WO2006106910A1 - 半導体磁器組成物の製造方法 - Google Patents

半導体磁器組成物の製造方法 Download PDF

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Publication number
WO2006106910A1
WO2006106910A1 PCT/JP2006/306816 JP2006306816W WO2006106910A1 WO 2006106910 A1 WO2006106910 A1 WO 2006106910A1 JP 2006306816 W JP2006306816 W JP 2006306816W WO 2006106910 A1 WO2006106910 A1 WO 2006106910A1
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Prior art keywords
composition
producing
semiconductor porcelain
porcelain composition
resistivity
Prior art date
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Ceased
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PCT/JP2006/306816
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English (en)
French (fr)
Inventor
Takeshi Shimada
Koichi Terao
Kazuya Toji
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Proterial Ltd
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Hitachi Metals Ltd
Neomax Co Ltd
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Application filed by Hitachi Metals Ltd, Neomax Co Ltd filed Critical Hitachi Metals Ltd
Priority to US11/910,222 priority Critical patent/US7700509B2/en
Priority to CN2006800110486A priority patent/CN101160270B/zh
Priority to EP06730764A priority patent/EP1873130A4/en
Priority to JP2007511158A priority patent/JP5163118B2/ja
Publication of WO2006106910A1 publication Critical patent/WO2006106910A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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Definitions

  • This invention has a positive resistance temperature used for PTC thermistors, PTC heaters, PTC switches, temperature detectors, and the like, and at the same time, greatly reduces the resistivity at room temperature, and is uniform even inside the material.
  • the present invention relates to a method for producing a semiconductor ceramic composition capable of imparting characteristics.
  • the Curie temperature can be shifted by adding SrTiO to BaTiO.
  • the Curie temperature shifts only in the negative direction and not in the positive direction.
  • PbTiO is known as an additive element that shifts the Curie temperature in the positive direction.
  • PbTiO contains elements that cause environmental pollution
  • BaTiO-based semiconductor porcelain that is sintered in nitrogen and then heat-treated in an oxidizing atmosphere with one or more of Nb, Ta, or rare earth elements in a composition in the range of 1-2X 3 and x ⁇ 0.15 Made of
  • Patent Document 1 A manufacturing method has been proposed.
  • Patent Document 1 Japanese Patent Laid-Open No. 56-169301
  • Patent Document 1 includes, as an example, Ba (BiNa) TiO (0 ⁇ x ⁇ 0.15), Nd 0 as 0.1 mol% as a semiconductor element.
  • the resistance value is considered to be caused by a Schottky barrier at the grain boundary.
  • grain boundary oxidation and reduction treatments have been proposed, and it has been reported that high PTC characteristics can be obtained with materials that have been subjected to acid and oxygen treatment in oxygen. (Non-patent document 1).
  • the processing speed in the heat treatment also affects the characteristics (Non-patent Document 2), and the heat treatment of the material becomes very complicated!
  • Non-Patent Document 1 Material of the Chitabari Study Group XVII-95-659 (1968)
  • Non-Patent Document 2 J. Am. Ceram. Soc. 48, 81 (1965)
  • the present invention solves the above-described conventional problems, can shift the Curie temperature without using Pb in the positive direction, and greatly reduces the resistivity at room temperature. It aims at providing the manufacturing method for obtaining.
  • the present invention provides a method for producing a semiconductor ceramic composition capable of imparting uniform characteristics to the inside of a material having a relatively large and thick shape without performing a complicated heat treatment.
  • the purpose is to provide.
  • the inventors placed a part of Ba with B to Na.
  • the inventors have conducted the sintering of the composition in an inert gas atmosphere having an oxygen concentration of 1% or less, so that the interior of the composition can be obtained. Uniform PTC characteristics can be given, complex atmosphere management and processing speed As a result, it was found that a semiconductor porcelain composition having excellent characteristics can be obtained.
  • a method for producing a semiconductor porcelain composition according to the present invention has a composition formula of [(Bi Na) (Ba R)].
  • the oxygen concentration is 10 ppm or less
  • Si oxide is 3.0 mol% or less
  • Ca oxide is 4.0 mol.
