WO2007023512A1 - 半導体磁器組成物 - Google Patents

半導体磁器組成物 Download PDF

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Publication number
WO2007023512A1
WO2007023512A1 PCT/JP2005/014769 JP2005014769W WO2007023512A1 WO 2007023512 A1 WO2007023512 A1 WO 2007023512A1 JP 2005014769 W JP2005014769 W JP 2005014769W WO 2007023512 A1 WO2007023512 A1 WO 2007023512A1
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Prior art keywords
composition
replaced
resistivity
room temperature
semiconductor ceramic
Prior art date
Application number
PCT/JP2005/014769
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English (en)
French (fr)
Inventor
Takeshi Shimada
Kei Matsumoto
Koichi Terao
Kazuya Toji
Kazuhiro Nishikawa
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Hitachi Metals, Ltd.
Priority date (The priority date 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 date listed.)
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Application filed by Hitachi Metals, Ltd. filed Critical Hitachi Metals, Ltd.
Priority to IN1545DEN2015 priority Critical patent/IN2015DN01545A/en
Priority to US12/063,494 priority patent/US7825054B2/en
Priority to KR1020127017389A priority patent/KR101197009B1/ko
Priority to CN2005800513054A priority patent/CN101272998B/zh
Priority to PCT/JP2005/014769 priority patent/WO2007023512A1/ja
Priority to KR1020117024173A priority patent/KR101118320B1/ko
Priority to EP12170169A priority patent/EP2497759A3/en
Priority to EP05770429.8A priority patent/EP1921052B8/en
Publication of WO2007023512A1 publication Critical patent/WO2007023512A1/ja
Priority to KR1020087002793A priority patent/KR101265369B1/ko
Priority to US12/855,182 priority patent/US7893001B2/en

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Definitions

  • the present invention relates to a semiconductor ceramic composition having a positive resistance temperature, which is used for a PTC thermistor, a PTC heater, a PTC switch, a temperature detector, and the like.
  • compositions have been proposed. Since these compositions have a Curie temperature of around 120 ° C, it is necessary to shift the Curie temperature depending on the application.
  • the Curie temperature can be shifted by adding SrTiO to BaTiO.
  • Nb, Ta, or rare earth elements was added to the composition in the range, sintered in nitrogen, and then heat treated in an oxidizing atmosphere.
  • Patent Document 1 Japanese Patent Laid-Open No. 56-169301
  • Patent Document 1 an example is Ba (BiNa) TiO (0 ⁇ x ⁇ 0.15), and a semiconductor element and l-2x 3
  • the present invention solves the above-mentioned problems of the conventional BaTiO-based semiconductor ceramic composition and uses Pb.
  • the object of the present invention is to provide a semiconductor ceramic composition that can shift the Curie temperature without being used in a positive direction and that has a greatly reduced resistivity at room temperature.
  • the inventors of the BaTiO-based semiconductor porcelain composition may use a part of Ba for example B to Na.
  • the part of Ba is replaced with A1 element (at least one of Na, K, Li). It was found that by substituting A2 element (Bi) and replacing Ba with a specific amount of Q element, optimal valence control can be achieved and resistivity at room temperature can be greatly reduced.
  • the inventors replaced part of Ba with A1 element (at least one of Na, K, Li) and Li2 element (Bi), and part of Ti with a specific amount of M element. As a result, it has been found that the same effect as described above can be obtained.
  • the present invention has been completed.
  • the present invention relates to a composition formula of [(A1 A2) (Ba Q)] TiO
  • x and y are 0 ⁇ x ⁇ 0.2, 0.002 ⁇ y ⁇ 0.01, more preferably, a semiconductor ceramic composition characterized in that y satisfies 0.005 ⁇ y ⁇ 0.01.
  • composition formula is represented as [(Al A2) Ba] [Ti M] 0
  • Al is one or more of Na, K and Li, A2 is Bi, M is one or more of Nb, Ta and Sb), and x and y are 0 ⁇ x ⁇ 0.2, It is a semiconductor ceramic composition characterized by satisfying 0 ⁇ z ⁇ 0.01, more preferably 0 ⁇ z ⁇ 0.005.
