JPS63315554A - Thermistor porcelain composition - Google Patents
Thermistor porcelain compositionInfo
- Publication number
- JPS63315554A JPS63315554A JP62151898A JP15189887A JPS63315554A JP S63315554 A JPS63315554 A JP S63315554A JP 62151898 A JP62151898 A JP 62151898A JP 15189887 A JP15189887 A JP 15189887A JP S63315554 A JPS63315554 A JP S63315554A
- Authority
- JP
- Japan
- Prior art keywords
- porcelain composition
- oxide
- thermistor
- resistance value
- elements
- 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 16
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract 2
- 229910052725 zinc Inorganic materials 0.000 claims abstract 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910020641 Co Zr Inorganic materials 0.000 description 1
- 229910020520 Co—Zr 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 238000005245 sintering Methods 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
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、Ｍｎ、 Ｎｉ、 Ｃｉｏ及びＺｒを主成分と
する酸化物系、いわゆるスピネル系サーミスタは一４０
〜１５０°Ｃ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。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an oxide thermistor containing Mn, Ni, Cio, and Zr as main components, so-called spinel-based thermistors.
The present invention relates to a thermistor ceramic composition that has recently come to be used in many devices such as liquid thermometers, switching power supply protection, etc., for temperature detection of ~150°C or as an inrush current prevention element.
従来の技術
従来、この種のＭｎ−Ｎｉ−Ｃｏ−Ｚｒ系サーミスタは
、各々の元素比率を変えることにより比抵抗及びサーミ
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。Conventional technology Conventionally, this type of Mn-Ni-Co-Zr based thermistor has been able to control the specific resistance and thermistor constant (B constant) over a wide range by changing the ratio of each element, making it easy to match the circuit. It is a widely used composition because it is easy to remove.
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）が大きいため、実際
の製造工程では焼結後に２００〜３００ ’Ｃ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。また、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 drawbacks in manufacturing, with large variations in characteristics (resistance value, B constant) during the completion process. 3 to 7
It required aging treatment for about a day, but even this was not sufficient. In addition, the finished product changes significantly over time.
It has been difficult to manufacture highly accurate thermistors.
この原因は明確ではないが、焼成時ておける元素成分の
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
ｉ、Ｃｏ及びＺｒ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、
問題点を解決するだめの手段
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。The present invention solves these problems, and is aimed at solving these problems.
It is an object of the present invention to provide a stable thermistor porcelain composition which reduces the variation (coefficient of variation) in the resistance value and B constant of a thermistor porcelain whose main component is an oxide solid solution of i, Co, and Zr, and whose resistance value changes over time. Means for Solving the Problem In order to solve this problem, the present invention provides a thermistor porcelain composition as follows.
（１） Ｍｎ、Ｎｉ、Ｇｏ及びＺｒ（７）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) Mn, Ni, Go, and Zr(7) oxide solid solution are the main components, 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、Ａｌ、 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, Al, Si, Ti, V, Or
, 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提供することができ
る。以下、バラツキは変動係実施例
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. Moreover, according to the above (2), the change over time can be further suppressed, and a highly accurate thermistor porcelain can be provided. Hereinafter, the present invention will be explained based on specific examples.
まず、市販の酸化マンガン、酸化ニッケル、酸化コバル
ト、酸化ジルコニウム、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。これを１５０〜２６
０°Ｃで乾燥させた後、７００〜８００°Ｃ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％ｉ度のＰ
、Ｖ 、Ａ（ポリビニルアルコール）溶液を１ｏ％加
えテ混合し、造粒を行った。そして、この造粒粉を直径
１０ＭＮ、厚さ１．５１１１１Ｉのディスク状に加圧成
形し、１０・Ｏｏ〜１２００’Ｃの温度で２時間焼成し
た後、銀電極を設けた。First, using commercially available manganese oxide, nickel oxide, cobalt oxide, zirconium 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. This is 150-26
After drying at 0°C, it was calcined at 700 to 800°C for 2 hours, and the calcined product was ground in a ball mill for 20 hours, and then dried. This calcined powder contains 10% i degree of P.
, V, A (polyvinyl alcohol) solution was added at 10% and mixed to perform granulation. Then, this granulated powder was pressure-molded into a disk shape with a diameter of 10 MN and a thickness of 1.51111 I, and after firing at a temperature of 10.00 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°Ｃ及び５０’Ｃのオ
イルパ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。さらに、各サーミス
タ素子を１５０’Ｃ・空気中に１０００時間放置し、抵
抗値変化率を時間後の抵抗値）を求めた結果を図に示す
。After leaving each disk-shaped thermistor element obtained in this way at room temperature for one day, the specific resistance value was measured in an oil path at 26°C and 50'C, and the B constant between these temperatures was calculated. . The results are shown in Table 2 below. In addition, these coefficients of variation are also listed at the same time. Furthermore, each thermistor element was left in air at 150'C for 1000 hours, and the results of determining the rate of change in resistance value (resistance value after time) are shown in the figure.