  • a semiconductor ceramic composition in which the Curie temperature can be increased without using Pb causing environmental pollution, and the resistivity at room temperature is greatly reduced. be able to.
  • One of the features of the present invention is that a part of Ba is substituted with Bi-Na to shift the Curie temperature in the positive direction, and the valence disturbed by the substitution of Bi-Na is optimized.
  • a part of Ba is substituted with a specific amount of R element (at least one of La, Dy, Eu, Gd, and Y) to obtain a [(Bi Na) (Ba R)] TiO composition. is there.
  • R element at least one of La, Dy, Eu, Gd, and Y
  • R is at least one of La ⁇ Dy ⁇ Eu ⁇ Gd, Y
  • X represents a component range of Bi + Na, and 0 and x ⁇ 0.14 is a preferable range. If X is 0, the Curie temperature cannot be shifted to the high temperature side, and if it exceeds 0.14, the resistivity at room temperature approaches 10 4 ⁇ cm, making it difficult to apply to a PTC heater or the like.
  • y represents the component range of R, and 0.002 ⁇ y ⁇ 0.02 is a preferred range. y is less than 0.002 Insufficient control of the valence of the composition increases the resistivity at room temperature. Further, if y exceeds 0.02, the resistivity at room temperature increases, which is not preferable. Preferably, 0.005 ⁇ y ⁇ 0.02, and the resistivity at room temperature can be further reduced. The above 0.002 ⁇ ⁇ 0.01 is 0.2 mol% to 2.0 mol% in terms of mol%.
  • Si oxide is contained in an amount of 3.0 mol% or less, and Ca is oxidized
  • Addition of Si oxide suppresses abnormal grain growth and facilitates control of resistivity, and addition of Ca oxide improves sinterability at low temperatures. Can do. In any case, adding more than the above-mentioned limit is not preferable because the composition does not exhibit semiconductor properties.
  • Another feature of the present invention is the method for producing the above [(Bi Na) (Ba R)] TiO composition
  • sintering is performed in an inert gas atmosphere having an oxygen concentration of 1% or less.
  • a more preferred oxygen concentration is lOppm. This eliminates the need for complicated heat treatment in an oxygen atmosphere, which has been conventionally performed, and can impart uniform characteristics to the inside of a material having a relatively large thickness.
  • the oxygen concentration exceeds 1%, it is not preferable because uniform characteristics cannot be imparted to the inside of the material.
  • Nitrogen, argon, helium, carbon dioxide, etc. can be used as the inert gas.
  • sintering it is preferable to use a sintering furnace having an airtight structure.
  • Each powder is mixed in a wet process and then dried. At this time, depending on the particle size of the raw material powder, it may be crushed simultaneously with mixing.
  • the mixing medium is preferably pure water or ethanol. O
  • the average particle size of the mixed powder after mixing or grinding is preferably 0.6 ⁇ m to 1.5 ⁇ m.
  • the mixed powder is calcined.
  • the calcining temperature is preferably 900 ° C to 1100 ° C.
  • the calcining time is preferably 2 to 6 hours.
  • the calcination atmosphere is preferably in the air or in oxygen! /.
  • the calcined body after calcining is finely pulverized and then dried.
  • the pulverization is preferably performed in a wet process.
  • the medium used for grinding is preferably pure water or ethanol.
  • the average particle size of the pulverized powder after pulverization is preferably 0.6 ⁇ m to 1.5 ⁇ m! / ⁇ .
  • the finely pulverized pulverized powder is molded by a desired molding means. Before molding, the pulverized powder may be granulated with a granulator if necessary.
  • the compact density after molding is preferably 2 to 3 g / cm 3 .
  • the molded body is sintered.
  • the inert gas is nitrogen
  • the sintering atmosphere is 99% or more of nitrogen and the oxygen concentration is 1% or less, preferably 10 ppm or less.
  • the sintering temperature is preferably 1200 ° C to 1400 ° C, and the sintering time is preferably 2 hours to 4 hours.
  • binder removal treatment it is preferable to perform binder removal treatment at 300 ° C to 700 ° C.
  • the mixed powder was calcined in the atmosphere at 1000 ° C for 4 hours.
  • the calcined powder obtained was pulverized to an average particle size of 0.9 m by wet pulverization, and then the pulverized powder was dried.