  • each semiconductor ceramic composition having the above-described configuration, Each is a semiconductor ceramic composition characterized in that Si oxide is added in an amount of 3.0 mol% or less and Ca oxide is added in an amount of 4.0 mol% or less.
  • the BaTiO-based semiconductor ceramic composition according to the present invention reaches room temperature and a predetermined temperature.
  • a feature of the present invention is that a part of Ba is replaced with an A1 element (at least one of Na, K, Li, ie, one or more) and an A2 element (Bi), thereby making the Curie temperature positive.
  • a part of Ba is replaced with a specific amount of Q element (at least one of La, Dy, Eu, and Gd)
  • Q element at least one of La, Dy, Eu, and Gd
  • Al is at least one of Na, K, Li, A2
  • Q is at least one of La, Dy, Eu, and Gd.
  • A1 is Na and Q is La.
  • X represents a component range of A1 + A2, and 0 ⁇ x ⁇ 0.2 is a preferable range. If x is 0, the Curie temperature cannot be shifted to the high temperature side, and if it exceeds 0.2, the resistivity at room temperature exceeds 10 3 ⁇ cm.
  • y represents the component range of Q, and 0.002 ⁇ y ⁇ 0.01 is a preferred range. If y is less than 0.002, the valence control of the composition is insufficient, and the resistivity at room temperature exceeds 10 3 ⁇ cm. On the other hand, if y exceeds 0.01, the composition becomes an insulator, and the resistivity at room temperature exceeds 10 3 ⁇ cm. Preferably 0.005 ⁇ y ⁇ 0.01. Can be reduced.
  • the above 0.002 ⁇ y ⁇ 0.01 is 0.2 mol% to 1.0 monole% in terms of mol%.
  • A1 is at least one of Na, K, Li, A2
  • M is at least one of Nb, Ta, Sb.
  • A1 is Na and M is Nb.
  • X represents a component range of A1 + A2, and 0 ⁇ x ⁇ 0.2 is a preferred range. If x is 0, the Curie temperature cannot be shifted to the high temperature side, and if it exceeds 0.2, the resistivity at room temperature exceeds 10 3 ⁇ cm. Z indicates the component range of M, and 0 ⁇ z ⁇ 0.01 is the preferred range. If z is 0, the valence cannot be controlled, the composition does not become a semiconductor, and if it exceeds 0.01, the resistivity at room temperature exceeds 10 3 ⁇ cm, which is not preferable. More preferably, 0 and z ⁇ 0.005. The above 0 ⁇ z ⁇ 0.01 is 0 to 1 mol% (not including 0) in terms of mol%.
  • the addition of element M (preferred addition amount 0 ⁇ z ⁇ 0.005) is intended to control the valence of Ti site, which is a tetravalent element. ) (Ba Q)
  • the mixed powder is calcined at 900 ° C-1100 ° C for 2-6 hours.
  • the calcined body is pulverized in pure water or ethanol and then dried.
  • the molded body is debindered at 300 ° C to 700 ° C, and then sintered at 1200 ° C to 1450 ° C for 2 to 6 hours in the air or in a reducing atmosphere.
  • BaCO TiO as main raw materials
  • La 0, Dy 0, Eu 0, Gd 0, Nb as semiconducting elements
  • the mixed powder was calcined at 900 ° C. to 1100 ° C. for 2 to 6 hours depending on the composition.
  • the obtained calcined powder was pulverized in pure water to an average particle size of 0.8 to 1.5 ⁇ m, and then the pulverized powder was dried.
  • PVA was added to the dried powder, mixed, and granulated with a granulator.
  • the obtained granulated powder was molded to a molding density of 2 to 3 g / cm 3 using a uniaxial press machine. After removing the binder from 300 ° C to 700 ° C in an atmosphere with an oxygen concentration of 75%, 13
  • the obtained sintered body was processed into a plate shape of 10 mm X 10 mm X 0.1 mm to obtain a test piece.
