JPS63117914A - Production of metal oxide powder for ptc-thermistor - Google Patents
Production of metal oxide powder for ptc-thermistorInfo
- Publication number
- JPS63117914A JPS63117914A JP26219386A JP26219386A JPS63117914A JP S63117914 A JPS63117914 A JP S63117914A JP 26219386 A JP26219386 A JP 26219386A JP 26219386 A JP26219386 A JP 26219386A JP S63117914 A JPS63117914 A JP S63117914A
- Authority
- JP
- Japan
- Prior art keywords
- alkoxide
- powder
- metal oxide
- ptc
- oxide powder
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- -1 barium alkoxide Chemical class 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 229910019351 (BaxSr1-x)TiO3 Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001354 calcination Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical group [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 3
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- OHULXNKDWPTSBI-UHFFFAOYSA-N strontium;propan-2-olate Chemical compound [Sr+2].CC(C)[O-].CC(C)[O-] OHULXNKDWPTSBI-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/025—Perovskites, e.g. titanates
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (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、ＰＴＣサーミスタに用いられるチタン酸バリ
ウムを主成分とする酸化物粉末の製造法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing oxide powder containing barium titanate as a main component and used in PTC thermistors.
従来の技術
チタン酸バリウムはキ。り一点付近で高誘電率を示し、
主にコンデンザ材料として利用されてきた。キュリー点
は、チタン酸ストロンチウムを固溶させることにより低
温側に、ヂタン酸鉛を固溶させることにより高温側に移
動できる。また、ニオブ、イツトリウム等の添加物を結
晶粒内に微量固溶させることにより原子価制御が行われ
、半導体化する。電気抵抗の温度係数は負であるが、粒
界の効果でキュリー点イ１近で温度係数が正の部分が出
現する。この現象はＰＴＣ効果と呼ばれ、無接点スイッ
チ素子、サーミスタ等の製品に応用されている。（増補
版ｒチタバリ系半導体」、ニレセラ出版委員会編、技献
（１９８０） ）ＰＴＣサーミスタの製造には、多くの
場合、所定量の炭酸バリウム、酸化チタン、酸化ニオブ
等を混合し、仮焼および焼成の段階で脱炭酸、相互拡散
させる手法（固相法）がとられている。反応を充分進行
させるためには仮焼を高温で長時間行うのが最も効果的
であるが、仮焼後の粉末が硬くなり粉砕に多大なエネル
ギーを要し、また粉砕時に粉砕装置から不純物が混入し
、特性の制御が困難となる。ナトリウム、カリウム、鉄
、マンガン、クロム等が結晶粒内に共存すると、原子価
補償を起こし、半導体化のために加えた元素の効果が打
ち消されてしまう。最低の電気抵抗を与える半導体化元
素の添加量は、大略０．２〜０．４ａｔｌという微量か
つ狭い範囲である。つまり、不純物混入はＰＴＣサーミ
スタの特性に決定的な影響を及ぼすと言える。Conventional technology barium titanate is ki. shows a high dielectric constant near one point,
It has been mainly used as a capacitor material. The Curie point can be moved to the low temperature side by dissolving strontium titanate in solid solution, and to the high temperature side by dissolving lead ditanate in solid solution. In addition, valence control is performed by solidly dissolving small amounts of additives such as niobium and yttrium within crystal grains, thereby converting the material into a semiconductor. Although the temperature coefficient of electrical resistance is negative, a portion where the temperature coefficient is positive appears near the Curie point I1 due to the effect of grain boundaries. This phenomenon is called the PTC effect, and is applied to products such as non-contact switching elements and thermistors. (Enlarged edition of "Titabari-based Semiconductors", edited by Nilesera Publishing Committee, Technical Reference (1980)) In many cases, PTC thermistors are manufactured by mixing a predetermined amount of barium carbonate, titanium oxide, niobium oxide, etc., and then calcining the mixture. A method of decarboxylation and interdiffusion (solid phase method) is used during the firing stage. In order for the reaction to proceed sufficiently, it is most effective to perform calcination at high temperature for a long time, but the powder after calcination becomes hard and requires a large amount of energy to grind, and impurities are released from the grinding equipment during grinding. It becomes difficult to control the characteristics. When sodium, potassium, iron, manganese, chromium, etc. coexist within crystal grains, valence compensation occurs and the effect of the elements added for semiconductor formation is canceled out. The amount of the semiconductor-forming element that provides the lowest electrical resistance is within a small and narrow range of about 0.2 to 0.4 atl. In other words, it can be said that the inclusion of impurities has a decisive effect on the characteristics of the PTC thermistor.
