JPH02222501A - Grain boundary oxidation type non-linear resistance element - Google Patents
Grain boundary oxidation type non-linear resistance elementInfo
- Publication number
- JPH02222501A JPH02222501A JP1044734A JP4473489A JPH02222501A JP H02222501 A JPH02222501 A JP H02222501A JP 1044734 A JP1044734 A JP 1044734A JP 4473489 A JP4473489 A JP 4473489A JP H02222501 A JPH02222501 A JP H02222501A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- resistance element
- voltage
- grain boundary
- moo3
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003647 oxidation Effects 0.000 title claims description 11
- 238000007254 oxidation reaction Methods 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052573 porcelain Inorganic materials 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 6
- 229910010252 TiO3 Inorganic materials 0.000 abstract 2
- -1 banadium oxide Chemical compound 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 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）
この発明は粒界酸化型電圧非直線抵抗素子に関し、特に
たとえば電子機器や電気機器で発生する異常電圧、ノイ
ズおよび静電気などを吸収または除去するためなどに用
いられるバリスタなどのような、粒界酸化型電圧非直線
抵抗素子に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a grain boundary oxidation type voltage nonlinear resistance element, and in particular, to absorb or remove abnormal voltage, noise, static electricity, etc. generated in electronic equipment or electrical equipment. The present invention relates to grain boundary oxidation type voltage nonlinear resistance elements, such as varistors used for various purposes.
（従来技術）
従来の粒界酸化型電圧非直線抵抗素子としては、たとえ
ば５ｒＴｉＯｓ系の半導体磁器の結晶粒界を空気中酸化
やＮａｚ Ｏなとの酸化剤によって酸化し、結晶粒界に
絶縁層を形成したものがあった。(Prior art) As a conventional grain boundary oxidation type voltage nonlinear resistance element, for example, the grain boundaries of a 5rTiOs semiconductor ceramic are oxidized in air or with an oxidizing agent such as Naz O, and an insulating layer is formed at the grain boundaries. There was something that formed the.
このような電圧非直線抵抗素子は、その素体がペロブス
カイト結晶構造を有し、強誘電性を示すため、単にバリ
スタとしての機能のみでなく、コンデンサとしての機能
も有する。したがって、この電圧非直線抵抗素子を用い
て、異常高電圧（サージ）の吸収や電圧の安定化などを
行うことができるという利点がある。Since such a voltage nonlinear resistance element has a perovskite crystal structure and exhibits ferroelectricity, it functions not only as a varistor but also as a capacitor. Therefore, there is an advantage that this voltage nonlinear resistance element can be used to absorb abnormally high voltage (surge), stabilize voltage, and the like.
（発明が解決しようとする課題）
しかしながら、従来のＳ ｒ Ｔ ｆ Ｏｊ系半導体磁
器を用いたものでは、磁器を構成する粒子間の抵抗が大
きいため、その非直線係数が小さい。また、５ｒＴｉＯ
ｓ系半導体磁器を用いたものでは、パルス電圧が印加さ
れることによってその電気的特性が劣化してしまう。(Problems to be Solved by the Invention) However, in those using conventional S r T f Oj based semiconductor ceramics, the resistance between particles constituting the ceramic is large, so the nonlinear coefficient is small. Also, 5rTiO
In devices using S-based semiconductor ceramics, the electrical characteristics deteriorate when a pulse voltage is applied.
それゆえに、この発明の主たる目的は、バリスタ特性と
コンデンサ特性の両方を備え、大きなバリスタ電圧と大
きな非直線係数を有し、かつ大きなサージ耐量を有する
、粒界酸化型電圧非直線抵抗素子を提供することである
。Therefore, the main object of the present invention is to provide a grain boundary oxidation type voltage nonlinear resistance element that has both varistor characteristics and capacitor characteristics, has a large varistor voltage, a large nonlinear coefficient, and has a large surge withstand capacity. It is to be.
（課題を解決するための手段）
この発明は、（Ｓｒｌ−ｘ−ｙ Ｂａ、ＩＣａ、）Ｔｉ
ＯＸ （ただし、０．００１≦ｘ≦０．３．ｙ≦０２
５）を９８．０〜９９．９モル％と、Ｎｂ。(Means for Solving the Problems) This invention provides (Srl-x-y Ba, ICa,)Ti
OX (However, 0.001≦x≦0.3.y≦02
5) and 98.0 to 99.9 mol% of Nb.