  • the change in resistance value was measured in the range from room temperature to 200 ° C.
  • Tables 1 to 6 show the measurement results.
  • Nos. 1 to 29 in Table 1 are [(Al Bi) Ba] [Ti Nb] 0 compositions,
  • ⁇ ⁇ 103 to 118 are [(Al Bi) (Ba Eu)] Ti ⁇ composition
  • BaCO TiO as main raw materials
  • La 0, Nb 0 semiconducting elements
  • Each powder of (Na 2 CO 3 —Bi 2 O 3 —TiO 2) was prepared as a catalyst. As shown in Table 7 to Table 8 for each powder The mixture was mixed, mixed in pure water and then dried to obtain a mixed powder having an average particle size of 0.6 to 1.2 i um.
  • the mixed powder was calcined at 900 ° C to 1100 ° C for 2 to 6 hours depending on the composition.
  • the obtained calcined powder was pulverized in pure water to an average particle size of 0.8 to 1.5 ⁇ m, and then the pulverized powder was dried.
  • PVA was added to the dried powder, mixed, and granulated with a granulator.
  • the obtained granulated powder was molded to a molding density of 2 to 3 g / cm 3 with a uniaxial press machine. After removing the binder from 300 ° C to 700 ° C in an atmosphere with an oxygen concentration of 75%, 13
  • the obtained sintered body was processed into a plate shape of 10 mm X 10 mm X 0.1 mm to obtain a test piece.
  • the resistance change of the obtained test piece was measured in the range from room temperature to 200 ° C by resistance measurement. The measurement results are shown in Table 7 to Table 8.
  • No. 136 and Table 8 are comparative examples.
  • the semiconductor ceramic composition according to the present invention can increase the Curie temperature when Pb is used, and greatly reduce the resistivity at room temperature. I understand.
  • PTC thermistor PTC heater
  • PTC switch temperature Detectors

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Abstract

　この発明は、BaTiO3系半導体磁器組成物において、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、半導体磁器組成物の提供することを目的とする。この発明は、Baの一部をA1元素(Na、K、Liの少なくとも一種)とA2元素(Bi)で置換するとともに、さらにBaを特定量のQ元素で置換するか、Baの一部をA1元素(Na、K、Liの少なくとも一種)とA2元素(Bi)で置換するとともに、Tiの一部を特定量のM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、PTCサーミスタ、PTCヒータ、PTCスイッチ、温度検知器など、特に自動車用ヒータなどの用途に最適である。

Description

半導体磁器組成物
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半導体磁器組成物に関する。
背景技術
[0002] 従来、正の PCTRを示す材料として、 BaTiOに様々な半導体ィ匕元素を置換した組
3