発明が解決しようとする問題点
近年、人工衛星搭載用のＰＴＣザーミスタとして、従来
よりも低抵抗かつ高信頼性のものが要求されている。従
来の固相法によるならば、焼結体への不純物混入の問題
は避けられず、電気抵抗が高くなり、信頼性には難があ
った。本発明はこれらの問題点を解決するものである。Problems to be Solved by the Invention In recent years, there has been a demand for PTC thermistors to be mounted on artificial satellites that have lower resistance and higher reliability than conventional ones. If the conventional solid phase method is used, the problem of impurities being mixed into the sintered body is unavoidable, resulting in high electrical resistance and poor reliability. The present invention solves these problems.
問題点を解決するだめの手段
バリウムアルコキシドおよびストロンチウムアルコキシ
ドのうちの少なくとも一種と、チタンアルコキシドと半
導体化元素Ｍ（ニオブあるいはイツトリウム）のアルコ
キシドの混合、加水分解を含む工程により、
（ＢａｘＳｒ＋−ｘ）ＴｉＯａ −ｎ Ｈ２Ｏ＋２Ｍ（
ただし、■≧Ｘ≧０、ｎ≧０．０．００４０≧ｚ≧０）
なる組成のＰＴＣサーミスタ用金属酸化物粉末を製造す
る。As a means to solve the problem, (BaxSr+-x)TiOa is produced by a process including mixing and hydrolyzing at least one of barium alkoxide and strontium alkoxide, titanium alkoxide, and an alkoxide of the semiconductor element M (niobium or yttrium). -n H2O+2M(
However, ■≧X≧0, n≧0.0.0040≧z≧0)
A metal oxide powder for a PTC thermistor having the following composition is manufactured.
作用
本発明によれば、ニオブまたはイツトリウムを半導体化
元素として含有し、バリウムあるいはストロンチウムと
、チタン七を主成分とするＰＴＣサーミスタ用金属酸化
物粉末を容易に製造することができる。得られた粉末を
原料とし、仮焼、成形、焼成することにより、電気抵抗
が低（高信頼性のＰＴＣサーミスタ材料を得ることがで
きる。According to the present invention, a metal oxide powder for a PTC thermistor containing niobium or yttrium as a semiconductor element, barium or strontium, and titanium 7 as main components can be easily produced. By using the obtained powder as a raw material and calcining, molding, and firing, a PTC thermistor material with low electrical resistance (high reliability) can be obtained.