Ｗ、Ｔａおよび希土類元素の中から選ばれる少なくとも
１種類の酸化物を０．１〜２．０モル％とからなる素体
に対して、酸化ナトリウム、酸化チタン・、酸化バナジ
ウム、酸化モリブデンをそれぞれＮ ａ ｘ Ｏ，Ｔ
ｉ Ｏｚ ＋ Ｖ！ Ｏ５およびＭｏＯ３ピに換算して
（Ｎ ａ ＊ Ｏ＞ Ｏ＋ Ｔ ＠ Ｏｔ ＞ ０ 、
Ｖ ｔ０５≧Ｏ＋ Ｍ ＯＯｓ≧０）総ｔＯ，０１〜２
．０モル％含有されてなる、粒界酸化型電圧非直線抵抗
素子である。Sodium oxide, titanium oxide, vanadium oxide, and molybdenum oxide are respectively added to an element body consisting of 0.1 to 2.0 mol% of at least one oxide selected from W, Ta, and rare earth elements. N a x O,T
i Oz + V! In terms of O5 and MoO3 pi, (N a * O > O + T @ Ot > 0,
V t05≧O+ M OOs≧0) Total tO, 01~2
．． This is a grain boundary oxidation type voltage non-linear resistance element containing 0 mol%.
（発明の効果）
この発明によれば、バリスタ特性とコンデンサ特性の両
方を備えた粒界酸化型電圧非直線抵抗素子を得ることが
できる。さらに、この粒界酸化型電圧非直線抵抗素子は
、大００〜３００ｖ程度の大きなバリスタ電圧を得るこ
とができ、さらに１５以上の大きな非直線係数を得るこ
とができる。(Effects of the Invention) According to the present invention, a grain boundary oxidation type voltage nonlinear resistance element having both varistor characteristics and capacitor characteristics can be obtained. Further, this grain boundary oxidation type voltage nonlinear resistance element can obtain a large varistor voltage of about 00 to 300 V, and can also obtain a large nonlinear coefficient of 15 or more.
また、この粒界酸化型電圧非直線抵抗素子では、５５０
０Ａ／ａＪまでのサージに耐えることができる。Moreover, in this grain boundary oxidation type voltage nonlinear resistance element, 550
Can withstand surges up to 0A/aJ.
この発明の上述の目的、その他の目的、特徴および利点
は、以下の実施例の詳細な説明から一層明らかとなろう
。The above objects, other objects, features and advantages of the present invention will become more apparent from the detailed description of the following embodiments.
（実施例）
まず、５ｒＣＯ，、ＢａＣ０，、Ｔｉｅ、、ＣａＣ０，
およびＮｂ、Ｗ、Ｔａ、希土類元素の酸化物粉末を別表
１に示す組成比のものが得られるように秤量して湿式混
合した。この混合物を乾燥後、１１５０℃で２時間仮焼
し、粉砕した。この粉砕物に酢酸ビニル系樹脂を５重量
％添加して造粒し、この造粒粉を１ｔｏｎ／ｃＪの圧力
で、直径１Ｑｍ、厚さ１．５ｍのベレット状に成形した
。この成形体を空気中において１０００℃で２時間焼成
した後、体積比でＨｚ ：Ｎｔ ＝１ ： １００の
雰囲気中において１４５０℃で２時間焼成し、半導体磁
器を得た。得られた半導体磁器に、別表１に示す割合で
Ｎａｇ Ｏ，Ｔｉ１ｔ ＋ Ｖ！ Ｏ８およびＭｏｂ、
の混合酸化物をフェスとともに塗布し、空気中において
１２００℃で２時間熱処理を行って、磁器ユニットを得
た。得られた磁器ユニットの対向面に銀ペーストを塗布
し、８００℃で焼き付けて銀電極を形成し、その電気的
特性を評価した。(Example) First, 5rCO,, BaC0,, Tie,, CaC0,
Then, oxide powders of Nb, W, Ta, and rare earth elements were weighed and wet-mixed to obtain the composition ratios shown in Attached Table 1. After drying this mixture, it was calcined at 1150° C. for 2 hours and pulverized. This pulverized product was granulated by adding 5% by weight of vinyl acetate resin, and the granulated powder was molded into a pellet shape with a diameter of 1 Qm and a thickness of 1.5 m under a pressure of 1 ton/cJ. This molded body was fired in air at 1000°C for 2 hours, and then fired at 1450°C for 2 hours in an atmosphere with a volume ratio of Hz:Nt=1:100 to obtain semiconductor porcelain. Nag O, Ti1t + V! was added to the obtained semiconductor porcelain in the proportions shown in Attached Table 1. O8 and Mob,
The mixed oxide was applied together with the face, and a heat treatment was performed at 1200° C. for 2 hours in the air to obtain a porcelain unit. A silver paste was applied to the facing surface of the obtained porcelain unit and baked at 800° C. to form a silver electrode, and its electrical characteristics were evaluated.
