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WO2009116452A1 - 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 - Google Patents

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 Download PDF

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WO2009116452A1
WO2009116452A1 PCT/JP2009/054809 JP2009054809W WO2009116452A1 WO 2009116452 A1 WO2009116452 A1 WO 2009116452A1 JP 2009054809 W JP2009054809 W JP 2009054809W WO 2009116452 A1 WO2009116452 A1 WO 2009116452A1
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ceramic composition
semiconductor ceramic
tio
calcined powder
heat treatment
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French (fr)
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武司 島田
健太郎 猪野
年紀 木田
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Proterial Ltd
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Hitachi Metals Ltd
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Priority to EP09723025.4A priority Critical patent/EP2253602A4/en
Priority to US12/920,366 priority patent/US8766145B2/en
Priority to CN2009801071730A priority patent/CN101959829A/zh
Publication of WO2009116452A1 publication Critical patent/WO2009116452A1/ja
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    • 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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/663—Oxidative annealing

Definitions

  • the present invention relates to a method for producing a semiconductor porcelain composition having a positive temperature coefficient of resistance (PTC) and a heater using the semiconductor porcelain composition.
  • PTC positive temperature coefficient of resistance
  • a BaTiO 3 -based semiconductor ceramic composition is known as a material exhibiting positive resistance temperature characteristics.
  • SrTiO 3 or PbTiO 3 is added to the BaTiO 3 based semiconductor ceramic composition, the Curie temperature can be shifted, but the only additive material that can be shifted in the positive direction is PbTiO 3 .
  • PbTiO 3 contains an element that causes environmental pollution, a material that does not use PbTiO 3 as an additive material is desired. Therefore, a semiconductor ceramic composition in which a part of Ba of BaTiO 3 is substituted with Bi—Na has been proposed (see Patent Document 1).
  • the present invention has been made in view of the above circumstances, BaTiO 3 - (Bi 1/2 Na 1/2) semiconductors a part of Ba of BaTiO 3 of TiO 3 based material comprising substituted with Bi-Na It aims at improving the jump characteristic of a porcelain composition.
  • the jump characteristic of the BaTiO 3 based material containing Pb depends on the amount of oxygen at the grain boundary, it is necessary to introduce oxygen into the grain boundary after reducing oxygen defects generated during sintering. For this reason, practical jump characteristics cannot be obtained unless heat treatment is performed at 800 ° C. or higher at which oxygen defects are recovered.
  • the BaTiO 3- (Bi 1/2 Na 1/2 ) TiO 3 system material not only the grain boundary oxygen amount but also the material component distribution affects the jump characteristics. For this reason, it is possible to improve jump characteristics simply by introducing oxygen into the grain boundary without recovering oxygen defects. For this reason, it has been found that jump characteristics can be improved even if heat treatment is performed at 600 ° C. or lower.
  • the present invention improves the jump characteristics by heat-treating a semiconductor ceramic composition in which a part of Ba is substituted with Bi-Na at 600 ° C. or lower.
  • the heat treatment may be performed in the air, but is preferably performed in an atmosphere containing oxygen, and more preferably heat treatment in an oxygen atmosphere.
  • the present invention improves jump characteristics by forming an electrode on a semiconductor ceramic composition in which a part of Ba is substituted with Bi-Na and then heat-treating it in the atmosphere at 600 ° C. or lower.
  • heat treatment in the atmosphere is preferable to avoid electrode deterioration.
  • the semiconductor ceramic composition manufactured according to the present invention is manufactured according to the present invention because it has a jump characteristic not found in the conventional semiconductor ceramic composition in which part of BaTiO 3 is replaced with Bi-Na.
  • a heater using a heating element made of a semiconductor ceramic composition is suitable for use in a higher temperature environment.
  • a BaTiO 3 — (Bi 1/2 Na 1/2 ) TiO 3 material obtained by substituting a part of Ba with Bi—Na is heat-treated at 600 ° C. or less.
  • the temperature exceeds 600 ° C. the BaTiO 3 — (Bi 1/2 Na 1/2 ) TiO 3 -based material gradually exhibits insulating properties and becomes an insulator at 1280 ° C.
  • the upper limit of the heat treatment temperature was set to 600 ° C., which is a practically acceptable range.
