JPS63315550A - Thermistor porcelain composition - Google Patents
Thermistor porcelain compositionInfo
- Publication number
- JPS63315550A JPS63315550A JP62151882A JP15188287A JPS63315550A JP S63315550 A JPS63315550 A JP S63315550A JP 62151882 A JP62151882 A JP 62151882A JP 15188287 A JP15188287 A JP 15188287A JP S63315550 A JPS63315550 A JP S63315550A
- Authority
- JP
- Japan
- Prior art keywords
- thermistor
- resistance value
- main component
- oxide
- porcelain composition
- 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 10
- 229910052573 porcelain Inorganic materials 0.000 title claims description 4
- 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
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000006104 solid solution Substances 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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
- 239000000843 powder Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 230000032683 aging Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 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
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002362 mulch 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-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
- 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
- 229910001928 zirconium oxide Inorganic materials 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、Ｃｕ、Ｇｏ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
〜１５Ｃ）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 an oxide thermistor containing Mn, Ni, Cu, Go and Zr as main components, a so-called spinel thermistor.
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 ~15C) or as an inrush current prevention element.
従来の技術
従来、この種のＭｎ−Ｎｉ−Ｃｕ−１０−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-Cu-10-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, and has been found to be highly compatible with the circuit. This composition is widely used because it is easy to match.
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℃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。まだ、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. Although aging treatment for about 3 to 7 days was required, even this was not sufficient. However, finished products still undergo significant changes 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
ｉ、Ｃｕ、Ｇｏ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。The present invention solves these problems, and is aimed at solving these problems.
To provide a stable thermistor ceramic composition which reduces variations (coefficient of variation) in the resistance value and B constant of a thermistor ceramic whose main components are an oxide solid solution of i, Cu, Go, and Zr, and whose resistance value changes over time. The purpose is to
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、Ｃｕ、Ｇｏ、Ｚｒの酸化物固溶
体を主成分とし、副成分としてＢｉｌ’［化物を加える
。(1) The main component is an oxide solid solution of Mn, Ni, Cu, Go, and Zr, and Bil' is added as a subcomponent.
（２） 上記構成中、主成分に更に元素成分としてＬ
ｉ、Ｂ、Ｍｇ、Ａｌ、Ｓｉ、Ｔｉ、Ｖ’、Ｃｒ、Ｚｎ
の内の１種もしくは２種以上を添加する。(2) In the above structure, L is added as an elemental component to the main component.
i, B, Mg, Al, Si, Ti, V', Cr, Zn
Add one or more of the following.
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、酸化銅、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１５
０〜２５０℃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、ム（ポリビニルアルコール）溶液を１０％加
えて混合し、造粒を行った。そして、この造粒粉を直径
１０ｗｍ、厚さ１．６閣のディスク状に加圧成形し、１
０００〜１２００℃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, copper oxide, cobalt oxide, zirconium oxide, bismuth oxide, etc., predetermined amounts were blended to have the composition shown in Table 1 below.
Mixing was carried out for 20 hours using a ball mill. This is 15
After drying at 0 to 250°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. A 10% p, v, mu (polyvinyl alcohol) solution with a concentration of 10% was added to this calcined powder and mixed to perform granulation. Then, this granulated powder was pressure-molded into a disk shape with a diameter of 10 wm and a thickness of 1.6 cm.
After baking at a temperature of 000 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６０℃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表に示しだ。まだ、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。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 60° C., and the B constant between these temperatures was calculated. The results are shown in Table 2 below. However, these coefficients of variation are also listed at the same time. Furthermore, each thermistor element was left in air at 160° C. for 1000 hours, and the results of determining the resistance value change rate 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）
第 ２ 表
（＊：従来例）
ここで、主成分に添加するＬｉ、Ｍｇ、Ｂ、ムｌ 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、ムｄ、Ｓｉ、Ｔｉ、Ｖ、Ｃｒ、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。(Left below) Table 2 (*: Conventional example) Here, regarding Li, Mg, B, mulch, etc. added to the main components, only one type of specific elements or a combination of two types are listed. However, the inventors have determined that Li,
By adding a predetermined amount of one or more of the elements B, Mg, Mud, Si, Ti, V, Cr, and Zn,
It was confirmed that effects similar to those shown in Table 2 above could be obtained.