成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
提案されているが、その場合、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!、。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用いられて!/ヽ るのは PbTiOだけである。しかし、 PbTiOは環境汚染を引き起こす元素を含有するた
3 3
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く x≤0.15の l-2x 3
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いる
特許文献 1：特開昭 56-169301号公報
発明の開示
発明が解決しょうとする課題
[0005] 特許文献 1には、その実施例である Ba (BiNa) TiO (0く x≤0.15)に、半導体元素と l-2x 3
して、 Nd 0を 0.1モル％添カ卩した組成物が開示されている力 他の Nb、 Taの添加量に
2 3
ついては同文献には何ら記載がなぐ半導体ィ匕が不明である。
[0006] そこで発明者らは、特許文献 1に記載の Baの一部を Bi-Naで置換した組成系につ ヽ て検討したところ、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化元素 として添加すると、半導体ィ匕の効果が 1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を有し、これに対して半導体元素として上記の Nd
2
0を 0.1モル %添加している力 これでは PTC用途として十分な半導体ィ匕を実現でき
3
ないことを知見した。
[0007] この発明は、上述した従来の BaTiO系半導体磁器組成物の問題を解決し、 Pbを使
3
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、半導体磁器組成物の提供を目的としている。
課題を解決するための手段
[0008] 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などによつ
3
て置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の一部を A1元素 (Na、 K、 Liの少なくとも一種) と A2元素 (Bi)で置換するとともに、さらに Baを特定量の Q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。
[0009] また、発明者らは、 Baの一部を A1元素 (Na、 K、 Liの少なくとも一種)と Α2元素 (Bi)で 置換するとともに、 Tiの一部を特定量の M元素で置換することにより、上記と同様な効 果が得られることを知見し、さらに、この場合、上記の Q元素による置換量よりも少量 の置換量で原子価制御ができるという利点があることを知見し、この発明を完成した。
[0010] すなわち、この発明は、組成式を、 [(A1 A2 ) (Ba Q ) ]TiO
0.5 0.5 x 1-y y 1-χ 3
(但し、 Alは Na、 K、 Liの一種又は二種以上、 A2は Bi、 Qは La、 Dy、 Eu、 Gdの一種又 は二種以上)と表し、前記 x、 yが、 0〈x≤0.2、 0.002≤y≤0.01、より好ましくは yが 0.005 ≤y≤0.01を満足することを特徴とする半導体磁器組成物である。
[0011] また、この発明は、組成式を、 [(Al A2 ) Ba ][Ti M ]0
0.5 0.5 x 1-x 1-z z 3
(但し、 Alは Na、 K、 Liの一種又は二種以上、 A2は Bi、 Mは Nb、 Ta、 Sbの一種又は二 種以上)と表し、前記 x、 yが、 0〈x≤0.2、 0〈z≤0.01、より好ましくは 0〈z≤0.005を満足 することを特徴とする半導体磁器組成物である。
[0012] さらに、この発明は、上記構成の各半導体磁器組成物において、 それぞれ Si酸化物を 3.0mol%以下、 Ca酸化物を 4.0mol%以下添カ卩したことを特徴とす る半導体磁器組成物である。
発明の効果
[0013] この発明によれば、 BaTiO系半導体磁器組成物において、環境汚染を引き起こす
3
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た半導体磁器組成物を提供することができる。
[0014] この発明による BaTiO系半導体磁器組成物は、室温並びに所定の温度に達する
3
までの範囲における抵抗率が十分に低ぐ且つ目的温度域では抵抗率が急激に高 くなる比抵抗特性を有し、 PTCサーミスタ、 PTCヒータ、 PTCスィッチ、温度検知器など
、特に自動車用ヒータなどの用途に最適である。
発明を実施するための最良の形態
[0015] この発明の特徴は、 Baの一部を A1元素 (Na、 K、 Liの少なくとも一種、すなわち一種 又は二種以上)と A2元素 (Bi)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 Al、 A2元素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 Q元素 (La、 Dy、 Eu、 Gdの少なくとも一種)で置換し、 [(Al A