  • the processing time is preferably about 12 hours because the jump characteristic is saturated even if it is too long. Note that the effect can be obtained if heat treatment is performed for a long time even near room temperature. Also, heat treatment in nitrogen is not preferable because it reduces the jump characteristics.
  • the step of preparing (BaQ) TiO 3 calcined powder (Q is a semiconducting element) is first performed by using raw material powders of BaCO 3 , TiO 2 and a semiconducting element, such as La 2 O 3 or Nb 2 O. 5 is mixed and a raw material powder is produced and calcined.
  • the calcination temperature is preferably in the range of 600 ° C. to 1000 ° C., and the calcination time is preferably 0.5 hours or more. When the calcining temperature is less than 600 ° C.
  • the step of preparing the (BiNa) TiO 3 calcined powder first comprises dry mixing the raw material powder Na 2 CO 3 , Bi 2 O 3 and TiO 2 to produce a mixed raw material powder and calcining it.
  • the calcination temperature is preferably in the range of 700 ° C. to 950 ° C., and the calcination time is preferably 0.5 hours to 10 hours.
  • the calcination temperature is less than 700 ° C. or the calcination time is less than 0.5 hour, unreacted NaO reacts with the solvent in the atmosphere or wet mixing, which is not preferable because the composition shifts and the characteristics vary.
  • the calcining temperature exceeds 950 ° C. or the calcining time exceeds 10 hours, the volatilization of Bi proceeds, the composition shifts, and the generation of the secondary phase is promoted.
  • the step of mixing (BaQ) TiO 3 calcined powder and (BiNa) TiO 3 calcined powder is performed after blending each calcined powder in a predetermined amount.
  • Mixing may be either wet mixing using pure water or ethanol, or dry mixing. However, it is preferable to perform dry mixing because the compositional deviation can be further prevented.
  • the particle size of the calcined powder after mixing, pulverization or mixing and pulverization may be performed simultaneously.
  • the average particle size of the mixed calcined powder after mixing and pulverization is preferably 0.6 ⁇ m to 1.5 ⁇ m.
  • Si oxide when Si oxide is added in an amount of 3.0 mol% or less and Ca carbonate or Ca oxide is added in an amount of 4.0 mol% or less, Si oxide suppresses abnormal growth of crystal grains and easily controls the resistivity.
  • Ca carbonate or Ca oxide is preferable because it can improve the sinterability at low temperatures. In any case, adding more than the above-mentioned limited amount is not preferable because the composition does not show semiconducting properties. The addition is preferably performed before mixing in each step.
  • the step of molding and sintering the calcined powder obtained by mixing the (BaQ) TiO 3 calcined powder and the (BiNa) TiO 3 calcined powder first forms the mixed calcined powder by a desired molding means. .
  • the compact density after molding is preferably 2 to 3 g / cm 3 .
  • Sintering can be performed in the air, in a reducing atmosphere, or in an inert gas atmosphere having a low oxygen concentration, with a sintering temperature of 1200 ° C. to 1400 ° C. and a sintering time of 2 hours to 6 hours.
  • the sintered body is processed into a plate shape to produce a test piece, and then an ohmic electrode is formed on the surface.
  • the ohmic electrode Ti, Cr, Ni, Al, Fe, Cu, Ag—Zn, or the like can be selected.
  • the ohmic electrode may be formed on the test piece by sputtering or vapor deposition.
  • the electrode is preferably covered with a cover electrode such as Ag, Al, Au, or Pt.
  • Example 1 A raw material powder of BaCO 3 as a main material and La 2 O 3 as a TiO 2 semiconducting element is prepared, blended so as to be (Ba 0.994 La 0.006 ) TiO 3, and further, if necessary, a sintering aid And CaCO 3 and SiO 2 were added and mixed in ethanol. The obtained mixed raw material powder was calcined in the atmosphere at 900 ° C. for 4 hours to prepare (BaLa) TiO 3 calcined powder.
  • the (BaLa) TiO 3 calcined powder and (BiNa) TiO 3 calcined powder are combined with [(Bi 0.5 Na 0.5 ) 0.1 (Ba 0.994 La 0.006 ) 0.9 ] TiO 3 .