実施例
実施例１
バリウムイソプロポキシドおよびストロンチウムイソプ
ロポキシドと、チタンイソプロポキシドとニオブイソプ
ロポキシドを
（ＢａｘＳｒ１−ｘ）ＴｉＯ３＋ｚＮ
ｂ（ｘ−０，６，０，００４０≧ｚ≧０）なる組成とな
るように不活性雰囲気中で配合し、その合計重量の２Ｏ
倍のベンゼンを溶媒として加え、８０℃に保持して撹拌
した。約２時間後、温度を８０℃に保持したまま、水を
１０重量％含むイソプロピルアルコールを滴下した。滴
下量は配合したアルコキシドがすべて加水分解されるの
に最低限必要な水量の３倍の水量とした。温度を８０℃
に保持し、６ 時間撹拌し、白色の沈殿を得た。２４
時間放置し得られた沈殿を沈降させ、うわずみ液を捨
てた。乾燥は空気中で１５０℃で５時間行った。乾燥後
の粉末のＢＥＴ粒径は約１０ｎｍであった。Ｘ線回折パ
ターンはぺＬ１ブスカイト構造を示し、副成分は認めら
れなかった。Examples Example 1 Composition of barium isopropoxide and strontium isopropoxide, titanium isopropoxide and niobium isopropoxide (BaxSr1-x)TiO3+zN b (x-0,6,0,0040≧z≧0) Blend in an inert atmosphere so that the total weight of 2O
Double the amount of benzene was added as a solvent, and the mixture was kept at 80°C and stirred. After about 2 hours, isopropyl alcohol containing 10% by weight of water was added dropwise while maintaining the temperature at 80°C. The amount of water added was three times the minimum amount of water required to completely hydrolyze the blended alkoxide. Temperature 80℃
The mixture was kept at a temperature of 100.degree. C. and stirred for 6 hours to obtain a white precipitate. 24
The resulting precipitate was allowed to settle for a period of time, and the suspension was discarded. Drying was performed in air at 150°C for 5 hours. The BET particle size of the powder after drying was approximately 10 nm. The X-ray diffraction pattern showed a PeL1 buskite structure, and no subcomponents were observed.
乾燥後の粉末を１１００℃で２時間仮焼した。仮焼後の
粉末は青味かかった白色を呈していた。発光分光分析に
より不純物は無視できるほど少なく、かつ配合組成どお
りの仮焼粉末が得られていることが確認できた。仮焼粉
末のＸ線回折パターンは、非常に鋭いペロブスカイトの
ピークのみであった。ＢＥＴ粒径は約１００ｒ＋ｍであ
った。仮焼粉末に対し約５重量％の３％ポリビニルアル
コール水溶液を加え、３２メツシユのふるいにかけ、−
軸加工プレスにより成形した。The dried powder was calcined at 1100° C. for 2 hours. The powder after calcining had a bluish white color. It was confirmed by emission spectroscopic analysis that impurities were negligible and that a calcined powder with the same composition was obtained. The X-ray diffraction pattern of the calcined powder contained only very sharp perovskite peaks. The BET particle size was approximately 100 r+m. Approximately 5% by weight of a 3% polyvinyl alcohol aqueous solution was added to the calcined powder, and the mixture was sieved through a 32-mesh sieve.
It was molded using a shaft processing press.
成形体を室温から１１００℃までは４００℃／ｈｒ１１
１００℃から１３００℃までは１００℃／ｈｒで昇温し
、１３００℃で１時間保持した後、４００℃／ｈｒで降
温し、濃い青色をした焼結体を得た。密度は理論密度の
９５％であった。インジウム−ガリウム合金を含む銀電
極を焼き付け、その上に銀電極を焼き付け、リード線を
はんだ付けした。ニオブの添加量２が０．００３２の時
の電気抵抗−温度特性を図に示す。固相法による原料粉
末から作製されたものと比べて、−桁以上比抵抗が低い
ものを得ることができた。（Ｅ。400℃/hr11 for molded products from room temperature to 1100℃
The temperature was raised from 100°C to 1300°C at a rate of 100°C/hr, held at 1300°C for 1 hour, and then lowered at a rate of 400°C/hr to obtain a dark blue sintered body. The density was 95% of the theoretical density. A silver electrode containing an indium-gallium alloy was baked, a silver electrode was baked on top of the silver electrode, and a lead wire was soldered. The figure shows the electrical resistance-temperature characteristics when the amount of niobium added is 0.0032. It was possible to obtain a product with a specific resistance that is more than 100% lower than that produced from raw material powder by the solid phase method. (E.