0.5
2 ) (Ba Q ) ]TiO組成とする力、または、 Tiの一部を特定量の M元素で置換し、 [(
0.5 1 1 3
Al A2 ) Ba ][Ti M ]0組成とすることにある。
0.5 0.5 x 1-x 1-z z 3
[0016] 各糸且成の限定理由は以下のとおりである。
[(Al A2 ) (Ba Q ) ]TiO組成物において、 Alは Na、 K、 Liの少なくとも一種、 A2
0.5 0.5 1 1 3
は Bi、 Qは La、 Dy、 Eu、 Gdの少なくとも一種である。好ましくは、 A1が Na、 Qが Laであ る。
[0017] 上記組成式中、 Xは A1+A2の成分範囲を示し、 0〈x≤ 0.2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、 0.2を超えると室温の抵抗率が 103 Ω cmを超えるため好ましくな!/、。
[0018] また、上記組成式中、 yは Qの成分範囲を示し、 0.002≤y≤0.01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 103 Ω c mを超えてしまう。また、 yが 0.01を超えると組成物が絶縁体ィ匕し、室温の抵抗率が 103 Ω cmを超えるため好ましくない。好ましくは 0.005≤y≤0.01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≤y≤0.01はモル％表記では 0.2モル％〜1.0 モノレ％となる。
[0019] [(Al A2 ) Ba ][Ti M ]0組成物において、 A1は Na、 K、 Liの少なくとも一種、 A2
0.5 0.5 X 1-x 1-z z 3
は Bi、 Mは Nb、 Ta、 Sbの少なくとも一種である。好ましくは、 A1が Na、 Mが Nbである。
[0020] 上記組成式中、 Xは A1+A2の成分範囲を示し、 0〈x≤ 0.2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、 0.2を超えると室温の抵抗率が 103 Ω cmを超えるため好ましくない。また、 zは Mの成分範囲を示し、 0〈z≤0.01が好ま しい範囲である。 zが 0では原子価制御ができず、組成物が半導体化せず、 0.01を超 えると室温の抵抗率が 103 Ω cmを超えるため好ましくない。より好ましくは 0く z≤ 0.005 である。なお、上記 0〈z≤0.01はモル％表記で 0〜1モル％(0を含まず)となる。
[0021] 上記 [(Al A2 ) Ba ][Ti M ]0組成物の場合、原子価制御を行うために、 Tiを M
0.5 0.5 X 1-x 1-z z 3
元素で置換するが、この場合、 M元素の添加 (好ましい添カ卩量 0〈z≤ 0.005)は、 4価の 元素である Tiサイトの原子価制御を目的としているため、前記 [(Al A2 ) (Ba Q )
0.5 0.5 X 1-y y 1-χ
]ΉΟ組成物における Q元素の添カ卩量 (0.002≤y≤0.01)よりも少量で原子価制御を行
3
うことができ、この発明による組成物の内部歪を軽減できるなどの利点を有する。
[0022] 前記の [(Al A2 ) (Ba Q ) ]TiO組成物及び [(Al A2 ) Ba ][Ti M ]0組成
0.5 0.5 x 1-y y 1-χ 3 0.5 0.5 x l-χ 1-z z 3 物において、 Si酸化物を 3.0mol%以下、 Ca酸化物を 4.0mol%以下添カ卩することにより、 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。
[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。
(1)各元素の酸化物粉末を準備し、それらを秤量の後、混合する。
(2)混合体を純水またはエタノール中でさらに混合した後、乾燥し、混合粉を得る。
(3)混合粉を 900°C〜1100°Cで 2〜6時間仮焼する。
(4)仮焼体を純水またはエタノール中で粉砕した後、乾燥する。
(5)粉砕粉を PVAなどを用いて造粒した後、一軸プレス機によって成形する。
(6)成形体を 300°C〜700°Cで脱バインダー処理を行った後、大気中または還元雰囲 気中で、 1200°C〜1450°Cで 2〜6時間焼結する。
実施例 [0024] 実施例 1
主原料として BaCO、 TiO、半導体化元素として La 0、 Dy 0、 Eu 0、 Gd 0、 Nb
3 2 2 3 2 3 2 3 2 3 2
O、 Ta O、 Sb O、焼結助剤として SiO、 CaO、さらにキュリー温度のシフタ一として (N
5 2 5 2 3 2
a CO -Bi O -TiO )、 (K CO -Bi O -TiO )、 (Li CO -Bi O -TiO )の各粉末を準備した
2 3 2 3 2 2 3 2 3 2 2 3 2 3 2
。各粉末を表 1〜表 6に示す如く配合し、純水中で混合した後乾燥し、平均粒径 0.6〜
1.2 /z mの混合粉を得た。
