JPS62248201A - Manufacture of positive characteristics thermistor - Google Patents
Manufacture of positive characteristics thermistorInfo
- Publication number
- JPS62248201A JPS62248201A JP9271686A JP9271686A JPS62248201A JP S62248201 A JPS62248201 A JP S62248201A JP 9271686 A JP9271686 A JP 9271686A JP 9271686 A JP9271686 A JP 9271686A JP S62248201 A JPS62248201 A JP S62248201A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- positive temperature
- temperature coefficient
- coefficient thermistor
- dried
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000010304 firing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は正特性サーミスタの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method of manufacturing a positive temperature coefficient thermistor.
従来の技術
チタン酸バリウム（ＢａＴｉＯｓ ）’を主成分とし、
これにチタニウム（Ｔｉ）の原子半径に近い原子半径を
有する６価の７ｉ：′繁寸たけバリウム（Ｂａ’）の原
子半径に近い３価の元素をドープすることにより。Conventional technology Barium titanate (BaTiOs) is the main component,
This is doped with a trivalent element having an atomic radius close to the atomic radius of titanium (Ti): hexavalent 7i, which has an atomic radius close to the atomic radius of barium (Ba').
Ｔ１ の原子価を制御することによって半導体化された
正特注サーミスタは、そのキュリ一温度付近で抵抗値の
異常増加を生じる半導体セラミックであることは公知で
ある。さらに、これにマンガン化合物や５ｉ０２．ムｒ
ｈｏｓを微量添加することにより。It is known that a custom-made thermistor made into a semiconductor by controlling the valence of T1 is a semiconductor ceramic that exhibits an abnormal increase in resistance near its Curie temperature. Furthermore, manganese compounds and 5i02. Mr.
By adding a small amount of hos.
上記抵抗値の異常増加が著しく改善されるとともに、製
造歩留りが著しく改善されることが知られている。It is known that the above-mentioned abnormal increase in resistance value is significantly improved and the manufacturing yield is also significantly improved.
ところで、このマンガン化合物（このマンガン化合物は
焼成後はマンガン酸化物として存在すると考えられてい
る。）やム１ｈＯｓａ ５ｉ０２は結晶粒界に均一に分
散して存在することが好ましい。By the way, it is preferable that this manganese compound (this manganese compound is thought to exist as a manganese oxide after firing) and M1hOsa5i02 exist in a uniformly dispersed manner at the grain boundaries.
一方、こうした従来の正特性サーミスタの製造方法は第
２図に示すように、焼成後所定の組成となるように各成
分を秤量しくここで、ム（ｌｚｏｓ ｒＭｎ０２ はム
ロ（ＮＯｓ）ｘやＭｎ（８０３）２ ｆｚどの化合物の
形で添加することもある。）、ボールミルで湿式混合後
、乾燥させる。その後、電気炉により仮焼し、これをボ
ールミルにより湿式粉砕し乾燥後、造粒し、成形した後
、焼成して正特性サーミスタを得ている。On the other hand, as shown in FIG. 2, the conventional manufacturing method for positive temperature coefficient thermistors involves weighing each component so as to obtain a predetermined composition after firing. 803)2fz may be added in the form of any compound), wet mixed in a ball mill and then dried. Thereafter, it is calcined in an electric furnace, wet-pulverized in a ball mill, dried, granulated, molded, and fired to obtain a positive temperature coefficient thermistor.
発明が解決しようとする間頂点
このような従来の構成では％ＭｎＯ２、Ａｌ２Ｏ５、Ｓ
ｉＯ□が偏析し磁器内谷部で斑点が生じたりして、これ
らの成分の分散が不均一になったり、結晶粒内への拡牧
が生じたりして、正特性サーミスタの常温における比抵
抗値が増加するばかりでなく、抵抗値の異常増加特性が
劣化するという問題があった。While the invention attempts to solve the apex in such conventional configurations, %MnO2, Al2O5, S
iO□ segregates and causes spots in the inner valleys of the porcelain, resulting in non-uniform dispersion of these components and expansion into the crystal grains, which may cause the specific resistance of the PTC thermistor to decrease at room temperature. There is a problem in that not only the resistance value increases, but also the abnormal increase characteristic of the resistance value deteriorates.