アンドリッチ（Ａｎｄｒｉｃｈ ） 、エレクトロニッ
ク アプリケーションズ（Ｅｌｅｃｔｒｏｎｉｃ Ａ＋
）＋）ｌｉｃａｔｉｏｎｓ） 。Andrich, Electronic Applications (Electronic A+)
)+)lications).
しかし、最低の比抵抗を与えるニオブの添加量は、固相
法の場合のそれに比べて多かった。信頼性の評価として
１２５℃放置試験を行った。５００時間後、１０００時
間後の抵抗変化率はそれぞれ、１．８６％、２．７１％
であった。However, the amount of niobium added that gave the lowest resistivity was higher than that in the solid phase method. As a reliability evaluation, a 125°C storage test was conducted. The resistance change rate after 500 hours and 1000 hours is 1.86% and 2.71%, respectively.
Met.
実施例２
はじめに、ニオブイソプロポキシドをベンゼン溶媒中に
溶かし、撹拌した。溶媒の量は、後に加えるバリウムイ
ソプロポキシド、ストロンチウムイソプロポキシドおよ
びチタンイソプロポキシドの合計重量の２Ｏ倍とした。Example 2 First, niobium isopropoxide was dissolved in a benzene solvent and stirred. The amount of solvent was 20 times the total weight of barium isopropoxide, strontium isopropoxide, and titanium isopropoxide to be added later.
約２時間後、ニオブイソプロポキシドがすべて加水分解
されるのに最低限必要な水量を含む、１０重量％Ｈ２Ｏ
−イソプロピルアルコールを滴下した。６時間後にバリ
ウムイソプロポキシド、ストロンチウムイソプロポキシ
ドおにびチタンイソプロポキシドを、（ＢａｘＳｒ１−
ｘ）ＴｉＯａ＋ｚＮ
ｂ（ｘ−０，６，０，００２Ｏ≧Ｚ≧０）なる組成とな
るように加えた。２時間後、アルコキシドがすべて加水
分解されるのに最低限必要な水量の３倍の水量を含む１
０重量％Ｈ２Ｏ−イソプロピルアルコールを滴下した。After about 2 hours, add 10% H2O by weight containing the minimum amount of water necessary for all of the niobium isopropoxide to be hydrolyzed.
- Isopropyl alcohol was added dropwise. After 6 hours, barium isopropoxide, strontium isopropoxide, and titanium isopropoxide were added to (BaxSr1-
x) TiOa+zN b (x-0,6,0,002O≧Z≧0). After 2 hours, 1 containing three times the minimum amount of water required for all the alkoxides to be hydrolyzed.
0% by weight H2O-isopropyl alcohol was added dropwise.
６時間撹拌し、白色の沈殿を得た。以−Ｈの工程は温度
を８０℃に保持したまま行った。得られた沈殿を、実施
例１の場合と同様にして、乾燥した。乾燥後の粉末の８
６１粒径は約１ＯｎＩ１１で、Ｘ線回折パターンはペロ
ブスカイト構造を示し、副成分は認められなかった。After stirring for 6 hours, a white precipitate was obtained. Steps from to to H were performed while maintaining the temperature at 80°C. The obtained precipitate was dried in the same manner as in Example 1. Powder 8 after drying
61 grain size was about 1 OnI11, the X-ray diffraction pattern showed a perovskite structure, and no subcomponents were observed.
得られた粉末を、実施例１の場合と同様にして、仮焼、
成形、焼成した。The obtained powder was calcined and
Shaped and fired.
得られた焼結体の密度は理論密度の９５％であった。ニ
オブの添加ｆｔｔｚが０．０００８の時、電気抵抗が最
低のものが得られた。その比抵抗−温度特性は、図に示
したものとほぼ同様であった。１２５℃における５００
時間後、１０００時間後の抵抗変化率はそれぞれ１．５
７％、２．２Ｏ％であった。The density of the obtained sintered body was 95% of the theoretical density. When the niobium addition fttz was 0.0008, the lowest electrical resistance was obtained. Its resistivity-temperature characteristics were almost the same as those shown in the figure. 500 at 125℃
The resistance change rate after 1000 hours is 1.5, respectively.