  • PVA was added to the dried powder and mixed, and then granulated by a granulator.
  • the obtained granulated powder was molded by a uniaxial press machine to obtain a molded body having dimensions of 28.5 mm X 28.5 mm X thickness of 0.7 mm to 18 mm and an development density of 2.5 to 3.5 g / cm 3 .
  • the binder was debindered at 300 ° C to 700 ° C, it was sintered in a nitrogen atmosphere having the oxygen concentration shown in Table 1 for 4 hours at 1280 to 1380 ° C depending on the composition.
  • a sintered body having a thickness of 23.0 mm X 2 3.0 mm X thickness 0.5 mm to 15 mm and a sintering density 5.5 g / cm 3 was obtained.
  • the obtained sintered body is processed into a plate shape of 10mm x 10mm x lmm (except when the thickness of the sintered body is lmm or less) A test piece was obtained.
  • sample number 52 is an example using Dy as R
  • sample number 53 is an example using Eu as R
  • sample number 54 is an example using Gd as R
  • sample number 55 is Y as R This is an example.
  • the semiconductor ceramic composition obtained according to the example of the present invention can increase the Curie temperature without using Pb and has a resistivity at room temperature. Can be greatly reduced.
  • the semiconductor ceramic composition obtained by the present invention is optimal as a material for PTC thermistors, PTC heaters, PTC switches, temperature detectors, and the like.
  • FIG. 1 is a graph showing a temperature change in resistivity of a semiconductor ceramic composition according to the present invention.

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Abstract

【課題】　Pbを使用することなく、キュリー温度を正の方向へシフトすることができ、室温における抵抗率を大幅に低下させた半導体磁器組成物を得る製造方法、及び複雑な熱処理を行うことなく、比較的大きな厚みのある形状の材料においても、材料内部にまで均一な特性を付与することができる半導体磁器組成物の製造方法の提供。 【解決手段】　組成式を[(Bi0.5Na0.5)x(Ba1-yRy)1-x]TiO3(但し、RはLa、Dy、Eu、Gd、Yの少なくとも一種)と表し、前記x、yが、0<x≦0.14、0.002<y≦0.02を満足する半導体磁器組成物の製造方法において、焼結を酸素濃度1%以下の不活性ガス雰囲気で行うことにより、室温における抵抗率を大幅に低下させかつ材料内部にまで均一な特性を付与する。

Description

明 細 書
半導体磁器組成物の製造方法
技術分野
[0001] この発明は、 PTCサーミスタ、 PTCヒータ、 PTCスィッチ、温度検知器などに用いられ る、正の抵抗温度を有するとともに、室温における抵抗率を大幅に低下させ、材料内 部にまで均一な特性を付与できる半導体磁器組成物の製造方法に関する。