本発明はこのような問題点を解決するもので、微量成分
でらるＭｎＯ２，ムｒｈｏｓ、 ５ｉ０２を結晶粒界に
均一に分散させて、抵抗値の異常増加特性に優れるとと
もに耐電圧特性が改良され、斑点が少なく、製造歩留り
の高い正特性サーミスタの製造方法を提供すること全目
的とするものである１゜問題点を解決するための手段
この問題点全解決するために本発明は、 Ａ（１２０ｓ
ａＭｎ０２，５ｉ０２以外の成分により作製した正特性
サーミスタの原料を成形後８００〜１２００’Ｃにて予
備焼成した後、これを５ｉ０２ のコロイド溶液に浸
漬含浸後’＋を燥し、さらに人１＜Ｎ０ｓ）ｓｒ Ｍｎ
（ＮＯ３）２ 溶液に浸責含没後乾燥した後、焼成す
るものである。、。The present invention solves these problems by uniformly dispersing trace components MnO2, Mrhos, and 5i02 in the grain boundaries, resulting in excellent resistance to abnormal increases in resistance and improved withstand voltage characteristics. The overall purpose of the present invention is to provide a method for manufacturing a positive temperature coefficient thermistor with fewer spots and a high manufacturing yield. (120s
After molding the raw material for a positive temperature thermistor made from components other than aMn02 and 5i02, it is pre-fired at 800 to 1200'C, and then immersed in a colloidal solution of 5i02 and dried after impregnation. )sr Mn
It is immersed in a (NO3)2 solution, dried, and then fired. ,.
作用
この構成により、微量成分でらるＭｎ０２１ Ａｄｚｅ
ｓ。Effect: With this configuration, trace amounts of Mn021 Adze
s.
５ｉ０２ が結晶粒界に均一に分散し、抵抗値の異常
増加特性に優れ、耐電圧特性が改善され、斑点などの発
生がなく、製造歩留りが改善されることとなる。5i02 is uniformly dispersed in the grain boundaries, exhibits excellent characteristics of abnormal increase in resistance value, improves withstand voltage characteristics, eliminates spots, etc., and improves manufacturing yield.
実施例
第１図は本発明による正特性サーミスタの製造方法を示
す製造工程図である。第１図に従って以下に実施例を説
明する。すなわち１例えば（Ｂａ０Ｌ７７Ｓｒ（１２５
）Ｔｉ０５ ＋ ０．００３０Ｙ２０５となるようにＢ
ａＣＯ３，５ｒＣＯ５，ＴｉＯ２，Ｙ２Ｏ５ｆそれぞれ
秤量し、ボールミルにて２４時時間式混合した後、２０
０℃にて２０時間乾燥した。さらに、この乾燥原料’ｉ
５１１００℃にて２時間仮焼し、再びボールミルにて２
０時時間式粉砕した後、２００℃にて２０時間乾燥した
。次に、この乾燥粉にポリビニルアルコール水溶液全添
加造粒した後、Ｂｏｏｋｔｉ／ｄにて加圧成形し、直径
２Ｏｆｆ％厚さ３ＭＮの円板を作製した。これを１ｏｏ
Ｏ℃、４時間予備焼成させた後、 ５ｉ０２ のコロ
イド溶液に浸漬し、 １０肩ｚＨｇにて３０分間真空含
浸した後、１６０℃にて２時間乾燥させた。次に、ム１
（ＮＯｘ）ｓ、 Ｍｎ（ＮＯ３）２ の混合溶液中に
浸漬し、１０ＪｆｆＨｇ にて３０分間真空含浸した後
、１５０℃にて２時間乾燥させた。ここで、含浸させる
５１０２ コロイド溶液やムＩＩｃＨＯｓ ）ｓ。Embodiment FIG. 1 is a manufacturing process diagram showing a method for manufacturing a positive temperature coefficient thermistor according to the present invention. An embodiment will be described below with reference to FIG. That is, 1 for example (Ba0L77Sr(125
) B so that Ti05 + 0.0030Y205
aCO3, 5rCO5, TiO2, Y2O5f were each weighed and mixed in a ball mill for 24 hours.
It was dried at 0°C for 20 hours. Furthermore, this dry raw material'i
51 Calcined at 100℃ for 2 hours, and then heated again in a ball mill for 2 hours.
After pulverizing at 0:00, it was dried at 200° C. for 20 hours. Next, a polyvinyl alcohol aqueous solution was completely added to this dry powder and granulated, and then pressure molded using Bookti/d to produce a disk having a diameter of 2Off% and a thickness of 3MN. 1oo of this
After preliminarily calcining at 0°C for 4 hours, it was immersed in a colloidal solution of 5i02, vacuum impregnated at 10 zHg for 30 minutes, and then dried at 160°C for 2 hours. Next, M1
It was immersed in a mixed solution of (NOx)s and Mn(NO3)2, vacuum impregnated at 10 JffHg for 30 minutes, and then dried at 150°C for 2 hours. Here, it is impregnated with 5102 colloidal solution or MuIIcHOs).
Ｍｎ（Ｈｏｇ）２ 混合溶液の濃度は予め含浸量を測
定し。The concentration of the Mn(Hog)2 mixed solution was determined by measuring the amount of impregnation in advance.