ここでは、磁器ユニットに１ｍＡの電流を流した時のバ
リスタ電圧Ｖ＋−ａ （Ｖ）、非直線係数αおよび静
電容量Ｃ−ｐ（ｎＦ）と５５００Ａ／ａｄのサージ電流
を印加した時のバリスタ電圧の変化率ΔＶ＋−ａ （
％）および非直線係数の変化率Δα（％）とを測定し、
別表２に示した。Here, the varistor voltage V+-a (V), nonlinear coefficient α and capacitance C-p (nF) when a current of 1 mA is applied to the ceramic unit, and the varistor voltage when a surge current of 5500 A/ad is applied. Voltage change rate ΔV+-a (
%) and the rate of change of the nonlinear coefficient Δα (%),
It is shown in Attached Table 2.
表の試料番号１〜８から明らかなように、Ｂａの添加量
が増加するとそれに従って静電容量が大きくなる。また
、Ｂａの添加量が少ない領域では、バリスタ電圧はあま
り変わらないが、その量が増加するに従って大きく変わ
る。そして、Ｓｒ、ＢａおよびＣａの原子数を１とした
ときのＢａの原子数Ｘが０．３を超えると、サージ電流
を印加したときのバリスタ電圧変化率および非直線係数
変化率が大きくなってしまう。As is clear from sample numbers 1 to 8 in the table, as the amount of Ba added increases, the capacitance increases accordingly. Further, in a region where the amount of Ba added is small, the varistor voltage does not change much, but it changes greatly as the amount increases. If the number of atoms of Ba, Put it away.
また、試料番号９〜１６から明らかなように、Ｃａの添
加量を増加するに従ってバリスタ電圧は小さくなる。そ
して、Ｓｒ、ＢａおよびＣａの原子数を１としたときの
Ｃａの原子数ｙが０．２５を超えると、サージ電流を印
加したときのバリスタ電圧変化率および非直線係数変化
率が大きくなってしまう。Moreover, as is clear from sample numbers 9 to 16, as the amount of Ca added increases, the varistor voltage decreases. If the number of Ca atoms y exceeds 0.25 when the number of Sr, Ba, and Ca atoms is 1, the varistor voltage change rate and nonlinear coefficient change rate will increase when a surge current is applied. Put it away.
また、試料番号２日のように、酸化（酸化促進）剤とし
て添加物（拡散物）を入れない場合には、バリスタ電圧
が小さく、非直線係数およびサージ耐量も小さい。Further, when no additive (diffusion material) is added as an oxidizing (oxidizing promoter) agent, as in sample number 2, the varistor voltage is small, and the nonlinear coefficient and surge resistance are also small.
それに対して、試料番号２９〜３３ないし試料番号３４
〜３８から明らかなように、Ｎａ２０およびＴｉ１ｔの
酸化剤を添加した場合には、バリスタ電圧が高くなり、
Ｎａｔ Ｏの添加量の増加あるいはＴｉＯ□の添加量の
増加にともなってバリスタ電圧が上昇することがわかる
。しかしながら、Ｎａ、ＯおよびＴｉＯ□の酸化剤の添
加量が２モル％を超えると、サージ耐量が低下してしま
う。On the other hand, sample numbers 29 to 33 to sample number 34
As is clear from ~38, when the oxidizing agents of Na20 and Ti1t are added, the varistor voltage increases,
It can be seen that the varistor voltage increases as the amount of added Nat 2 O or TiO□ increases. However, if the added amount of the oxidizing agents Na, O, and TiO□ exceeds 2 mol %, the surge resistance decreases.