7% and 2.2O%.
実施例３
ニオブの添加量Ｚを０．００３２とし、実施例１の場合
と同様にして、金属アルコキシドの混合から沈殿を得る
までの工程を４０℃に保持したまま行った。乾燥後の粉
末の８６１粒径は約６ｎｍで、Ｘ線回折パターンは、半
値幅の広いペロブスカイトのピークのみであった。得ら
れた粉末を同様にして仮焼、成形、焼成した。得られた
焼結体の密度は理論密度の９８．９％以上であった。−
２５℃における比抵抗値は９．８２Ω・Ｃｌｌ１であっ
た。１２５℃における５００時間後、１０００時間後の
抵抗変化率はそれぞれ０．８６％、１．４９％であった
。Example 3 The amount Z of niobium added was set to 0.0032, and the steps from mixing the metal alkoxide to obtaining the precipitate were carried out in the same manner as in Example 1 while maintaining the temperature at 40°C. The 861 particle size of the powder after drying was about 6 nm, and the X-ray diffraction pattern had only a perovskite peak with a wide half-width. The obtained powder was calcined, shaped and fired in the same manner. The density of the obtained sintered body was 98.9% or more of the theoretical density. −
The specific resistance value at 25°C was 9.82Ω·Cll1. The resistance change rates after 500 hours and 1000 hours at 125°C were 0.86% and 1.49%, respectively.
実施例４
ニオブの添加量２を０．０００８とし、実施例２の場合
と同様にして、ニオブアルコキシドと溶媒との混合から
沈殿を得るまでの工程を４０℃に保持したまま行った。Example 4 The addition amount 2 of niobium was set to 0.0008, and the steps from mixing niobium alkoxide and a solvent to obtaining a precipitate were performed in the same manner as in Example 2 while maintaining the temperature at 40°C.
乾燥後の粉末の８６１粒径は約５ｎｍで、Ｘ線回折パタ
ーンは、半値幅の広いペロブスカイトのピークのみであ
った。得られた粉末を同様にして仮焼、成形、焼成した
。得られた焼結体の密度は理論密度の９９．１％以上で
あった。−２５℃における比抵抗値は７．５５Ω・ｃｍ
であった。１２５℃における５００時間後、１０００時
間後の抵抗変化率はそれぞれ０．８３％、１．２１％で
あった。The 861 particle size of the powder after drying was about 5 nm, and the X-ray diffraction pattern had only a perovskite peak with a wide half-width. The obtained powder was calcined, shaped and fired in the same manner. The density of the obtained sintered body was 99.1% or more of the theoretical density. Specific resistance value at -25℃ is 7.55Ω・cm
Met. The resistance change rates after 500 hours and 1000 hours at 125°C were 0.83% and 1.21%, respectively.
実施例５
半導体化元素をイツトリウムとし、実施例２の場合と同
様にして、イツトリウムアルコキシドと溶媒との混合か
ら沈殿を得るまでの工程を４０℃に保持したまま行った
。乾燥後の粉末の８６１粒径は約５ｎｍで、Ｘ線回折パ
ターンは、半値幅の広いペロブスカイＩ・のピークのみ
であった。得られた粉末を同様にして仮焼、成形、焼成
した。得られた焼結体の密度は理論密度の９８．８％以
上であった。イツトリウムの添加量Ｚが０．００１０の
時、電気抵抗が最低のものが得られた。−２５℃におけ
る比抵抗値は９．１１Ω・Ｃ１１１であった。１２５℃
における５００時間後、１０００時間後の抵抗変化率は
それぞれ０．８９％、１．３４％であった。Example 5 Yttrium was used as the semiconductor element, and the steps from mixing yttrium alkoxide and a solvent to obtaining a precipitate were carried out in the same manner as in Example 2 while maintaining the temperature at 40°C. The 861 particle size of the powder after drying was about 5 nm, and the X-ray diffraction pattern had only a perovskie I peak with a wide half-width. The obtained powder was calcined, shaped and fired in the same manner. The density of the obtained sintered body was 98.8% or more of the theoretical density. When the amount Z of yttrium added was 0.0010, the lowest electrical resistance was obtained. The specific resistance value at -25°C was 9.11Ω·C111. 125℃
The resistance change rates after 500 hours and 1000 hours were 0.89% and 1.34%, respectively.
