlinear resistors having different composition ratios and evaluating their characteristics.
（試料の作製）
まず、５ｒＴｉＯａ及びＣａＴｉ０−の各チタン酸金属
酸化物粉末と、Ｎｂ、Ｌａ、Ｔａの各元素の酸化物のう
ち少なくとも１種類の粉末と、Ｃｕ、Ｍｏ％Ｆｅ、Ｍｎ
の各元素の酸化物のうち少なくとも１種類の粉末と、Ｃ
ｕ、Ｍｏ、Ｆｅ、Ｍｎの各元素の酸化物粉末のうち少な
くとも１種類の粉末を、試料１から試料５６までの５６
種類それぞれ所定の組成比となるように秤量し、これら
を湿式ボールミルにより１５時間混合した。(Preparation of Samples) First, each titanate metal oxide powder of 5rTiOa and CaTi0-, powder of at least one type of oxide of each element of Nb, La, Ta, Cu, Mo%Fe, Mn
a powder of at least one kind of oxide of each element;
At least one type of oxide powder of each element of u, Mo, Fe, and Mn was added to 56 powders from sample 1 to sample 56.
Each type was weighed so as to have a predetermined composition ratio, and mixed in a wet ball mill for 15 hours.
上記のようにして得られた各混合物を大気中で温度１５
０℃で乾燥した後、酢酸ビニル系バインダーを添加して
混合、造粒して原料粉末とした。Each mixture obtained as described above was heated in the atmosphere at a temperature of 15%.
After drying at 0° C., a vinyl acetate binder was added, mixed, and granulated to obtain a raw material powder.
さらに上記各原料粉末を、金型を用いて所定形状に成型
した。具体的には、乾式プレスにより、］、、５００Ｋ
ｇ／ｃｍ２の圧力で外径１２．２５ｍｍ％内径７．７５
ｍｍ、厚さ１．０４ｍｍ、成形体密度３．３０ｇ／ｃｍ
″のリング状成形体に成型した。Furthermore, each of the above raw material powders was molded into a predetermined shape using a mold. Specifically, by dry pressing, ],,500K
Outer diameter 12.25mm% Inner diameter 7.75 at g/cm2 pressure
mm, thickness 1.04mm, compact density 3.30g/cm
It was molded into a ring-shaped molded body.
続いて、これらのリング状成形体を、窒素ガス９６容積
％と水素ガス４容積％とからなる混合ガス雰囲気中で温
度１４１Ｏ℃で６時間焼成しくこれを「第１熱処理」と
いう。）、焼結体を得た。Subsequently, these ring-shaped molded bodies were fired at a temperature of 1410° C. for 6 hours in a mixed gas atmosphere consisting of 96% by volume of nitrogen gas and 4% by volume of hydrogen gas, and this was called "first heat treatment." ), a sintered body was obtained.
さらに、これらの焼結体を、９５０ないし１ｏｏｏ℃で
３時間の熱処理（これを「第２熱処理」、という。〕を
２ないし数回施し、バリスタ電圧が７０〜１００Ｖの範
囲内となるように調整した。Furthermore, these sintered bodies were subjected to heat treatment at 950 to 100°C for 3 hours (this is referred to as "second heat treatment") two to several times, so that the varistor voltage was within the range of 70 to 100V. It was adjusted.
このようにして得られた電圧依存非直線抵抗体の各試料
の上下両面に銀電極材を塗布後、温度１８０℃で１０分
間乾燥し、さらに温度７８０℃で１０分間焼付けて銀電
極を形成した。After applying silver electrode material to the upper and lower surfaces of each sample of the voltage-dependent nonlinear resistor thus obtained, it was dried at a temperature of 180°C for 10 minutes, and then baked at a temperature of 780°C for 10 minutes to form a silver electrode. .