[0025] 次 、で、該混合粉を組成に応じて 900°C〜1100°Cで 2〜6時間仮焼した。得られた 仮焼粉を純水中で平均粒径 0.8〜1.5 μ mになるまで粉砕した後、粉砕粉を乾燥させ た。次に、乾燥粉に PVAを添加し、混合した後、造粒装置によって造粒した。
[0026] 得られた造粒粉を一軸プレス装置により、成形密度 2〜3g/cm3に成形した。得られ た成形体を 300°C〜700°Cで脱バインダー後、酸素濃度 75%の雰囲気中において、 13
00°C〜1360°Cで 4時間焼結し、焼結体を得た。
[0027] 得られた焼結体を 10mm X 10mm X 0.1mmの板状に加工し、試験片を得た。得られ た試験片を抵抗測定に際し、室温から 200°Cまでの範囲で抵抗値の変化を測定した
。測定結果を表 1〜表 6に示す。
[0028] 表 1の No.l〜29が、 [(Al Bi ) Ba ][Ti Nb ]0組成物の場合、
0.5 0.5 X 1-x 1-z z 3
表 2の No.30〜56が、 [(Al Bi ) Ba ][Ti Sb ]0組成物の場合、
0.5 0.5 x 1-x 1-z z 3
表 3の No57〜86が、 [(Al Bi ) (Ba La ) ]Ti〇組成物の場合、
0.5 0.5 x 1-y y 1-χ 3
表 4の Νο·87〜： 102が、 [(Al Bi ) (Ba Gd ) ]Ti〇組成物の場合、
0.5 0.5 x 1-y y 1-χ 3
表 5の Νο·103〜118が、 [(Al Bi ) (Ba Eu ) ]Ti〇組成物の場合、
0.5 0.5 x 1-y y 1-χ 3
表 6の Νο·119〜134が、 [(Al Bi ) (Ba Dy ) ]Ti〇組成物の場合を示す。
0.5 0.5 X 1-y y 1-χ 3
[0029] 比較例 1
表 1〜表 6中、 No.欄に *印を付してあるものは比較例である。すなわち、表 1で No.l 〜4、 No.ll、表 2で No.30、 No.31、 No.44、表 3で No.57、 No.58、表 4で No.87、 No.88、 表 5で No.103、 No.104、表 5で No.119、 No.120は比較例である。
[0030] 実施例 2
主原料として BaCO、 TiO、半導体化元素として La 0、 Nb 0、キュリー温度のシフ
3 2 2 3 2 5
ターとして (Na CO -Bi O -TiO )の各粉末を準備した。各粉末を表 7〜表 8に示す如く 配合し、純水中で混合した後乾燥し、平均粒径0.6〜1.2 iu mの混合粉を得た。
[0031] 次 、で、該混合粉を組成に応じて 900°C〜1100°Cで 2〜6時間仮焼した。得られた 仮焼粉を純水中で平均粒径 0.8〜1.5 μ mになるまで粉砕した後、粉砕粉を乾燥させ た。次に、乾燥粉に PVAを添加し、混合した後、造粒装置によって造粒した。
[0032] 得られた造粒粉を一軸プレス装置により、成形密度 2〜3g/cm3に成形した。得られ た成形体を 300°C〜700°Cで脱バインダー後、酸素濃度 75%の雰囲気中において、 13
80°C〜1450°Cで 4時間焼結し、焼結体を得た。
[0033] 得られた焼結体を 10mm X 10mm X 0.1mmの板状に加工し、試験片を得た。得られ た試験片を抵抗測定で室温から 200°Cまでの範囲で抵抗値の変化を測定した。測定 結果を表 7〜表 8に示す。
表 7の Νο.135〜144が、 [(Al Bi ) Ba ][Ti Nb ]0組成物の場合、
0.5 0.5 1 1 3
表 8の Νο·145〜154が、 [(Al Bi ) (Ba La ) ]Ti〇組成物の場合を示す。
0.5 0.5 1 1 3
[0034] 比較例 2
表 7〜表 8中、 No.欄に *印を付してあるものは比較例である。すなわち、表 7で No.13
5、 No.136、表 8で No.145、 No.146は比較例である。
[0035] 表 1〜表 8から明らかなように、本発明による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 低下させることが分かる。
[0036] [表 1]
Figure imgf000008_0001
Figure imgf000008_0002
69.M0/S00Zdf/X3d L
[ε挲] [8εοο]
Figure imgf000009_0001
69Z.riO/SOOZdf/X3d 8
Figure imgf000010_0001
Figure imgf000010_0002
69LPW/S ZdT/13d 6 ZTSCZO/.OOZ OAV [9挲] [IW)0]
Figure imgf000011_0001
69.M0/S00Zdf/X3d [sm [ε濯]
] 濯]
Figure imgf000012_0001
69Z.M0/S00Zdf/X3d ZTSCZO/ .OOZ OAV Al=Na i.a.bKaLib Si02 CaO p 30 Tc
No. y
a b (mol%) (mol%) ( Ω cm) (°C)
145* 0 0 0 0 0 0 絶縁物 -
146* 0 0 0 0.005 0 0 333 111
147 0 0 0.02 0.002 0 0 82 131
148 0 0 0.02 0.005 0 0 72 131
149 0 0 0.02 0.008 0 0 69 132