  • the mixture was mixed and pulverized with a pot mill using pure water as a medium until the mixed calcined powder became 1.0 ⁇ m to 2.0 ⁇ m, and then dried.
  • PVA was added to and mixed with the pulverized powder of the mixed calcined powder, and then granulated by a granulator.
  • the obtained granulated powder was molded with a uniaxial press machine, and the molded body was debindered at 700 ° C.
  • (BaLa) TiO 3 calcining temperature is 900 ° C. or lower, BaCO 3 and TiO 2 can remain in the calcined powder, or (BaLa) TiO 3 calcining temperature is 1000 ° C. or higher and 1200 ° C. or lower.
  • the properties can be stabilized by adding BaCO 3 and TiO 2 to the calcined powder.
  • the obtained sintered body is processed into a 10 mm ⁇ 10 mm ⁇ 1 mm plate to create a test piece, and an ohmic electrode composed of Ag—Zn and a cover electrode containing Ag as a main component are simultaneously baked thereon.
  • the temperature change of the specific resistance value was measured with a resistance meter in the range from room temperature to 270 ° C., and the PTC was specified as room temperature specific resistance, Curie temperature, resistance temperature coefficient ((lnR 1 -lnR c ) ⁇ 100 / (T 1 -T c ), R 1 : maximum resistance ratio, R c : specific resistance at T c , T 1 : temperature showing R 1 , T c : Curie temperature).
  • the electrode was removed and heat treatment was performed from room temperature to 800 ° C. After the heat treatment, an electrode was formed again on the material, and the PTC characteristics were evaluated.
  • Table 1 shows PTC characteristics when heat treatment is performed at 20 ° C. to 600 ° C. in an oxygen atmosphere
  • Table 2 shows PTC characteristics when heat treatment is performed at 20 ° C. to 800 ° C. in air, and resistance temperature coefficient. It was confirmed that both the samples subjected to the heat treatment in the atmosphere and the air showed higher values than the resistance temperature coefficient before the heat treatment.
  • Example 2 PTC characteristics were measured in the same manner as in Example 1. After the measurement, heat treatment was performed from room temperature to 800 ° C. without removing the electrode. When heat treatment was performed in an oxygen atmosphere with the electrode formed, the electrode deteriorated, and even if the treatment was performed in nitrogen, there was no effect, so the heat treatment was performed in the atmosphere. After the heat treatment, the PTC characteristics were evaluated.
  • Table 3 shows the PTC characteristics when heat treatment is performed at 20 ° C. to 800 ° C. in the atmosphere. Focusing on the temperature coefficient of resistance, it was confirmed that all samples subjected to heat treatment in the atmosphere showed higher values than the temperature coefficient of resistance before heat treatment up to 600 ° C. However, it was confirmed that a value lower than the temperature coefficient of resistance before heat treatment was exhibited at 800 ° C.
  • FIG. 1 shows the configuration of the heater element, and the heater element 15 is sandwiched between a pair of casings 13 (13 a, 13 b) provided with heat radiation fins 11.
  • the heater element 15 can generate heat by applying a voltage to the heater element 15 via the power supply terminal 17a provided on one casing 13a and the power supply terminal 17b provided on the other casing 13b.
  • the prepared heater element was placed in a thermostatic chamber, and after raising the temperature to a predetermined temperature, a voltage of 13 volts was applied to the power feeding element, and changes in voltage and current with respect to temperature were observed (see Table 4).
  • FIG. 2 is a graph showing changes in voltage and current (vertical axis) with respect to temperature (horizontal axis). The characteristics of the case with heat treatment ((b) in the figure) are higher than those without heat treatment ((a) in the figure). On the side, the current value is extremely low, and it can be seen that the safety at high temperature is improved.
  • the semiconductor ceramic composition according to the present invention has jump characteristics that are not found in the conventional semiconductor ceramic composition in which part of BaTiO 3 is replaced with Bi—Na.
  • a heater using a heating element made of this semiconductor ceramic composition is suitable for use in a higher temperature environment.

