JPS63315559A - Thermistor porcelain composition - Google Patents
Thermistor porcelain compositionInfo
- Publication number
- JPS63315559A JPS63315559A JP62151905A JP15190587A JPS63315559A JP S63315559 A JPS63315559 A JP S63315559A JP 62151905 A JP62151905 A JP 62151905A JP 15190587 A JP15190587 A JP 15190587A JP S63315559 A JPS63315559 A JP S63315559A
- Authority
- JP
- Japan
- Prior art keywords
- thermistor
- oxide
- resistance value
- elements
- component
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 229910052573 porcelain Inorganic materials 0.000 title claims description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract 2
- 239000000919 ceramic Substances 0.000 claims description 3
- -1 In addition Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、Ｍｎ 、 Ｎｉ 、 Ｃｕ ｆ主成分とす
る酸化物系、いわゆるスピネル系サーミスタは−４０〜
１５０℃の温度検出用、あるいは突入電流防止用素子と
して、液温計、スイッチング電源保護用等、近年多くの
機器に用いられるようになってきているサーミスタ磁器
組成物に関するものである０従来の技術
従来、この種のＭｎ−Ｎｉ−Ｃｕ系サーミスタは、各々
の元素比率を変えることによジ比抵抗及びサーミスタ定
数（Ｂ定数）を広範囲にコントロールすることができ、
回路とのマツチングをとりやすいため、広く用いられて
いる組成である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to an oxide-based thermistor containing Mn, Ni, and Cu as main components, so-called spinel-based thermistors.
This relates to thermistor ceramic compositions that have been used in many devices in recent years, such as for detecting a temperature of 150°C or as an inrush current prevention element, for liquid thermometers, for protecting switching power supplies, etc.0Prior art Conventionally, in this type of Mn-Ni-Cu-based thermistor, the resistivity and thermistor constant (B constant) can be controlled over a wide range by changing the ratio of each element.
This composition is widely used because it is easy to match with circuits.
発明が解決しようとする問題点
しかし、このサーミスタは製造上の欠点もあり、完成工
程時の特性変動（抵抗値、Ｂ定数）が太きいため、実際
の製造工程では焼結後に２００〜３ｏｏ℃で３〜７日程
度のエージング処理を必要としていたが、これでも充分
ではなかった。捷た、完成品の経時変化も大きく、高精
度のサーミスタを製造することが困難であった。Problems to be Solved by the Invention However, this thermistor also has manufacturing drawbacks, and the characteristic fluctuations (resistance value, B constant) during the completion process are large. This required aging treatment for about 3 to 7 days, but even this was not sufficient. The finished product deteriorated significantly over time, making it difficult to manufacture highly accurate thermistors.
この原因は明確ではないが、焼成時における元素成分の
飛散、陽イオン分布の安定性、焼結反応性等が複雑に絡
みあって起因しているものと考えられる。The cause of this is not clear, but it is thought to be caused by a complex interaction of scattering of elemental components during firing, stability of cation distribution, sintering reactivity, etc.
本発明はこのような問題点を解決するもので、Ｍｎ、Ｎ
工及びＣｕの酸化物固溶体を主成分とするサーミスタ磁
器の抵抗値及びＢ定数のバラツキ（（変動係数）を小さ
くし、また抵抗値経時変化の小さい安定なサーミスタ磁
器組成物を提供することを目的とするものである。The present invention solves these problems, and is aimed at solving these problems.
The purpose of this invention is to reduce the variation (coefficient of variation) in the resistance value and B constant of a thermistor porcelain mainly composed of an oxide solid solution of copper and Cu, and to provide a stable thermistor porcelain composition with a small change in resistance value over time. That is.
問題点を解決するための手段
この問題点を解決するために本発明は、サーミスタ磁器
組成物を以下のようにしたものである。Means for Solving the Problem In order to solve this problem, the present invention provides a thermistor ceramic composition as follows.
（１） Ｍｎ 、 Ｎｉ及びＣｕの酸化物固溶体を主
成分とし、副成分としてＢｉ酸化物を加える。(1) The main component is an oxide solid solution of Mn, Ni, and Cu, and Bi oxide is added as a subcomponent.
（２）上記構成中、主成分にさらに元素成分としてＬｉ
、 Ｂ 、 Ｍｇ 、 ｋｌ 、 Ｓｉ 、 Ｔｉ
、 Ｖ 、 Ｏｒ 、 Ｚｎの内の１種もしくは２種以
上を添加する。(2) In the above structure, Li is further added as an elemental component to the main component.