150 0 0 0.02 0.001 0 0 91 133
151 0 0 0.06 0.002 0 0 103 161
152 0 0 0.06 0.005 0 0 88 160
153 0 0 0.06 0.008 0 0 70 161
154 0 0 0.06 0.01 0 0 86 160 産業上の利用可能性
この発明によると、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に、室温における抵抗率を大幅に低下させることができる ので、 PTCサーミスタ、 PTCヒータ、 PTCスィッチ、温度検知器など利用することができ る。特に自動車用ヒータなど、人体への影響が懸念される用途には最適である。

Claims

請求の範囲
[1] 組成式を、 [(Al A2 ) (Ba Q ) ]TiO
0.5 0.5 x 1-y y 1-x 3
(但し、 Alは Na、 K、 Liの一種又は二種以上、 A2は Bi、 Qは La、 Dy、 Eu、 Gdの一種又 は二種以上)と表し、前記 x、 yが、 0く x≤0.2、 0.002≤y≤ 0.01を満足する半導体磁器 組成物。
[2] yが、 0.005≤y≤ 0.01を満足する請求項 1に記載の半導体磁器組成物。
[3] 組成式を、 [(Al A2 ) Ba ][Ti M ]0
0.5 0.5 x 1-x 1-z z 3
(但し、 Alは Na、 K、 Liの一種又は二種以上、 A2は Bi、 Mは Nb、 Ta、 Sbの一種又は二 種以上)と表し、前記 x、 yが、 0く x≤0.2、 0く z≤0.01を満足する半導体磁器組成物。
[4] zが、 0く z≤0.005を満足する請求項 3に記載の半導体磁器組成物。
[5] Si酸化物を 3.0mol%以下、 Ca酸化物を 4.0mol%以下添カ卩した請求項 1または請求項 3 に記載の半導体磁器組成物。
PCT/JP2005/014769 2004-03-12 2005-08-11 半導体磁器組成物 WO2007023512A1 (ja)

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KR1020127017389A KR101197009B1 (ko) 2005-08-11 2005-08-11 반도체 자기 조성물
CN2005800513054A CN101272998B (zh) 2005-08-11 2005-08-11 半导体瓷器组成物
PCT/JP2005/014769 WO2007023512A1 (ja) 2005-08-11 2005-08-11 半導体磁器組成物
KR1020117024173A KR101118320B1 (ko) 2005-08-11 2005-08-11 반도체 자기 조성물
EP12170169A EP2497759A3 (en) 2005-08-11 2005-08-11 Semiconductor porcelain composition
EP05770429.8A EP1921052B8 (en) 2005-08-11 2005-08-11 Semiconductor ceramic composition
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP2159207A1 (en) * 2007-06-14 2010-03-03 Murata Manufacturing Co. Ltd. Semiconductor ceramic material
JP5223927B2 (ja) * 2008-09-30 2013-06-26 株式会社村田製作所 チタン酸バリウム系半導体磁器組成物及びｐｔｃサーミスタ

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5590494B2 (ja) * 2008-03-27 2014-09-17 日立金属株式会社 半導体磁器組成物−電極接合体の製造方法
US8076257B1 (en) * 2008-04-23 2011-12-13 MRA Laboratories, Inc High temperature ceramic dielectric composition and capacitors made from the composition
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WO2012140811A1 (ja) * 2011-04-14 2012-10-18 パナソニック株式会社 圧電体膜、インクジェットヘッド、角速度センサ、圧電発電素子
CN104370539A (zh) * 2013-09-12 2015-02-25 铜仁学院 一种高使用温度无铅ptcr陶瓷及其制备方法
JP6337689B2 (ja) 2013-10-03 2018-06-06 Tdk株式会社 半導体磁器組成物およびｐｔｃサーミスタ
KR102166127B1 (ko) * 2015-12-28 2020-10-15 삼성전기주식회사 유전체 조성물 및 이를 포함하는 적층 세라믹 커패시터
CN105967681B (zh) * 2016-05-10 2019-02-05 湖北天瓷电子材料有限公司 一种抗还原x9r型介质陶瓷材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5058106A (ja) * 1973-09-24 1975-05-20