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ー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
を同時に測定し併記した。For comparison with the thermistor according to the present invention, a thermistor element made of a conventional composition was prepared by the same method,
The resistance value, the B constant, their coefficient of variation, and the rate of change in resistance value were simultaneously measured and recorded.
（以下金 白）
く第２表〉
（＊：従来例）
ここで、主成分に添加するＬｉ、 Ｍｇ、 Ｂ、ムを等
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、本発明者らはＬｉ
、 Ｂ、 Ｍｇ、人ｌ、 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。(Hereinafter referred to as "Kinshiro") Table 2> (*: Conventional example) Here, regarding Li, Mg, B, Mu, etc. added to the main components, only one or a combination of two specific elements are added. Although not described, the inventors have discovered that Li
, B, Mg, Personl, Si, Ti, V, Or
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０．１ｍ０Ｌ％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１０ｍ０ｔ％を超えた場合には、逆に変動係
数が犬きくなるために本発明の請求範囲外としだ。また
、特許請求の範囲の第２項に示したＬｉ、Ｍｇ等の添加
元素景において、０．１原子チ未満ではＢ１酸化物と同
様に効果が見られず、一方１ｏ原子チを超えた場合は電
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, in the present invention, if Bi oxide is less than 0.1 m0L%, no effect on the coefficient of variation and aging of electrical properties is observed, and if it exceeds 10 m0L%, the coefficient of variation becomes sharper. Therefore, it is outside the scope of the present invention. In addition, in the additive element landscape such as Li, Mg, etc. shown in the second claim, if it is less than 0.1 atomic Ti, the same effect as B1 oxide is not seen, but on the other hand, if it exceeds 10 atomic Ti Since the coefficient of variation of the electrical characteristics became large, it was excluded from the scope of the present invention.
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１５０°Ｃ・空気中放置における抵抗
値経時変化率を示す図である。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 150°C.
Claims (2)
分とし、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) The main components are Mn, Ni, Co, and Zr as metal elements, and 0.1 to 10 mol% of Bi element as a subcomponent.
A thermistor porcelain composition characterized by the following:
とし、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。(2) The main metal elements are Mn, Ni, Co and Zr, with Li, B, Mg, Al, Si, Ti, V,
0.1 to 1 or more of Cr and Zn elements
1. A thermistor porcelain composition containing 10 atomic % of Bi element and 0.1 to 10 mol % of Bi element added as a subcomponent to these main components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151898A JPS63315554A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151898A JPS63315554A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63315554A true JPS63315554A (en) | 1988-12-23 |
Family
ID=15528601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151898A Pending JPS63315554A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63315554A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231905A (en) * | 1991-09-24 | 1994-08-19 | Tdk Corp | Composition for thermistor |
| US6181859B1 (en) | 1997-01-20 | 2001-01-30 | Sumitomo Electric Industries, Ltd. | Coated optical fiber and method of making the same |
| JPWO2008041481A1 (en) * | 2006-09-29 | 2010-02-04 | 株式会社村田製作所 | NTC thermistor porcelain and NTC thermistor using it |
| CN111116173A (en) * | 2019-12-16 | 2020-05-08 | 深圳顺络电子股份有限公司 | Low-temperature sintered NTC thermistor ceramic material and preparation method thereof |
-
1987
- 1987-06-18 JP JP62151898A patent/JPS63315554A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231905A (en) * | 1991-09-24 | 1994-08-19 | Tdk Corp | Composition for thermistor |
| US6181859B1 (en) | 1997-01-20 | 2001-01-30 | Sumitomo Electric Industries, Ltd. | Coated optical fiber and method of making the same |
| JPWO2008041481A1 (en) * | 2006-09-29 | 2010-02-04 | 株式会社村田製作所 | NTC thermistor porcelain and NTC thermistor using it |
| US8258915B2 (en) | 2006-09-29 | 2012-09-04 | Murata Manufacturing Co., Ltd. | NTC thermistor ceramic and NTC thermistor using the same |
| CN111116173A (en) * | 2019-12-16 | 2020-05-08 | 深圳顺络电子股份有限公司 | Low-temperature sintered NTC thermistor ceramic material and preparation method thereof |
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