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Abstract

　ＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料のジャンプ特性を向上させる。 　ＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換した半導体磁器組成物の製造方法であって、（ＢａＱ）ＴｉＯ３仮焼粉（Ｑは半導体化元素）を用意する工程、（ＢｉＮａ）ＴｉＯ３仮焼粉を用意する工程、前記（ＢａＱ）ＴｉＯ３仮焼粉及び前記（ＢｉＮａ）ＴｉＯ３仮焼粉を混合する工程、混合した仮焼粉を成形し焼結する工程、得られた焼結体を６００°C以下で熱処理する工程、前記工程で作製した素子を用いたＰＴＣヒータを含む。

Description

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
　本発明は正の抵抗温度係数（ＰＴＣ）を有する半導体磁器組成物の製造方法及び該半導体磁器組成物を用いたヒータに関する。
　正の抵抗温度特性を示す材料としてＢａＴｉＯ３系半導体磁器組成物が知られている。ＢａＴｉＯ３系半導体磁器組成物にＳｒＴｉＯ３やＰｂＴｉＯ３を添加するとキュリー温度をシフトさせることができるが、正方向へシフトできる添加材料はＰｂＴｉＯ３だけである。しかし、ＰｂＴｉＯ３は環境汚染を引き起こす元素を含有するため、添加材料としてＰｂＴｉＯ３を使用しない材料が望まれる。そこで、ＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換して成る半導体磁器組成物が提案されている（特許文献１参照）。
　ＢａＴｉＯ３系材料において、還元雰囲気中で焼結するなど、室温比抵抗が小さくなるように処理すると、抵抗温度係数（ジャンプ特性）が低下するという問題がある。ジャンプ特性が低下すると目的温度でスイッチングしないという問題がある。そこで、ジャンプ特性を改善するために、１１００℃を越える高温で熱処理を行うことが提案されている（特許文献２）
ＷＯ２００６－１０６９１０号公報 特開昭５６－１６９３０１号公報
　近年、ＰＴＣ材料の耐熱特性が向上したこともあり、高温環境で使用されることが多くなっているが、更に高い温度環境で使用を可能とするためにさらなるジャンプ特性の改善が望まれている。Ｐｂを含まずＢａの一部をＢｉ-Ｎａで置換して成るＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料は、それ自体、十分なジャンプ特性を有するものの、上述の要望からジャンプ特性を向上させる必要がある。ジャンプ特性向上のためには、上述のような熱処理が考えられるが、Ｐｂを含むＢａＴｉＯ３系材料に対する熱処理をそのまま適用してもジャンプ特性の改善に至らないことが確認できた。
　本発明は、上記事情に鑑みてなされたもので、ＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料等のＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換して成る半導体磁器組成物のジャンプ特性を向上させることを目的とする。
　本発明者らが、ＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料に対する熱処理を行ったところ、素子が処理温度１２８０℃で絶縁体となるなど、高温熱処理によりＰＴＣ特性が損なわれることが確認された。この理由として、原子価制御により生成した３価のＴｉが４価に酸化し、キャリアが減少することが考えられる。
　また、Ｐｂを含むＢａＴｉＯ３系材料のジャンプ特性は粒界の酸素量に依存しているため、焼結中に生じた酸素欠陥を低減した後、粒界に酸素を導入する必要がある。このため、酸素欠陥が回復する８００℃以上で熱処理を行わなければ実用可能なジャンプ特性を得ることができない。一方、ＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料は粒界酸素量のみならず材料の成分分布もジャンプ特性に影響を与えている。このため、酸素欠陥を回復させずに粒界に酸素を導入するだけでもジャンプ特性を改善することが可能となる。このため、６００℃以下で熱処理を行ってもジャンプ特性を改善することができるとの知見を得た。