, B, Mg, kl, Si, Ti
, V, Or, and Zn.
作用
上記（１）により、抵抗値及びＢ定数のバラツキは小さ
くなり、また抵抗値経時変化も著しく小さくなる。また
、上記（２によりさらに経時変化を小さく抑えることが
でき、高精度なサーミスタ磁器を実施例
以下、本発明を具体的な実施例に基づいて説明する。Effect: Due to the above (1), variations in resistance value and B constant are reduced, and changes in resistance value over time are also significantly reduced. Further, according to (2) above, the change over time can be further suppressed and the thermistor porcelain is highly accurate.Examples The present invention will be described below based on specific examples.
まず、市販の酸化マンガン、酸化ニッケル、酸化銅、酸
化ビスマス等を用い、下記の第１表に示す組成となるよ
うに所定量配合し、ボールミルによって２０時時間式混
合し、た。これｉｌ ６０〜２５０℃で乾燥させた後、
７００〜８００℃で２時間仮焼し、この仮焼物をボール
ミルによって２０時時間式粉砕した後、乾燥させた。こ
の仮焼粉末に１０％濃度のｐ、ｖ、人（ポリビニルアル
コール）溶液ｉ１０％加えて混合し、造粒を行った。First, using commercially available manganese oxide, nickel oxide, copper oxide, bismuth oxide, etc., predetermined amounts were blended so as to have the composition shown in Table 1 below, and the mixture was mixed in a ball mill for 20 hours. After drying this at 60-250℃,
The calcined product was calcined at 700 to 800° C. for 2 hours, and the calcined product was pulverized for 20 hours using a ball mill, and then dried. To this calcined powder, 10% of a 10% concentration of p, v, and human (polyvinyl alcohol) solution i was added and mixed to perform granulation.
そして、この造粒粉を直径１ｏ■、厚さ１．６ｆｉのデ
ィスク状に加圧成形し、１０００〜１２００℃の温度で
２時間焼成した後、銀電極を設けた。Then, this granulated powder was pressure-molded into a disc shape with a diameter of 1o and a thickness of 1.6fi, and after baking at a temperature of 1000 to 1200°C for 2 hours, a silver electrode was provided.
このようにして得られた各々のディスク状サーミスタ素
子を室温に１日放置した後、２６℃及び５０℃のオイル
バス中で比抵抗値を測定し、この温度間のＢ定数を算出
した。その結果を下記の第２表に示した。また、これら
の変動係数も同時に記載した０さらに、各サーミスタ素
子を１６０℃・空気中に１０００時間放置し、抵抗値変
化率Ｒｔ：を時間後の抵抗値）を求めた結果を図に示す
０
本発明によるサーミスタとの比較のために、従来の組成
物で構成されたサーミスタ素子を同一方法で作製し、抵
抗値、Ｂ定数とそれらの変動係数、及び抵抗値変化率を
同様に測定し併記した。After leaving each disk-shaped thermistor element thus obtained at room temperature for one day, the specific resistance value was measured in an oil bath at 26° C. and 50° C., and the B constant between these temperatures was calculated. The results are shown in Table 2 below. Furthermore, each thermistor element was left in air at 160°C for 1000 hours, and the resistance value change rate Rt: (resistance value after time) was determined. The results are shown in the figure. For comparison with the thermistor according to the present invention, a thermistor element made of a conventional composition was manufactured using the same method, and the resistance value, B constant, coefficient of variation thereof, and rate of change in resistance value were measured in the same manner and are also listed. did.
（以下金 白）
〈第１表〉
（＊：従来例）
〈第２表〉
（＊：従来例）
ここで、主成分に添加するＬｉ 、 Ｍｇ 、 Ｂ 、
人１等については、特定の元素の１種もしくは２種の組
合せについてのみしか記載されていないが、本発明者ら
ｔｒｉ、 Ｌｉ ＋ Ｂ 、 Ｍｇ 、ムｌ 、 Ｓｉ
、 Ｔｉ 、 Ｖ 、 Ｏｒ 。(hereinafter referred to as gold white) <Table 1> (*: Conventional example) <Table 2> (*: Conventional example) Here, Li, Mg, B,
Regarding people 1, etc., only one type or combination of two specific elements is described, but the present inventors have described tri, Li + B, Mg, Mul, Si.
, Ti, V, Or.
Ｚｎ元素の内の１種もしくは２種以上を所定量添加する
ことにより、上記の第２表に示す特性と同様な効果が得
られることを確認した。It was confirmed that effects similar to those shown in Table 2 above can be obtained by adding a predetermined amount of one or more of the Zn elements.