背景技術
[0002] 従来、正の PCTRを示す材料として、 BaTiOに様々な半導体化元素を加えた組成
3
物が提案されている。これらの組成物は、キュリー温度が 120°C前後であるため、用途 に応じてキュリー温度をシフトさせることが必要になる。
[0003] 例えば、 BaTiOに SrTiOを添加することによってキュリー温度をシフトさせることが
3 3
提案されている力 この場合、キュリー温度は負の方向にのみシフトし、正の方向に はシフトしない。現在、キュリー温度を正の方向にシフトさせる添加元素として知られ ているのは PbTiOだけである。し力し、 PbTiOは環境汚染を引き起こす元素を含有
3 3
するため、近年、 PbTiOを使用しない材料が要望されている。
3
[0004] BaTiO系半導体磁器において、 Pb置換による抵抗温度係数の低下を防止するとと
3
もに、電圧依存性を小さくし、生産性や信頼性を向上させることを目的として、 BaTiO
3 の Baの一部を Bi-Naで置換した Ba (BiNa) TiOなる構造において、 xを 0
1-2X 3 く x≤0.15の 範囲とした組成物に Nb、 Taまたは希土類元素の ヽずれか一種または一種以上をカロ えて窒素中で焼結した後酸化性雰囲気中で熱処理する BaTiO系半導体磁器の製
3
造方法が提案されて!ヽる (特許文献 1)。
特許文献 1：特開昭 56-169301号公報
[0005] Baの一部を Bi-Naで置換した系にお 、て、組成物の原子価制御を行う場合、 3価の 陽イオンを半導体ィ匕元素として添加すると半導体ィ匕の効果力 Si価の Naイオンの存在 のために低下し、室温における抵抗率が高くなるという問題がある。特許文献 1には、 実施例として、 Ba (BiNa) TiO (0〈x≤0.15)に、半導体元素として、 Nd 0を 0.1モル％
1-2X 3 2 3 添加した組成物が開示されて!ヽるが、 PTC用途として十分な半導体ィ匕を実現できる 添加量ではない。
[0006] 上述した材料において、その抵抗値は粒界のショットキー障壁に起因すると考えら れている。このショットキー障壁をコントロールする手段として、粒界の酸化'還元処理 が提案されており、一般的に酸素中で酸ィ匕処理を行った材料で高い PTC特性が得ら れることが報告されている (非特許文献 1)。また、その熱処理における処理速度も特 性に影響を与えることも報告されており (非特許文献 2)、材料の熱処理が非常に複雑 になって!/、ると!/、う問題がある。
非特許文献 1：チタバリ研究会資料 XVII-95-659(1968)
非特許文献 2 : J. Am.Ceram. Soc. 48, 81 (1965)
[0007] また、上記熱処理によれば、比較的小さな形状であれば、熱処理による効果が材 料内部にまで均一に作用させることができる力 PTCヒータなどの用途へ応用される 比較的大きな形状 (厚みのある形状)の場合は、材料内部にまで均一な PTC特性を持 たせることが困難であるという問題がある。
発明の開示
[0008] この発明は、上述した従来の問題を解決し、 Pbを使用することなぐキュリー温度を 正の方向へシフトすることができるとともに、室温における抵抗率を大幅に低下させた 半導体磁器組成物を得るための製造方法の提供を目的とする。
[0009] また、この発明は、複雑な熱処理を行うことなぐ比較的大きな、厚みのある形状の 材料においても、材料内部にまで均一な特性を付与することができる半導体磁器組 成物の製造方法の提供を目的とする。
[0010] 発明者らは、 BaTiO系半導体磁器組成物において、 Baの一部を Bト Naによって置
3
換した場合の原子価制御に着目し、最適な原子価制御を行うための添加元素の含 有量について鋭意研究の結果、 Baを特定量の R元素で置換することにより、最適な 原子価制御ができ、室温における抵抗率を大幅に低下させることができることを知見 した。
[0011] また、発明者らは、上記半導体磁器組成物の製造方法について研究の結果、上記 組成物の焼結を酸素濃度 1%以下の不活性ガス雰囲気で行うことにより、組成物内部 にまで均一な PTC特性を付与することができるとともに、複雑な雰囲気管理、処理速 度などを行うことなぐ優れた特性を有する半導体磁器組成物が得られることを知見 し、この発明を完成した。
[0012] この発明による半導体磁器組成物の製造方法は、組成式を [(Bi Na ) (Ba R ) ]
0.5 0.5 x 1-y y 1-χ
TiO (但し、 Rは La、 Dy、 Eu、 Gd、 Yの少なくとも一種)と表し、前記 x、 yが、 0<x≤0.14,