比較例
−］Ｏ＝−
比較のために、固相法により原料を製造し、その焼結体
を作製し、特性を調べた。炭酸バリウム、炭酸ストロン
チウム、酸化チタンおよび酸化ニオブを
（ＢａｘＳｒｓ−ｘ）ＴｉＯｓ＋ｚＮｂ（ｘ−０，６、
ｚ−０，００２２）
なる組成となるように配合し、さらにその８ｍｏ １％
にあたるアルミナ、シリカ、酸化チタンを１／３ Ａｌ
２Ｏａ ： ３／４５ｉ０２： ｌ／４ ＴｉＯ
２なる割合で添加し、蒸留水を溶媒としてポリエチレン
製容器とメノウを用いてＩＯ時間混合した。乾燥は、２
Ｏ０℃で６時間行った。１１００℃で２時間仮焼した後
、混合と同様にして３時間粉砕を行った。Comparative Example-]O=- For comparison, a raw material was produced by a solid phase method, a sintered body thereof was produced, and its properties were investigated. Barium carbonate, strontium carbonate, titanium oxide and niobium oxide (BaxSrs-x)TiOs+zNb(x-0,6,
z-0,0022) and further add 8mo 1%
1/3 of alumina, silica, and titanium oxide
2Oa: 3/45i02: l/4 TiO
They were added in two ratios and mixed for 10 hours using a polyethylene container and agate using distilled water as a solvent. Drying is 2
The test was carried out at 00°C for 6 hours. After calcining at 1100° C. for 2 hours, pulverization was performed in the same manner as mixing for 3 hours.
成形、焼成は実施例１の場合と同様にして行った。得ら
れた焼結体の密度は理論密度の９２％であった。比抵抗
は一２６℃で極小値８４０Ω・ｃａｎを示した。１２５
℃における５００時間後、１０００時間後の抵抗変化率
はそれぞれ２．５３％、３．７６％であった。Molding and firing were performed in the same manner as in Example 1. The density of the obtained sintered body was 92% of the theoretical density. The specific resistance showed a minimum value of 840 Ω·can at -26°C. 125
The resistance change rates after 500 hours and 1000 hours at °C were 2.53% and 3.76%, respectively.
発明の効果
本発明によれば、ニオブまたはイツトリウムを半導体化
元素として含有し、バリウムあるいはストロンチウムと
、チタンとを主成分とするＰＴＣザーミスタ用金属酸化
物粉末を容易に製造することができる。得られた粉末は
高純度のものであり、これを原料とし仮焼、成形、焼成
することにより電気抵抗が低くかつ高信頼性のＰＴＣサ
ーミスタ材料を得ることができる。Effects of the Invention According to the present invention, a metal oxide powder for a PTC thermistor containing niobium or yttrium as a semiconductor element and having barium or strontium and titanium as main components can be easily produced. The obtained powder is of high purity, and by using it as a raw material and calcining, molding, and firing, a PTC thermistor material with low electrical resistance and high reliability can be obtained.
図は本発明の一実施例において製造されたＰＴＣサーミ
スタ用金純金属酸化物粉末作製した焼結体の比抵抗と温
度の関係を示すグラフである。The figure is a graph showing the relationship between specific resistance and temperature of a sintered body made of pure gold metal oxide powder for a PTC thermistor manufactured in an example of the present invention.