　上記知見に基づき、本発明はＢａの一部をＢｉ-Ｎａで置換した半導体磁器組成物を６００℃以下で熱処理することでジャンプ特性を向上させるものである。熱処理は大気中でもよいが、酸素を含む雰囲気中が好ましく、より速効的には酸素雰囲気中の熱処理が好ましい。
　また、本発明はＢａの一部をＢｉ-Ｎａで置換した半導体磁器組成物に電極を形成した後、大気中６００℃以下で熱処理することでジャンプ特性を向上させるものである。電極を形成した場合、電極劣化を避けるため、大気中での熱処理が好ましい。
　本発明により製造された半導体磁器組成物は、ＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換した従来の半導体磁器組成物には見られないジャンプ特性を有することから、本発明により製造された半導体磁器組成物からなる発熱体を用いたヒータは、より高温環境下での使用に適したものとなる。
　本発明によれば、Ｂａの一部をＢｉ-Ｎａで置換した半導体磁器組成物のジャンプ特性を向上させることができる。
ヒータ素子の構成を示す概略図である。 ヒータ素子の温度に対する電圧、電流の変化を示すグラフである。
符号の説明
　１１　放熱フィン
　１３ａ、１３ｂ　ケーシング
　１５　ヒータ素子
　１７ａ、１７ｂ　給電素子
　本発明は、Ｂａの一部をＢｉ-Ｎａで置換して成るＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料を６００℃以下で熱処理するものである。６００℃を越えるとＢａＴｉＯ３－（Ｂｉ１/２Ｎａ１/２）ＴｉＯ３系材料は次第に絶縁特性を呈し、１２８０℃で絶縁体となる。このため、実用上問題のない範囲である６００℃を熱処理温度の上限とした。処理時間については余り長くてもジャンプ特性が飽和することから１２時間程度が好ましい。なお、室温付近でも長時間、熱処理を行えば効果を得ることができる。また窒素中での熱処理はジャンプ特性を低下させるため好ましくない。
　本発明において、（ＢａＱ）ＴｉＯ３仮焼粉（Ｑは半導体化元素）を用意する工程は、まず、ＢａＣＯ３、ＴｉＯ２と半導体化元素の原料粉末、例えば、Ｌａ２Ｏ３やＮｂ２Ｏ５を混合して原料粉末を作成し仮焼する。仮焼温度は６００℃から１０００℃の範囲が好ましく、仮焼時間は０．５時間以上が好ましい。仮焼温度が６００℃未満あるいは仮焼時間が０．５時間未満では（ＢａＱ）ＴｉＯ３が殆ど形成されず、未反応のＢａＣＯ３、ＢａＯ、ＴｉＯ２が（ＢｉＮａ）ＴｉＯ３との均一反応を阻害し、ＰＴＣ特性の発現を妨げるため好ましくない。また、仮焼温度が１０００℃を越えると、Ｂｉ揮散を調整する効果がなくなり安定な（ＢａＱ）ＴｉＯ３－（ＢｉＮａ）ＴｉＯ３を生成の妨げになり好ましくない。
　本発明において、（ＢｉＮａ）ＴｉＯ３仮焼粉を用意する工程は、まず、原料粉末となるＮａ２ＣＯ３、Ｂｉ２Ｏ３、ＴｉＯ２を乾式混合して混合原料粉末を作製し仮焼する。仮焼温度は７００℃から９５０℃の範囲が好ましく、仮焼時間は０．５時間から１０時間が好ましい。仮焼温度が７００℃未満あるいは仮焼時間が０．５時間未満では未反応のＮａＯが雰囲気の水分あるいは湿式混合の場合は、その溶媒と反応し、組成ずれや特性のバラツキを生じるため好ましくない。また、仮焼温度が９５０℃を越えるかあるいは仮焼時間が１０時間を越えると、Ｂｉの揮散が進み、組成ずれを起こし、二次相の生成が促進されるため好ましくない。
　本発明において、（ＢａＱ）ＴｉＯ３仮焼粉及び（ＢｉＮａ）ＴｉＯ３仮焼粉を混合する工程は、各仮焼粉を所定量に配合した後、混合する。混合は、純水やエタノールを用いた湿式混合または乾式混合のいずれでもよいが、乾式混合を行うと、組成ずれをより防止することができ好ましい。また、仮焼粉の粒度に応じて、混合の後、粉砕あるいは混合と粉砕を同時に行ってもよい。混合、粉砕後の混合仮焼粉の平均粒度は、０．６μｍから１．５μｍが好ましい。