3
0.002く y≤ 0.02を満足する半導体磁器組成物の製造方法であって、焼結を酸素濃度
1%以下の不活性ガス雰囲気で行うことを特徴とする。
[0013] また、この発明は、上記構成の半導体磁器組成物の製造方法において、酸素濃度 が lOppm以下であることを特徴とする構成、 Si酸化物を 3.0mol%以下、 Ca酸化物を 4.0 mol%以下含有することを特徴とする構成を併せて提案する。
[0014] この発明によれば、環境汚染を引き起こす Pbを使用することなぐキュリー温度を上 昇させることができるととも〖こ、室温における抵抗率を大幅に低下させた半導体磁器 組成物を提供することができる。
[0015] この発明によれば、比較的大きな、厚みのある形状の半導体磁器糸且成物において も、材料内部にまで均一な特性を付与することができる。
[0016] この発明によれば、複雑な熱処理を行う必要がな!、ので、安価にして優れた特性を 有する半導体磁器組成物を提供することができる。
発明を実施するための最良の形態
[0017] この発明の特徴の一つは、 Baの一部を Bi-Naで置換することにより、キュリー温度を 正の方向にシフトさせるとともに、該 Bi-Naの置換によって乱れた原子価を最適に制 御するために、 Baの一部を特定量の R元素 (La、 Dy、 Eu、 Gd、 Yの少なくとも一種)で 置換した [(Bi Na ) (Ba R ) ]TiO組成とすることにある。各組成の限定理由は以
0.5 0.5 1 1 3
下の通りである。
[0018] [(Bi Na ) (Ba R ) ]TiO組成において、 Rは、 Laゝ Dyゝ Euゝ Gd、 Yの少なくとも一
0.5 0.5 1 1 3
種である。好ましい形態は Rが Laの場合である。組成式中、 Xは Bi+Naの成分範囲を 示し、 0く x≤ 0.14が好ましい範囲である。 Xが 0ではキュリー温度を高温側へシフトする ことができず、 0.14を超えると室温の抵抗率が 104 Ω cmに近づき、 PTCヒーターなどに 適用することが困難となるため好ましくない。
[0019] yは、 Rの成分範囲を示し、 0.002≤y≤ 0.02が好ましい範囲である。 yが 0.002未満で は組成物の原子価制御が不充分となり室温の抵抗率が大きくなる。また、 yが 0.02を 超えると室温の抵抗率が大きくなるため好ましくない。好ましくは 0.005≤y≤ 0.02であ り、室温の抵抗率をより低下することができる。なお、上記 0.002≤ ≤0.01はモル％表 記では 0.2モル％〜2.0モル％となる。
[0020] 前記 [(Bi Na ) (Ba R ) ]TiO組成において、 Si酸化物を 3.0mol%以下、 Ca酸化
0.5 0.5 x 1-y y 1-χ 3
物を 4.0mol%以下添加することが好まし 、。 Si酸ィ匕物の添カ卩は結晶粒の異常成長を 抑制するとともに抵抗率のコントロールを容易にすることができ、 Ca酸ィ匕物の添カロは 低温での焼結性を向上させることができる。いずれも上記限定量を超えて添加すると 、組成物が半導体ィ匕を示さなくなるため好ましくない。
[0021] この発明のもう一つの特徴は、上記 [(Bi Na ) (Ba R ) ]TiO組成物の製造方法
0.5 0.5 1 1 3
において、焼結を酸素濃度 1%以下の不活性ガス雰囲気で行うことにある。より好まし い酸素濃度は lOppmである。これにより、従来行われていた酸素雰囲気中における 複雑な熱処理が不要となるとともに、比較的大きな、厚みのある形状の材料において も、材料内部にまで均一な特性を付与することができる。
[0022] 酸素濃度が 1%を超えると、材料内部にまで均一な特性を付与することができないの で好ましくない。不活性ガスとしては、窒素、アルゴン、ヘリウム、炭酸ガスなどを用い ることができる。焼結に際しては、気密構造を有する焼結炉を用いることが好ましい。
[0023] この発明による半導体磁器組成物の製造方法の一例を以下に説明する。焼結ェ 程以外の工程については、以下に限定されるものではなぐ公知の方法を採用する ことができる。
[0024] (1)主原料として BaCO、 TiO、半導体化元素及び原子価制御元素として La 0、 Dy
3 2 2 3 2
O、 Eu O、 Gd O、 Y Oの少なくとも一種、焼結助剤として SiO、 CaO、さらにキュリー
3 2 3 2 3 2 3 2
温度のシフタ一として (Na CO -Bi O -TiO )の各粉末を準備する。
2 3 2 3 2
[0025] (2)各粉末を湿式中で混合した後、乾燥する。この時、原料粉末の粒度によっては、 混合と同時に粉砕を施してもょ 、。混合時の媒体は純水またはエタノールが好ま ヽ o混合または粉砕後の混合粉末の平均粒径は 0.6 μ m〜1.5 μ mが好ま 、。
