JPS63315555A - Thermistor porcelain composition - Google Patents
Thermistor porcelain compositionInfo
- Publication number
- JPS63315555A JPS63315555A JP62151899A JP15189987A JPS63315555A JP S63315555 A JPS63315555 A JP S63315555A JP 62151899 A JP62151899 A JP 62151899A JP 15189987 A JP15189987 A JP 15189987A JP S63315555 A JPS63315555 A JP S63315555A
- Authority
- JP
- Japan
- Prior art keywords
- porcelain composition
- thermistor
- resistance value
- elements
- main 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 16
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract 4
- 239000000919 ceramic Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 229910000416 bismuth oxide Inorganic materials 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
- 239000007788 liquid Substances 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
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 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
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 101000958041 Homo sapiens Musculin Proteins 0.000 description 1
- 229910018651 Mn—Ni 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 102000046949 human MSC Human genes 0.000 description 1
- 230000003993 interaction Effects 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、Ｎｉｉ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 is directed to the use of oxide-based, so-called spinel-based thermistors containing Mn and Ni as main components, for detecting temperatures between -40 and 150°C, or as inrush current prevention elements. The present invention relates to a thermistor ceramic composition that has been used in many devices in recent years, such as liquid thermometers, switching power supply protection, and the like.
従来の技術
従来、この種のＭｎ−Ｎｉ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ＣＢ
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 based thermistor has been developed by changing the specific resistance and thermistor constant CB by changing the ratio of each element.
It is a widely used composition because it can control the constant (constant) over a wide range and is easy to match with the circuit.
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２ｏｏ〜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 has drawbacks in manufacturing, with large variations in characteristics (resistance value, B constant) during the completion process. 3-7
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 、
Ｎｉ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.
To reduce the variation (coefficient of variation) in the resistance value and B constant of the thermistor ceramic whose main component is an oxide solid solution of Ni,
Another object of the present invention is to provide a stable thermistor ceramic composition whose resistance value changes little over time.
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。Means for Solving the Problem In order to solve this problem, the present invention provides a thermistor porcelain composition as follows.
（１） Ｍｎ 、 Ｎｉ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) An oxide solid solution of Mn and Ni is the main component, 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 、ムｌ 、 Ｓｉ 、 Ｔｉ 、
Ｖ 、 Ｏｒ 、 ＺｎＯ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, Mul, Si, Ti,
One or more of V, Or, and ZnO are added.
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。First, using commercially available manganese oxide, nickel 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.
これを１５０〜２５０°Ｃで乾燥させた後、７００〜８
００″Ｃで２時間仮焼し、この仮焼物をボールミルによ
って２Ｑ時間湿式粉砕した後、乾燥させた。この仮焼粉
末に１０チ濃度のｐ、ｖ、ム（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。そして、こ
の造粒粉を直径１０１ｕ、厚さ１．６Ｂ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。After drying this at 150-250°C,
Calcined at 00''C for 2 hours, this calcined product was wet-pulverized for 2Q hours using a ball mill, and then dried. P, V, Mu (polyvinyl alcohol) with a concentration of 10% was added to this calcined powder.
10% Solution I was added and mixed to perform granulation. Then, this granulated powder was pressure-molded into a disk shape with a diameter of 101 u and a thickness of 1.6 B, 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、２５°Ｃ及び５ｏ″Ｃ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。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Ｒｔ−Ｒ。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 25°C and 5o''C, and the B constant between these temperatures was calculated. The results are shown in Table 2 below.The 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 rate of change in resistance value Rt-R.
（Ｉ Ｒｏ １Ｘ１００％； Ｒｏ ：初期抵抗値、
Ｒｔ：を時間後の抵抗値）を求めた結果を図に示す。(I Ro 1X100%; Ro: initial resistance value,
The results of determining Rt (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。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.
（以下余白）
く第１表〉
（＊：従来例）
く第２表〉
（＊：従来例）
ここで、主成分に添加するＬ工、 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、本発明者らは
Ｌｉ 、 Ｂ 、 Ｍｇ 、 ｋｌ 、 Ｓｉ 、 Ｔ
ｉ 、 Ｖ 。(Left below) Table 1〉 (*: Conventional example) Table 2〉 (*: Conventional example) Here, for L, Mg, B, human 1, etc. added to the main components, specific elements Although only one type or a combination of two types are described, the present inventors have discovered that Li, B, Mg, kl, Si, T
i, 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 elements Or and Zn.
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、Ｂ１酸化物が０．１ｍｏｌ％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１ ０ ｍ０１％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 B1 oxide content is less than 0.1 mol%, no effect on the coefficient of variation and aging of electrical properties is observed, and when it exceeds 10 m01%, the coefficient of variation becomes large. Therefore, it is excluded from the scope of the present invention.
さらに、特許請求の範囲の第２項に示したＬｉ 、 Ｍ
ｇ等の添加元素量において、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％を超え
た場合には電気特性の変動係数が犬きくなったため、本
発明の請求範囲外とした。Furthermore, Li, M shown in the second claim
If the amount of added elements such as g is less than 0.1 atomic titanium, B1
Similar to oxides, no effect was observed, and on the other hand, when the amount exceeded 10 atom %, the coefficient of variation of electrical properties became too large, so it was excluded from the scope of the claims 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。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名１−
１５一本発明
１６〜２０−従来例
一放置叶間ｆｈｓＪThe 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. Name of agent: Patent attorney Toshio Nakao and 1 other person 1 −
15-Invention 16-20-Conventional example-Idle leaves fhsJ
Claims (2)
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 and Ni as main components as metal elements, and 0.1 to 10 mol% of Bi element added as a subcomponent.
ｉ、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) Mn and Ni are the main metal elements, and L
Contains 0.1 to 10 atom% of one or more of the following elements: A thermistor porcelain composition characterized by adding 0.1 to 10 mol% of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151899A JPS63315555A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151899A JPS63315555A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63315555A true JPS63315555A (en) | 1988-12-23 |
Family
ID=15528623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151899A Pending JPS63315555A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63315555A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006085507A1 (en) * | 2005-02-08 | 2006-08-17 | Murata Manufacturing Co., Ltd. | Surface mounting-type negative characteristic thermistor |
| US8354891B2 (en) | 2010-07-20 | 2013-01-15 | Murata Manufacturing Co., Ltd. | Nonreciprocal circuit element |
-
1987
- 1987-06-18 JP JP62151899A patent/JPS63315555A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006085507A1 (en) * | 2005-02-08 | 2006-08-17 | Murata Manufacturing Co., Ltd. | Surface mounting-type negative characteristic thermistor |
| JP2008177611A (en) * | 2005-02-08 | 2008-07-31 | Murata Mfg Co Ltd | Surface mounting type negative characteristic thermistor |
| KR100894967B1 (en) * | 2005-02-08 | 2009-04-24 | 가부시키가이샤 무라타 세이사쿠쇼 | Surface mounting-type negative characteristic thermistor |
| US7548149B2 (en) | 2005-02-08 | 2009-06-16 | Murata Manufacturing Co., Ltd. | Surface-mount negative-characteristic thermistor |
| US7948354B2 (en) | 2005-02-08 | 2011-05-24 | Murata Manufacturing Co., Ltd. | Surface-mount negative-characteristic thermistor |
| US8354891B2 (en) | 2010-07-20 | 2013-01-15 | Murata Manufacturing Co., Ltd. | Nonreciprocal circuit element |
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