Claims (3)
コキシドのうちの少なくとも一種と、チタンアルコキシ
ドと半導体化元素Ｍ（ニオブあるいはイットリウム）の
アルコキシドを混合、加水分解する工程を含み、 （ＢａｘＳｒ＿１＿−＿ｘ）ＴｉＯ＿３・ｎＨ＿２Ｏ＋
ＺＭ（ただし、１≧ｘ≧０、ｎ≧０、０．００４０≧ｚ
≧０）なる組成の粉末を作製することを特徴とするＰＴ
Ｃサーミスタ用金属酸化物粉末の製造方法。(1) Includes a step of mixing and hydrolyzing at least one of barium alkoxide and strontium alkoxide, titanium alkoxide and alkoxide of semiconductor element M (niobium or yttrium), (BaxSr_1_-_x)TiO_3・nH_2O+
ZM (however, 1≧x≧0, n≧0, 0.0040≧z
PT characterized by producing a powder having a composition of ≧0)
Method for manufacturing metal oxide powder for C thermistor.
水分解を行った後に、バリウムアルコキシドおよびスト
ロンチウムアルコキシドのうちの少なくとも一種と、チ
タンアルコキシドとを加え、混合、加水分解することを
特徴とする特許請求の範囲第１項記載のＰＴＣサーミス
タ用金属酸化物粉末の製造方法。(2) After first mixing and hydrolyzing alkoxides of semiconductor-forming elements, at least one of barium alkoxide and strontium alkoxide and titanium alkoxide are added, mixed, and hydrolyzed. A method for producing a metal oxide powder for a PTC thermistor according to Item 1.
特許請求の範囲第１項記載のＰＴＣサーミスタ用金属酸
化物粉末の製造方法。(3) The method for producing metal oxide powder for PTC thermistors according to claim 1, wherein the temperature during mixing and hydrolysis is 40° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26219386A JPS63117914A (en) | 1986-11-04 | 1986-11-04 | Production of metal oxide powder for ptc-thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26219386A JPS63117914A (en) | 1986-11-04 | 1986-11-04 | Production of metal oxide powder for ptc-thermistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63117914A true JPS63117914A (en) | 1988-05-21 |
Family
ID=17372366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26219386A Pending JPS63117914A (en) | 1986-11-04 | 1986-11-04 | Production of metal oxide powder for ptc-thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63117914A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991013043A1 (en) * | 1990-02-28 | 1991-09-05 | E.I. Du Pont De Nemours And Company | Improved ceramic dielectric compositions and method for enhancing dielectric properties |
| WO1991013042A1 (en) * | 1990-02-28 | 1991-09-05 | E.I. Du Pont De Nemours And Company | Improved ceramic dielectric composition and method of preparation |
| WO1993004490A1 (en) * | 1991-08-26 | 1993-03-04 | Nippon Tungsten Co., Ltd. | Heating apparatus using ptc thermistor |
-
1986
- 1986-11-04 JP JP26219386A patent/JPS63117914A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991013043A1 (en) * | 1990-02-28 | 1991-09-05 | E.I. Du Pont De Nemours And Company | Improved ceramic dielectric compositions and method for enhancing dielectric properties |
| WO1991013042A1 (en) * | 1990-02-28 | 1991-09-05 | E.I. Du Pont De Nemours And Company | Improved ceramic dielectric composition and method of preparation |
| WO1993004490A1 (en) * | 1991-08-26 | 1993-03-04 | Nippon Tungsten Co., Ltd. | Heating apparatus using ptc thermistor |
| US5592647A (en) * | 1991-08-26 | 1997-01-07 | Nippon Tungsten Co., Ltd. | PTC panel heater with small rush current characteristic and highly heat insulating region corresponding to heater location to prevent local overheating |
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