[0026] (3)混合粉末を仮焼する。仮焼温度は 900°C〜1100°Cが好ましい。仮焼時間は 2時間 〜6時間が好ま 、。仮焼雰囲気は大気中あるいは酸素中が好まし!/、。 [0027] (4)仮焼後の仮焼体を微粉砕の後乾燥する。微粉砕は湿式中で行うことが好ましい。 粉砕時の媒体は純水またはエタノールが好まし ヽ。微粉砕後の粉砕粉の平均粒径 は 0.6 μ m〜1.5 μ mが好まし!/ヽ。
[0028] (5)微粉砕後の粉砕粉を所望の成形手段によって成形する。成形前に、必要に応じ て粉砕粉を造粒装置によって造粒してもょ ヽ。成形後の成形体密度は 2〜3g/cm3が 好ましい。
[0029] (6)成形体を焼結する。焼結雰囲気は、上述したように、例えば不活性ガスが窒素の 場合、 99%以上の窒素、酸素濃度が 1%以下、好ましくは lOppm以下の雰囲気中で行う 。焼結温度は 1200°C〜1400°Cが好ましぐ焼結時間は 2時間〜 4時間が好ましい。造 粒を行った場合は、 300°C〜700°Cで脱バインダー処理を行うことが好ま U、。
[0030] 上記の焼結工程を必須工程として含むことにより、室温における抵抗率を大幅に低 下させた、 [(Bi Na ) (Ba R ) ]TiO組成を有する半導体磁器組成物を得ることが
0.5 0.5 1 1 3
できる。
実施例
[0031] 主原料として BaCO、 TiO、半導体化元素及び原子価制御元素として La 0、 Dy 0
3 2 2 3 2
、 Eu O、 Gd O、 Y O、焼結助剤として SiO、 CaO、さらにキュリー温度のシフターと
3 2 3 2 3 2 3 2
して (Na CO ·Βί Ο ·ΤίΟ )の各粉末を準備した。各粉末を [(Bi Na ) (Ba R ) ]TiO
2 3 2 3 2 0.5 0.5 x 1-y y 1-χ 3 組成となるように、表 1に示す如く配合し、エタノール中で混合した後乾燥し、平均粒 径 9.0 μ m程度の混合粉を得た。
[0032] 上記混合粉を大気中で 1000°Cで 4時間仮焼し、得られた仮焼粉を湿式粉砕により 平均粒径 0.9 mに粉砕した後、粉砕粉を乾燥させた。次いで、乾燥粉に PVAを添カロ 、混合した後、造粒装置によって造粒した。得られた造粒粉を一軸プレス装置で成形 し、寸法 28.5mm X 28.5mm X厚み 0.7mm〜18mm、成开密度 2.5〜3.5g/cm3の成形体 を得た。
[0033] 上記成形体を 300°C〜700°Cで脱バインダー後、表 1に示す酸素濃度を有する窒素 雰囲気中において、各組成に応じて 1280〜1380°Cで 4時間焼結し、寸法 23.0mm X 2 3.0mm X厚み 0.5mm〜15mm、焼結密度 5.5g/cm3の焼結体を得た。得られた焼結体 を 10mm X 10mm X lmmの板状に加工 (但し、焼結体の厚みが lmm以下の場合は除く) し、試験片を得た。
[0034] 各試験片を抵抗測定器で室温から 270°Cまでの範囲で抵抗値の温度変化を測定し た。測定結果を表 1に示す。表 1において、試料番号 52は Rとして Dyを用いた例、試 料番号 53は Rとして Euを用いた例、試料番号 54は Rとして Gdを用いた例、試料番号 5 5は Rとして Yを用 V、た例である。
[0035] また、表 1において、試料番号の横に *印を付したものは比較例である。図 1は [(Bi
0.5
Na ) (Ba La ) ]TiO組成において、 yを 0.006とし、 xの値を 0·02(黒丸 a)、 0·075(黒
0.5 1 1 3
丸 b)、 0.875(黒菱形 c)、 0.1(黒四角 d)、 0.1375(黒三角 、 0.2(白丸!)とした場合の、抵 抗率の温度変化を示すグラフである。
[0036] 表 1及び図 1から明らかなように、この発明の実施例により得られた半導体磁器組成 物は、 Pbを使用することなぐキュリー温度を上昇させることができるとともに、室温に おける抵抗率を大幅に低下させることできる。
[0037] また、表 1又は図 1から明らかなように、 Xが 0〈x≤0.14の範囲、 yが 0.002〈y≤0.02の 範囲で良好な特性が得られて ヽる。
[0038] さらに、表 1から明らかなように、酸素濃度が 1%以下の雰囲気中で焼結した場合に、 良好な特性が得られており、また、厚み 15mmの比較的大きな材料でも、良好な特性 が得られていることが分かる。これは、焼結を酸素濃度 1%以下の不活性ガス雰囲気 中で行ったことにより、材料内部にまで均一な特性を付与することができた力もである
[0039] [表 1]
Figure imgf000009_0001
産業上の利用可能性