発明の効果
以上の結果から明らかなように、本発明によるサーミス
タは抵抗値、Ｂ定数のバラツキが小さく、製造上安定し
ており、抵抗値経時変化も小さいことから、昨今のサー
ミスタに対する電気特性の高精度化という要望に対して
多大な貢献ができるものである。Effects of the Invention As is clear from the above results, the thermistor according to the present invention has small variations in resistance value and B constant, is stable in manufacturing, and has small changes in resistance value over time. This can greatly contribute to the demand for higher precision.
なお、本発明において、Ｂｉ酸化物が０．１ ｍｏｌチ
未満では電気特性の変動係数及び経時変化への効果が見
られず、また１ｏｍｏ７Ｂ％を超えた場合には、逆に変
動係数が大きくなるために本発明の請求範囲外とした。In addition, in the present invention, when the Bi oxide is less than 0.1 mol, no effect on the coefficient of variation and aging of electrical properties is observed, and when it exceeds 1omo7B%, the coefficient of variation becomes large. Therefore, it is excluded from the scope of the present invention.
また、特許請求の範囲の第２項に示したＬｉ 、 Ｍｇ
等の添加元素量において、０．１原子チ未満ではＢｉ酸
化物と同様に効果が見られず、一方１０原子％を超えた
場合には電気特性の変動係数が大きくなったため、本発
明の請求範囲外とした。In addition, Li, Mg shown in the second claim
When the amount of added elements is less than 0.1 at. It was out of range.
図は本発明の一実施例によるサーミスタ素子及び従来の
サーミスタ素子の１６０℃・空気中放置における抵抗値
経時変化率を示す図である０代理人の氏名 弁理士 中
尾 敏 男 ほか１名１〜１５″一本発明
＋６−２０ ・・・従来例The figure shows the rate of change in resistance value over time of a thermistor element according to an embodiment of the present invention and a conventional thermistor element when left in air at 160°C. 0 Name of agent: Patent attorney Toshio Nakao and 1 other person 1 - 15″ 1 Invention + 6-20 ・・・Conventional example
Claims (2)
、副成分としてＢｉ元素を０．１〜１０ｍｏｌ％加えた
ことを特徴とするサーミスタ磁器組成物。(1) A thermistor ceramic composition comprising Mn, Ni, and Cu as main components as metal elements, and 0.1 to 10 mol% of Bi element added as a subcomponent.
これにＬｉ、Ｂ、Ｍｇ、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｃｒ、
Ｚｎ元素の内の１種もしくは２種以上を０．１〜１０原
子％含有し、かつこれら主成分に対して副成分としてＢ
ｉ元素を０．１〜１０ｍｏｌ％加えたことを特徴とする
サーミスタ磁器組成物。(2) Mainly containing Mn, Ni and Cu as metal elements,
In addition, Li, B, Mg, Al, Si, Ti, V, Cr,
Contains 0.1 to 10 at% of one or more of the Zn elements, and B as a subcomponent to these main components.
A thermistor porcelain composition characterized in that 0.1 to 10 mol% of element i is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151905A JPS63315559A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151905A JPS63315559A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63315559A true JPS63315559A (en) | 1988-12-23 |
Family
ID=15528756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151905A Pending JPS63315559A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63315559A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH047803A (en) * | 1990-04-25 | 1992-01-13 | Koa Corp | Thick film thermistor composite |
| JP2013534508A (en) * | 2010-06-24 | 2013-09-05 | エプコス アクチエンゲゼルシャフト | Cobalt-free NTC ceramic and method for producing cobalt-free NTC ceramic |
| CN114751724A (en) * | 2022-05-31 | 2022-07-15 | 汕头市瑞升电子有限公司 | NTC thermistor medium material and preparation method thereof |
-
1987
- 1987-06-18 JP JP62151905A patent/JPS63315559A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH047803A (en) * | 1990-04-25 | 1992-01-13 | Koa Corp | Thick film thermistor composite |
| JP2013534508A (en) * | 2010-06-24 | 2013-09-05 | エプコス アクチエンゲゼルシャフト | Cobalt-free NTC ceramic and method for producing cobalt-free NTC ceramic |
| US9058913B2 (en) | 2010-06-24 | 2015-06-16 | Epcos Ag | Cobalt-free NTC ceramic and method for producing a cobalt-free NTC ceramic |
| CN114751724A (en) * | 2022-05-31 | 2022-07-15 | 汕头市瑞升电子有限公司 | NTC thermistor medium material and preparation method thereof |
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