　上記工程において、Ｓｉ酸化物を３．０ｍｏｌ％以下、Ｃａ炭酸塩またはＣａ酸化物を４．０ｍｏｌ％以下添加すると、Ｓｉ酸化物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炭酸塩またはＣａ酸化物は低温での焼結性を向上させることができ好ましい。いずれも上記限定量を超えて添加すると、組成物が半導体化を示さなくなるため好ましくない。添加は各工程における混合前に行うことが好ましい。
　本発明において、（ＢａＱ）ＴｉＯ３仮焼粉及び（ＢｉＮａ）ＴｉＯ３仮焼粉を混合した仮焼粉を成形し焼結する工程は、まず、混合仮焼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よい。成形後の成形体密度は２～３ｇ／ｃｍ３が好ましい。焼結は、大気中または還元雰囲気中あるいは低酸素濃度の不活性ガス雰囲気中で、焼結温度１２００℃から１４００℃、焼結時間は２時間から６時間で行うことができる。なお、成形前に造粒を行った場合は、焼結前に３００℃から７００℃で脱バインダー処理を行うことが好ましい。
　本発明において、半導体磁器組成物に電極を形成する工程は、焼結体を板状に加工して試験片を作製した後、表面にオーミック電極を形成する。オーミック電極として、Ｔｉ、Ｃｒ、Ｎｉ、Ａｌ、Ｆｅ、Ｃｕ、Ａｇ－Ｚｎ等が選択し得る。オーミック電極の形成は試験片に焼き付ける他、スパッタや蒸着でもよい。オーミック電極を保護するため同電極をカバー電極、例えば、ＡｇやＡｌ、Ａｕ、Ｐｔで覆うことが好ましい。
（実施例１）
　主材料としてＢａＣＯ３、ＴｉＯ２半導体化元素としてＬａ２Ｏ３の原料粉末を準備し、（Ｂａ０．９９４Ｌａ０．００６）ＴｉＯ３となるように配合し、さらに、必要により焼結助剤としてＣａＣＯ３、ＳｉＯ２を添加し、エタノール中で混合した。得られた混合原料粉末を９００℃で４時間大気中仮焼し、（ＢａＬａ）ＴｉＯ３仮焼粉を用意した。
　Ｎａ２ＣＯ３、Ｂｉ２Ｏ３、ＴｉＯ２の原料粉末を準備し、（Ｂｉ０．５Ｎａ０．５）ＴｉＯ３となるように配合し、さらに、必要により焼結助剤を添加し、大気中又はエタノール中で混合した。得られた混合原料粉末を８００℃で４時間大気中仮焼し、（ＢｉＮａ）ＴｉＯ３仮焼粉を用意した。
　上記（ＢａＬａ）ＴｉＯ３仮焼粉と（ＢｉＮａ）ＴｉＯ３仮焼粉を[（Ｂｉ０．５Ｎａ０．５）０．１（Ｂａ０．９９４Ｌａ０．００６）０．９] ＴｉＯ３となるように配合し、純水を媒体としてポットミルにより、混合仮焼粉が１．０μｍから２．０μｍになるまで混合、粉砕した後、乾燥させた。この混合仮焼粉の粉砕粉にＰＶＡを添加、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、上記成形体を７００℃で脱バインダー後、窒素中で、焼結温度１３４０℃で４時間焼結し、焼結体を得た。なお、（ＢａＬａ）ＴｉＯ３仮焼温度が９００℃以下では、ＢａＣＯ３、ＴｉＯ２が仮焼粉中に残存させることができ、あるいは、（ＢａＬａ）ＴｉＯ３仮焼温度が１０００℃以上１２００℃以下の仮焼粉にはＢａＣＯ３、ＴｉＯ２を後添加すると特性を安定させることができる。
　得られた焼結体を１０ｍｍ×１０ｍｍ×１ｍｍの板状に加工して試験片を作成し、Ａｇ－Ｚｎで構成されたオーミック電極と、その上にＡｇを主成分とするカバー電極を同時に焼き付け試験素子とした後、試験片を抵抗測定器で室温から２７０℃までの範囲で比抵抗値の温度変化を測定し、ＰＴＣ特定として室温比抵抗、キュリー温度、抵抗温度係数（（ｌｎＲ１－ｌｎＲｃ）×１００／（Ｔ１－Ｔｃ）、Ｒ１：最大抵抗比、Ｒｃ：Ｔｃにおける比抵抗、Ｔ１：Ｒ１を示す温度、Ｔｃ：キュリー温度）を測定した。測定後、電極を取り除き、室温から８００℃で熱処理を行った。熱処理後、材料に再度電極を形成し、上記ＰＴＣ特性を評価した。