[0040] この発明により得られる半導体磁器組成物は、 PTCサ一ミスタ、 PTCヒータ、 PTC スィッチ、温度検知器などの材料として最適である。
図面の簡単な説明
[0041] [図 1]この発明による半導体磁器組成物の抵抗率の温度変化を示すグラフである。
差 Iえ用弒 («26^

Claims

請求の範囲
[1] 組成式を [(Bi Na ) (Ba R ) ]TiO (但し、 Rは La、 Dy、 Eu、 Gd、 Yの少なくとも一種）
0.5 0.5 χ 1-y y 1-χ 3
と表し、前記 x、 yが、 0く x≤0.14、 0.002く y≤ 0.02を満足する半導体磁器組成物の製 造方法であって、焼結を酸素濃度 1%以下の不活性ガス雰囲気で行う半導体磁器組 成物の製造方法。
[2] 酸素濃度が lOppm以下である請求項 1に記載の半導体磁器組成物の製造方法。
[3] Si酸ィ匕物を 3.0mol%以下、 Ca酸ィ匕物を 4.0mol%以下含有する請求項 1に記載の半導体 磁器組成物の製造方法。
PCT/JP2006/306816 2005-03-31 2006-03-31 半導体磁器組成物の製造方法 Ceased WO2006106910A1 (ja)

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WO2008050877A1 (en) * 2006-10-27 2008-05-02 Hitachi Metals, Ltd. Semiconductor ceramic composition and method for producing the same
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WO2009116452A1 (ja) 2008-03-19 2009-09-24 日立金属株式会社 半導体磁器組成物の製造方法及び半導体磁器組成物を用いたヒータ
KR100941522B1 (ko) 2008-01-17 2010-02-10 한국세라믹기술원 납성분을 포함하지 않는 ｐｔｃ 써미스터용 세라믹 조성물및 이에 의해 제조되는 ｐｔｃ 세라믹 써미스터
JP2010083737A (ja) * 2008-10-02 2010-04-15 Hitachi Metals Ltd 半導体磁器組成物
US8093170B2 (en) 2007-06-14 2012-01-10 Murata Manufacturing Co., Ltd. Semiconductor ceramic material
CN101395100B (zh) * 2006-10-27 2013-03-27 日立金属株式会社 半导体陶瓷组合物及其制备方法
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WO2007097462A1 (ja) * 2006-02-27 2007-08-30 Hitachi Metals, Ltd. 半導体磁器組成物
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US8076256B2 (en) 2006-10-27 2011-12-13 Hitatchi Metals, Ltd. Semiconductor ceramic composition and method for producing the same
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KR20080010388A (ko) 2008-01-30
EP1873130A4 (en) 2012-01-04
US20080286185A1 (en) 2008-11-20
JPWO2006106910A1 (ja) 2008-09-11
JP5163118B2 (ja) 2013-03-13
EP2502893A3 (en) 2013-04-03
EP2502893A2 (en) 2012-09-26
JP2013014508A (ja) 2013-01-24
EP1873130A9 (en) 2012-06-27
US7700509B2 (en) 2010-04-20
KR101039951B1 (ko) 2011-06-09
CN101160270A (zh) 2008-04-09
CN101160270B (zh) 2012-04-04
EP2502893B1 (en) 2014-07-30
JP5445640B2 (ja) 2014-03-19
EP1873130A1 (en) 2008-01-02

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