含浸後の組成がＣＢ＆Ｌ７７ ｓｒＱ、２５ ）Ｔｉ０
３ ＋ ０．００３０ Ｙ２Ｏ３＋ α０２０５ｉ０２
＋０ＯＯ０６Ｍｎ（ＮＯ５）２ ＋ ０．００１ Ａ
ｅ（ＮＯ３）５となるように調整されたものである。さ
らに、これ１１３６０’ｃで１時間焼成して正特性サー
ミスタを得た。この素子に銀電翫を形成し、２６℃にお
ける比抵抗、耐電圧特性を測定するとともに、素子１ｏ
ｏ個について外観の目視検査をし０斑点の発生状況を確
認した。The composition after impregnation is CB&L77 srQ, 25) Ti0
3 + 0.0030 Y2O3+ α0205i02
+0OO06Mn(NO5)2 + 0.001 A
It is adjusted so that it becomes e(NO3)5. Further, this was fired at 11360'c for 1 hour to obtain a positive temperature coefficient thermistor. A silver wire was formed on this element, and the resistivity and withstand voltage characteristics at 26°C were measured.
The appearance of o pieces was visually inspected to confirm the occurrence of zero spots.
上記のようにして本発明により作製された素子（本発明
の実施例）と、 （ＢａＬ７７Ｓｒｏ、ｚ３）ＴｉＯ
３＋ＱＯ３０Ｙ２Ｏ５＋ ＱＯ２０Ｓｉ０２ ＋ ０−
０００６ Ｍｎ（ＮＯ５）２ ＋０００１ Ａ６（ＮＯ
ｓ）５トｆｘ ル、！： ’） Ｋ秤量 シテ、 第２
図に示す従来の方法にて作製した素子（従来例）との比
較を第１表に示す。A device manufactured according to the present invention as described above (an example of the present invention), and (BaL77Sro, z3)TiO
3+QO30Y2O5+ QO20Si02 + 0-
0006 Mn(NO5)2 +0001 A6(NO
s) 5 torfx le! : ') K weighing shite, 2nd
Table 1 shows a comparison with the device manufactured by the conventional method shown in the figure (conventional example).
〈第１表〉
第１表から明らかなように、本発明によれば微量添加物
であるム１２０３． ＭｎＯ２，５ｉ０２を結晶粒界に
均一に分散させることができるために、素子に斑点の発
生が抑制され、製造歩留りが改善されるとともに耐電圧
特性の良好な素子を得ることができるなどの効果がある
。<Table 1> As is clear from Table 1, according to the present invention, the trace additive Mu1203. Since MnO2, 5i02 can be uniformly dispersed in the grain boundaries, the occurrence of spots on the device is suppressed, the manufacturing yield is improved, and devices with good withstand voltage characteristics can be obtained. be.
尚１本実施例では、予備焼成温度１ｏＯｏ℃の場合につ
いてのみ述べたが、ＳＯＯ℃〜１２００℃の温度でも同
様の効果が得られることは言うまでもない。ところで予
備焼成温度’１８００〜１２００℃としたのは、８００
’Ｃ未満の温度では造粒時に用いる有機バインダーの分
解が不充分で多孔質化が進行せず、各溶液の含浸を阻害
したり。In this embodiment, only the case where the preliminary firing temperature was 100°C was described, but it goes without saying that the same effect can be obtained at a temperature of SOO°C to 1200°C. By the way, the pre-firing temperature of 1800-1200℃ is 800℃.
If the temperature is lower than 'C, the decomposition of the organic binder used during granulation will be insufficient and porosity will not proceed, which may inhibit impregnation with each solution.
素子強度が低く、焼成前の工程処理中に素子にクラスフ
が発生したりするためである。一方、１０００℃を超え
る温度では焼結反応が進行し開気孔が減少し、閉気孔が
増大し溶液の含浸を阻害するためである。This is because the element strength is low and cracks may occur in the element during processing before firing. On the other hand, at a temperature exceeding 1000° C., the sintering reaction progresses, the number of open pores decreases, and the number of closed pores increases, which inhibits solution impregnation.
さらに、不実施例ではム１（ＮＯｓ）ｓとＭｎ（［０５
）２の混合溶液に素体を浸漬含浸させだが、それぞれ個
別の溶液にて浸漬含浸させてもよい。また、５ｉ０２の
含浸は、５ｉ０２ コロイド溶液の対イオン安定性カ
好’ｊ Ｌ ＜ ｆｘ、イタｋｂ、 ＡＪｌ？（ＮＯ３
）ｓ溶液やＭｎ（ＮＯ３）２溶液よりも先に含浸させる
のが好ましい。Furthermore, in the non-example, M1(NOs)s and Mn([05
Although the element body is immersed in the mixed solution of 2), it may be immersed in a separate solution. The impregnation of 5i02 also affects the counterion stability of the 5i02 colloidal solution: L < fx, kb, AJl? (NO3
)S solution or Mn(NO3)2 solution is preferably impregnated.