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１本発明において、Ｂｉ酸化物がｏ、 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１０ｍｏｌ％ 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だ。Note that in the present invention, Bi oxide is o, 1 mol%
If it is less than 10 mol %, no effect on the coefficient of variation and changes over time of electrical properties will be observed, and if it exceeds 10 mol %, the coefficient of variation will become large and therefore outside 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％未満ではＢ１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
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 amount of added elements such as Li and Mg shown in the second claim, if it is less than 0.1 atomic %, no effect will be seen as with B1 oxide, whereas if it exceeds 10 atomic % 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１５０１：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 is a diagram showing the rate of change in resistance value over time of the thermistor element according to an embodiment of the present invention and the conventional thermistor element 1501 when left in air.
Claims (2)
を主成分とし、副成分としてＢｉ元素を０．１〜１０ｍ
ｏｌ％加えたことを特徴とするサーミスタ磁器組成物。(1) Mn, Ni, Cu, Co and Zr as metal elements
as the main component and 0.1 to 10 m of Bi element as a subcomponent.
A thermistor porcelain composition characterized by adding ol%.
を主体とし、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、かつこれらを主成分に対して
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, Ni, Cu, Co and Zr as metal elements
The main component is Li, B, Mg, Al, Si, Ti.
, V, Cr, and Zn elements.
．． 1. A thermistor ceramic composition containing 1 to 10 atomic % of Bi as a main component and 0.1 to 10 mol % of Bi as a subcomponent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151882A JPS63315550A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151882A JPS63315550A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63315550A true JPS63315550A (en) | 1988-12-23 |
Family
ID=15528266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151882A Pending JPS63315550A (en) | 1987-06-18 | 1987-06-18 | Thermistor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63315550A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231905A (en) * | 1991-09-24 | 1994-08-19 | Tdk Corp | Composition for thermistor |
| WO2006085507A1 (en) * | 2005-02-08 | 2006-08-17 | Murata Manufacturing Co., Ltd. | Surface mounting-type negative characteristic thermistor |
| WO2009119681A1 (en) * | 2008-03-28 | 2009-10-01 | 株式会社 村田製作所 | Ntc thermistor porcelain, process for producing ntc thermistor porcelain, and ntc thermistor |
| US8115587B2 (en) | 2008-03-28 | 2012-02-14 | Murata Manufacturing Co., Ltd. | NTC thermistor ceramic, method for producing NTC thermistor ceramic, and NTC thermistor |
| US8354891B2 (en) | 2010-07-20 | 2013-01-15 | Murata Manufacturing Co., Ltd. | Nonreciprocal circuit element |
| 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 JP62151882A patent/JPS63315550A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231905A (en) * | 1991-09-24 | 1994-08-19 | Tdk Corp | Composition for thermistor |
| 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 |
| WO2009119681A1 (en) * | 2008-03-28 | 2009-10-01 | 株式会社 村田製作所 | Ntc thermistor porcelain, process for producing ntc thermistor porcelain, and ntc thermistor |
| US8115587B2 (en) | 2008-03-28 | 2012-02-14 | Murata Manufacturing Co., Ltd. | NTC thermistor ceramic, method for producing NTC thermistor ceramic, and NTC thermistor |
| JP5083639B2 (en) * | 2008-03-28 | 2012-11-28 | 株式会社村田製作所 | NTC thermistor porcelain, NTC thermistor porcelain manufacturing method, and NTC thermistor |
| US8354891B2 (en) | 2010-07-20 | 2013-01-15 | Murata Manufacturing Co., Ltd. | Nonreciprocal circuit element |
| 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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