（試料の特性評価）
次に、各試料の特性評価を行うために、バリスタ電圧Ｅ
１０、非直線抵抗係数ａ、バリスタ電圧Ｅ １０の温
度変化率△Ｅ ｔｏを測定した。(Characteristics evaluation of samples) Next, in order to evaluate the characteristics of each sample, the varistor voltage E
10, non-linear resistance coefficient a, varistor voltage E, and temperature change rate ΔE to of 10 were measured.
なお、非直線係数αと、バリスタ電圧Ｅ１゜の変化率の
測定は、定電流電源装置で行った。Note that the nonlinear coefficient α and the rate of change of the varistor voltage E1° were measured using a constant current power supply device.
また、非直線係数αは、次式により求めた。In addition, the nonlinear coefficient α was determined using the following equation.
ここでＥｌは電流１が１ｍＡのときの電圧■の値である
。Here, El is the value of voltage ■ when current 1 is 1 mA.
さらに、バリスタ電圧Ｅ ＩＱの温度変化率△Ｅ１゜は
、温度変化１℃当たりのバリスタ電圧Ｅ、。値の変化率
（％／”Ｃ）であり、次式により求めた。Furthermore, the temperature change rate ΔE1° of the varistor voltage E IQ is the varistor voltage E per 1°C of temperature change. It is the rate of change in value (%/''C) and was determined by the following formula.
ｂ ｔｏ（ａｔ ２５℃ｌ Ｘ ｆ５０−２５１
ここでＥ、。（ａｔ ２５℃）は２５℃におけるバリス
タ電圧Ｅ ｔｏであり、Ｅ ｔｏ（ａｔ ５０℃）は５
０℃におけるバリスタ電圧である。b to(at 25℃l X f50-251
E here. (at 25°C) is the varistor voltage E to at 25°C, and E to (at 50°C) is 5
This is the varistor voltage at 0°C.
第１表（１）ないし第１表（１１）は、組成比の異なる
試料１ないし５６について、組成比、試料作製時におけ
る第２熱処理の回数、バリスタ電圧Ｅ ｔｏ、非直線係
数α及びバリスタ電圧の温度変化率△Ｅ １０を示した
ものである。なお各表は、所定成分の添加量の変化に注
目し、添加量を変えた所定成分ごとに（１）ないしく１
１）に分けて示している。従って、他の成分の添加量は
一定とし、残余はＳ ｒ Ｔ ｉ Ｏｘとなっている。Table 1 (1) to Table 1 (11) show the composition ratio, number of second heat treatments during sample preparation, varistor voltage E to, nonlinear coefficient α, and varistor voltage for samples 1 to 56 with different composition ratios. The figure shows the temperature change rate ΔE10. In addition, each table focuses on changes in the added amount of a given ingredient, and shows (1) or 1 for each given ingredient whose added amount has been changed.
1). Therefore, the amounts of other components added are constant, and the remainder is S r T i Ox.
まず第１表（１）から分かるように、
ＣａＴ ｉ Ｏ３のみの添加量を変化させ、その他の添
加剤の添加量を一定とし、残りをＳｒＴｉＯ３としたと
きには、ＣａＴｉ０．の添加量が１５．００モル％より
少ない場合には、所定のバリスタ電圧値を得るための熱
処理回数が５ないし８回と多く、非直線係数αも比較的
小さ（、バリスタ電圧の温度変化率△Ｅ、。の絶対値も
大きい。First, as can be seen from Table 1 (1), when only the amount of CaT i O3 added is changed, the amounts of other additives are constant, and the rest is SrTiO3, CaTi0. When the amount of addition is less than 15.00 mol%, the number of heat treatments to obtain a predetermined varistor voltage value is as large as 5 to 8 times, and the nonlinear coefficient α is also relatively small (temperature change rate of varistor voltage The absolute value of ΔE, . is also large.
また、Ｃａ Ｔ ｉ Ｏ３の添加量が２６．００モル％
より大きい場合には、やはり非直線係数ａは比較的小さ
（、バリスタ電圧の温度変化率△Ｅ ｔ。In addition, the amount of Ca Ti O3 added was 26.00 mol%
If larger, the nonlinear coefficient a is still relatively small (the rate of temperature change of the varistor voltage ΔE t).