発明の効果
以上のように本発明によれば、ム１２０５ｒ ”０２＋
５ｉ０２ ｋ除く成分を予備焼成したのち、 ＳｉＯ
□ コロイド溶Ｗ 、 Ａ６（ＮＯｓ）ｓ溶液、 Ｍｎ
（ＮＯｓ）ｚ溶液に浸漬含浸サセるコトにより、Ａ／２
０５． ＭｎＯ２，５ｉ０２を結晶粒界に均一に分散さ
せることができ、製造歩留りが向上するとともに、耐電
圧特性の良好な素子が得られるという特有の効果が得ら
れる。Effects of the Invention As described above, according to the present invention, the M1205r ”02+
After pre-calcining the components except 5i02k, SiO
□ Colloidal solution W, A6(NOs)s solution, Mn
(NOs) By dipping and impregnating in z solution, A/2
05. MnO2, 5i02 can be uniformly dispersed in the grain boundaries, which has the unique effect of improving manufacturing yield and providing an element with good withstand voltage characteristics.
第１図は本発明による正特性サーミスタの製造方法を示
す製造工程図、第２図は従来の正特性サーミスタの製造
方法を示す製造工程図である。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
第２図FIG. 1 is a manufacturing process diagram showing a method for manufacturing a positive temperature coefficient thermistor according to the present invention, and FIG. 2 is a manufacturing process diagram showing a conventional method for manufacturing a positive coefficient thermistor. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2
Claims (1)
を含有するチタン酸バリウム系正特性サーミスタの製造
工程において、Ａｌ＿２Ｏ＿３、ＭｎＯ＿２、ＳｉＯ＿
２以外の成分により作製した正特性サーミスタの原料を
成形後８００〜１２００℃にて予備焼成した後、これを
ＳｉＯ＿２のコロイド溶液に浸漬含浸後乾燥し、さらに
Ａｌ（ＮＯ＿３）＿３、Ｍｎ（ＮＯ＿３）＿２溶液に浸
漬含浸後乾燥した後、焼成することを特徴とする正特性
サーミスタの製造方法。At least Al_2O_3, MnO_2, SiO_2
In the manufacturing process of a barium titanate-based positive temperature coefficient thermistor containing Al_2O_3, MnO_2, SiO_
After molding the raw material for a positive temperature coefficient thermistor made with components other than 2, it was pre-fired at 800 to 1200°C, and then immersed in a colloidal solution of SiO_2, impregnated and dried, and further formed with Al(NO_3)_3 and Mn(NO_3). _2 A method for producing a positive temperature coefficient thermistor, which comprises immersing it in a solution, drying it, and then firing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9271686A JPS62248201A (en) | 1986-04-22 | 1986-04-22 | Manufacture of positive characteristics thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9271686A JPS62248201A (en) | 1986-04-22 | 1986-04-22 | Manufacture of positive characteristics thermistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62248201A true JPS62248201A (en) | 1987-10-29 |
Family
ID=14062178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9271686A Pending JPS62248201A (en) | 1986-04-22 | 1986-04-22 | Manufacture of positive characteristics thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62248201A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03155352A (en) * | 1989-11-13 | 1991-07-03 | Nkk Corp | Small direct current motor |
| JPH0661010A (en) * | 1992-08-07 | 1994-03-04 | Sekisui Plastics Co Ltd | Manufacture of positive temperature coefficient thermistor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5726402A (en) * | 1980-07-23 | 1982-02-12 | Matsushita Electric Ind Co Ltd | Method of producing positive temperature coefficient thermistor |
| JPS5785201A (en) * | 1980-11-18 | 1982-05-27 | Matsushita Electric Ind Co Ltd | Method of producing barium titanate semiconductor porcelain |
-
1986
- 1986-04-22 JP JP9271686A patent/JPS62248201A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5726402A (en) * | 1980-07-23 | 1982-02-12 | Matsushita Electric Ind Co Ltd | Method of producing positive temperature coefficient thermistor |
| JPS5785201A (en) * | 1980-11-18 | 1982-05-27 | Matsushita Electric Ind Co Ltd | Method of producing barium titanate semiconductor porcelain |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03155352A (en) * | 1989-11-13 | 1991-07-03 | Nkk Corp | Small direct current motor |
| JPH0661010A (en) * | 1992-08-07 | 1994-03-04 | Sekisui Plastics Co Ltd | Manufacture of positive temperature coefficient thermistor |
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