JPS56169301A (en) 1980-06-02 1981-12-26 Tohoku Metal Ind Ltd Method of producing barium titanate semiconductor porcelain
JPS5916303A (ja) * 1982-07-19 1984-01-27 松下冷機株式会社 半導体磁器材料の製造方法
JP2002160967A (ja) * 2000-11-20 2002-06-04 Matsushita Electric Ind Co Ltd 圧電磁器組成物
JP2005255493A (ja) * 2004-03-12 2005-09-22 Neomax Co Ltd 半導体磁器組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020036282A1 (en) * 1998-10-19 2002-03-28 Yet-Ming Chiang Electromechanical actuators
TWI389868B (zh) * 2005-04-28 2013-03-21 Hitachi Metals Ltd Semiconductor porcelain composition and method of manufacturing the same
JP5228917B2 (ja) * 2006-10-27 2013-07-03 日立金属株式会社 半導体磁器組成物とその製造方法
EP2077256B1 (en) * 2006-10-27 2013-09-04 Hitachi Metals, Ltd. Semiconductor ceramic composition and method for producing the same
KR20090082198A (ko) * 2006-11-01 2009-07-29 히다찌긴조꾸가부시끼가이사 반도체 자기 조성물과 그 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5058106A (ja) * 1973-09-24 1975-05-20
JPS56169301A (en) 1980-06-02 1981-12-26 Tohoku Metal Ind Ltd Method of producing barium titanate semiconductor porcelain
JPS5916303A (ja) * 1982-07-19 1984-01-27 松下冷機株式会社 半導体磁器材料の製造方法
JP2002160967A (ja) * 2000-11-20 2002-06-04 Matsushita Electric Ind Co Ltd 圧電磁器組成物
JP2005255493A (ja) * 2004-03-12 2005-09-22 Neomax Co Ltd 半導体磁器組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AOTO A. ET AL.: "(Na1/2Bi1/2)TiO3-BaTiO3 Ceramics no Sakusei to Handotaika", THE CERAMIC SOCIETY OF JAPAN 2005 NEN NENKAI KOEN YOKOSHU, 22 March 2005 (2005-03-22), pages 81, XP008077275 *
See also references of EP1921052A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2159207A1 (en) * 2007-06-14 2010-03-03 Murata Manufacturing Co. Ltd. Semiconductor ceramic material
EP2159207A4 (en) * 2007-06-14 2014-06-18 Murata Manufacturing Co CERAMIC MATERIAL FOR SEMICONDUCTORS
KR100941522B1 (ko) * 2008-01-17 2010-02-10 한국세라믹기술원 납성분을 포함하지 않는 ｐｔｃ 써미스터용 세라믹 조성물및 이에 의해 제조되는 ｐｔｃ 세라믹 써미스터
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
US8766145B2 (en) 2008-03-19 2014-07-01 Hitachi Metals, Ltd. Process for producing semiconductive porcelain composition and heater employing semiconductive porcelain composition
JP5223927B2 (ja) * 2008-09-30 2013-06-26 株式会社村田製作所 チタン酸バリウム系半導体磁器組成物及びｐｔｃサーミスタ

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