の絶対値も大きい。The absolute value of is also large.
以上から、ＣａＴｉＯｓの添加量は１５．００〜２６．
００モル％の範囲が適当である。From the above, the amount of CaTiOs added is 15.00 to 26.00.
A range of 0.00 mol% is suitable.
次に、第１表（２）ないし第１表（４）から分かるよう
に、Ｎ ｂ ｚ Ｏｓ Ｌ ＆ ２０ ｍ及びＴａ１
ｌｓのうちの１種類を添加する場合の添加量は、いずれ
も０．０５〜０．５０モル％の範囲が適当である。Ｎｂ
２０ｓ 、Ｌａ２Ｏ３及び丁ａ ｚ ０３の添加量が上
記の範囲外であると、非直線係数ａが低く、バリスタ電
圧の温度変化率△Ｅ ｔｏの絶対値も大きくなるからで
ある。Next, as can be seen from Table 1 (2) to Table 1 (4), N b z Os L & 20 m and Ta1
When one type of ls is added, the appropriate amount is in the range of 0.05 to 0.50 mol%. Nb
This is because if the addition amounts of 20s, La2O3, and Dz03 are outside the above range, the nonlinear coefficient a will be low and the absolute value of the temperature change rate ΔE to of the varistor voltage will also be large.
次に、第１表（５）ないし第１表（８）から分かるよう
に、Ｃｕ Ｏ、Ｆ ｅ ２０ ａ 、 Ｍ ｎ ０２、
Ｍ ｏ Ｏ３のうちの１種印を添加する場合の添加量に
ついても、いずれも０．０５〜０．５０モル％の範囲が
適当である。Ｃｕｂ、Ｆｅｚ Ｏｓ、Ｍ ｎ ０２ 、
Ｍ ｏ Ｏｚの添加量が上記の範囲外であると、やはり
非直線係数ａが低く、バリスタ電圧の温度変化率△Ｅ１
゜の絶対値も太き（なるからである。Next, as can be seen from Table 1 (5) to Table 1 (8), CuO, Fe20a, Mn02,
The addition amount in the case of adding type 1 of MoO3 is also suitably in the range of 0.05 to 0.50 mol%. Cub, Fez Os, M n 02,
If the amount of M o Oz added is outside the above range, the nonlinear coefficient a will still be low, and the temperature change rate of varistor voltage △E1
The absolute value of ° is also thick.
次に、第１表（９）から分かるように、３ ｉ ０２の
添加量は、０．５０〜１．００モル％の範囲が適当であ
る。この範囲外であると、やはり非直線係数αが低く、
バリスタ電圧の温度変化率△Ｅ、。の絶対値も大きくな
るからである。Next, as can be seen from Table 1 (9), the appropriate amount of 3i02 to be added is in the range of 0.50 to 1.00 mol%. Outside this range, the nonlinear coefficient α is still low;
Temperature change rate △E of varistor voltage. This is because the absolute value of will also increase.
さらに、第１表（１０）及び第１表（１１）から、Ｎｂ
ｚ Ｏｓ 、Ｌａｇ Ｏｓ及びＴａ２０ｘのうちの２種
又は全種を添加する場合、及びＣｕ、 ０１Ｆｅ２０ｓ
、Ｍｎ０ｚ 、ＭｏＯ３のうちの２種又は全種を添加
する場合でも、相互に影響を及ぼすことなく大きな非直
線係数ａが得られ、バリスタ電圧の温度変化率△Ｅ１゜
も十分低いものであることが分かる。Furthermore, from Table 1 (10) and Table 1 (11), Nb
When adding two or all of zOs, LagOs and Ta20x, and Cu, 01Fe20s
, Mn0z, and MoO3, even if two or all of them are added, a large nonlinear coefficient a can be obtained without affecting each other, and the temperature change rate △E1° of the varistor voltage is also sufficiently low. I understand.