また、試料番号３９〜４８から明らかなように、■、０
．およびＭｏＯ３の酸化剤には、サージ耐量を下げない
でバリスタ電圧を上昇させる効果があるが、■２０．お
よびＭｏｂ、を含む酸化剤の添加量が２モル％を超える
と、やはりサージ耐量は低下してしまう。Also, as is clear from sample numbers 39 to 48, ■, 0
．． And the MoO3 oxidizing agent has the effect of increasing the varistor voltage without reducing the surge resistance, but ■20. If the amount of the oxidizing agent added exceeds 2 mol %, the surge resistance will also decrease.
また、Ｂａを含む試料は、Ｂａを含まない従来例に比べ
て、同様なバリスタ電圧で２倍以上の静電容量を得るこ
とができる。In addition, the sample containing Ba can obtain a capacitance that is more than twice that of a conventional example that does not contain Ba at the same varistor voltage.
以上のように、この発明の粒界酸化型電圧非直線抵抗素
子では、５５００ Ａ／ｃｍ！までのサージ電流に耐え
ることができ、かつ非直線係数αが１５以上と大きい。As described above, the grain boundary oxidation type voltage nonlinear resistance element of the present invention has a power of 5500 A/cm! It can withstand surge currents up to 1000 ft, and has a large nonlinear coefficient α of 15 or more.
また、酸化剤として、■！０．あるいはＭ ｏ ０、を
含む場合、■２０．あるいはＭｏｂ、の添加量によって
、バリスタ電圧をコントロールすることができる。特に
、酸化剤としてＭｏＯ３を含む場合には、Ｍｏｂ、が静
電容量を増大させるので、Ｍｏ５ｓの添加量によって目
的に応じた静電容量にコントロールすることも可能であ
る。Also, as an oxidizing agent, ■! 0. Or if it includes M o 0, ■20. Alternatively, the varistor voltage can be controlled by the amount of Mob added. In particular, when MoO3 is included as an oxidizing agent, Mob increases the capacitance, so it is possible to control the capacitance to suit the purpose by adjusting the amount of Mo5s added.
特許出願人 株式会社 村田製作所 代理人 弁理士 岡 １） 全 啓Patent applicant Murata Manufacturing Co., Ltd. Agent: Patent Attorney Oka 1) Zenhiro
Claims (1)
Ｏ＿３（ただし、０．００１≦ｘ≦０．３，ｙ≦０．２
５）を９８．０〜９９．９モル％と、Ｎｂ，Ｗ，Ｔａお
よび希土類元素の中から選ばれる少なくとも１種類の酸
化物を０．１〜２．０モル％とからなる素体に対して、
酸化ナトリウム，酸化チタン，酸化バナジウム，酸化モ
リブデンをそれぞれＮａ＿２Ｏ，ＴｉＯ＿２，Ｖ＿２Ｏ
＿５およびＭｏＯ＿３に換算して（Ｎａ＿２Ｏ＞０，Ｔ
ｉＯ＿２＞０，Ｖ＿２Ｏ＿５≧０，ＭｏＯ＿３≧０）総
量０．０１〜２．０モル％含有されてなる、粒界酸化型
電圧非直線抵抗素子。(Sr_1_-_x_-_yBa_xCa_y)Ti
O_3 (However, 0.001≦x≦0.3, y≦0.2
5) for an element body consisting of 98.0 to 99.9 mol% and 0.1 to 2.0 mol% of at least one kind of oxide selected from Nb, W, Ta and rare earth elements. hand,
Sodium oxide, titanium oxide, vanadium oxide, and molybdenum oxide are Na_2O, TiO_2, and V_2O, respectively.
_5 and MoO_3 (Na_2O>0, T
A grain boundary oxidation type voltage nonlinear resistance element containing iO_2>0, V_2O_5≧0, MoO_3≧0) in a total amount of 0.01 to 2.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044734A JPH02222501A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044734A JPH02222501A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02222501A true JPH02222501A (en) | 1990-09-05 |
Family
ID=12699679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1044734A Pending JPH02222501A (en) | 1989-02-23 | 1989-02-23 | Grain boundary oxidation type non-linear resistance element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02222501A (en) |
-
1989
- 1989-02-23 JP JP1044734A patent/JPH02222501A/en active Pending
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