以上のように、各添加剤の添加量が上述の所定の範囲内
であれば、製作時に必要な熱処理の回数も２ないし３回
と少なくて済み、バリスタ電圧も８以上を確保しつつ非
直線係数も高く、バリスタ電圧の温度変化率も十分低い
電圧依存非直線抵抗体として使用することができるもの
である。As described above, if the amount of each additive is within the specified range mentioned above, the number of heat treatments required during manufacturing can be as few as 2 or 3 times, and the varistor voltage can be maintained at 8 or higher while maintaining non-linear It has a high coefficient and a sufficiently low temperature change rate of varistor voltage, so it can be used as a voltage-dependent nonlinear resistor.
［発明の効果コ
このように本発明により、非直線係数が大きく、かつバ
リスタ電圧も高いチタン酸ストロンチウム系電圧依存非
直線抵抗体を提供することができた。[Effects of the Invention] As described above, according to the present invention, it was possible to provide a strontium titanate-based voltage-dependent nonlinear resistor having a large nonlinear coefficient and a high varistor voltage.
Claims (1)
する電圧依存比直線抵抗体において、チタン酸カルシウ
ム（ＣａＴｉＯ＿３）を５．００〜２６．００モル％、
ニオブ（Ｎｂ）、ランタン（Ｌａ）及びタンタル（Ｔａ
）の各元素の酸化物からなるグループから選択した１種
又は２種以上の酸化物の総量を０．０５〜０．５０モル
％、銅（Ｃｕ）、モリブデン（Ｍｏ）、鉄（Ｆｅ）及び
マンガン（Ｍｎ）の各元素の酸化物からなるグループか
ら選択した１種又は２種以上の酸化物の総量を０．０５
〜０．５０モル％、二酸化ケイ素（ＳｉＯ＿２）を０．
５０〜１．００モル％それぞれ含有することを特徴とす
る電圧依存非直線抵抗体。In a voltage-dependent specific linear resistor mainly composed of strontium titanate (SrTiO_3), calcium titanate (CaTiO_3) is contained in an amount of 5.00 to 26.00 mol%,
Niobium (Nb), lanthanum (La) and tantalum (Ta)
), the total amount of one or more oxides selected from the group consisting of oxides of each element is 0.05 to 0.50 mol%, copper (Cu), molybdenum (Mo), iron (Fe) and The total amount of one or more oxides selected from the group consisting of oxides of each element of manganese (Mn) is 0.05
~0.50 mol%, silicon dioxide (SiO_2) 0.
A voltage-dependent nonlinear resistor characterized by containing 50 to 1.00 mol% of each.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2076777A JP2585121B2 (en) | 1990-03-28 | 1990-03-28 | Method of manufacturing voltage-dependent nonlinear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2076777A JP2585121B2 (en) | 1990-03-28 | 1990-03-28 | Method of manufacturing voltage-dependent nonlinear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03278403A true JPH03278403A (en) | 1991-12-10 |
| JP2585121B2 JP2585121B2 (en) | 1997-02-26 |
Family
ID=13615025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2076777A Expired - Fee Related JP2585121B2 (en) | 1990-03-28 | 1990-03-28 | Method of manufacturing voltage-dependent nonlinear resistor |
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| Country | Link |
|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01226120A (en) * | 1988-03-07 | 1989-09-08 | Matsushita Electric Ind Co Ltd | Voltage-dependent non-linear resistor ceramic composition |
-
1990
- 1990-03-28 JP JP2076777A patent/JP2585121B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01226120A (en) * | 1988-03-07 | 1989-09-08 | Matsushita Electric Ind Co Ltd | Voltage-dependent non-linear resistor ceramic composition |
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| Publication number | Publication date |
|---|---|
| JP2585121B2 (en) | 1997-02-26 |
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