　表１は酸素雰囲気中で２０℃から６００℃で熱処理をしたときのＰＴＣ特性、表２は大気中で２０℃から８００℃で熱処理を行ったときのＰＴＣ特性、抵抗温度係数に着目すると、酸素雰囲気中及び大気中で熱処理を行った試料は、何れも熱処理前の抵抗温度係数よりも高い値を示すことが確認できた。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
（実施例２）
　実施例１と同様にしてＰＴＣ特性を測定した。測定後、電極を取り除くことなくそのままの状態で、室温から８００℃で熱処理を行った。電極を形成した状態で、酸素雰囲気中で熱処理を行うと、電極が劣化するため、また窒素中で処理を行っても効果が無いため、大気中で熱処理を行った。熱処理後、上記ＰＴＣ特性を評価した。
Figure JPOXMLDOC01-appb-T000003
　表３は大気中で２０℃から８００℃で熱処理をしたときのＰＴＣ特性を示す。抵抗温度係数に着目すると、大気中で熱処理を行った試料は、６００℃までは、何れも熱処理前の抵抗温度係数よりも高い値を示すことが確認できた。しかし、８００℃では熱処理前の抵抗温度係数よりも低い値を示すことが確認できた。
（実施例３）
　４００℃で熱処理した材料と熱処理していない材料の端面に電極を形成し、ヒータ素子を作製した。図１はヒータ素子の構成を示しており、放熱フィン１１を備えた一対のケーシング１３（１３ａ、１３ｂ）で、ヒータ素子１５を挟持して構成される。一方のケーシング１３ａに設けられた給電端子１７ａと、他方のケ－シング１３ｂに設けられた給電端子１７ｂとを介してヒータ素子１５に電圧を印加することでヒータ素子１５を発熱させることができる。作製したヒータ素子を恒温槽の中へ設置し、所定の温度まで昇温した後、給電素子に１３ボルトの電圧を印加し温度に対する電圧、電流の変化を観察した（表４参照）。
Figure JPOXMLDOC01-appb-T000004
　図２は温度（横軸）に対する電圧、電流（縦軸）の変化を示す図であり、熱処理無し(図中（ａ）)に比べて熱処理有り（図中（ｂ））の特性は、高温側で極めて電流値が低くなっており、高温時の安全性が向上していることが分かる。
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、2008年3月19日出願の日本特許出願（特願2008－071353）に基づくものであり、その内容はここに参照として取り込まれる。
　以上のように、本発明に係る半導体磁器組成物は、ＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換した従来の半導体磁器組成物には見られないジャンプ特性を有している。この半導体磁器組成物からなる発熱体を用いたヒータは、より高温環境下での使用に適したものとなる。

Claims (6)

  1. 　Ｂａの一部をＢｉ－Ｎａで置換した半導体磁器組成物の製造方法であって、
    　前記半導体磁器組成物を６００℃以下で熱処理する工程を含む半導体磁器組成物の製造方法。
  2. 　前記工程は、酸素を含む雰囲気中で熱処理する工程である請求項１記載の半導体磁器組成物の製造方法。
  3. 　前記工程は、大気中で熱処理する工程である請求項１記載の半導体磁器組成物の製造方法。
  4. 　Ｂａの一部をＢｉ-Ｎａで置換した半導体磁器組成物の製造方法であって、
    　前記半導体磁器組成物に電極を形成する工程と、
    　前記半導体磁器組成物を大気中６００℃以下で熱処理する工程を含む電極付き半導体磁器組成物の製造方法。
  5. 　ＢａＴｉＯ３のＢａの一部をＢｉ-Ｎａで置換した半導体磁器組成物の製造方法であって、
    　（ＢａＱ）ＴｉＯ３仮焼粉（Ｑは半導体化元素）を用意する工程、
    　（ＢｉＮａ）ＴｉＯ３仮焼粉を用意する工程、
    　前記（ＢａＱ）ＴｉＯ３仮焼粉及び前記（ＢｉＮａ）ＴｉＯ３仮焼粉を混合する工程、
    　混合した仮焼粉を成形し焼結する工程、
    　得られた焼結体を６００℃以下で熱処理する工程を含む半導体磁器組成物の製造方法。
  6. 　請求項１から５の何れか一項に記載の製造方法で得られた電極付き半導体磁器組成物からなる発熱体を有するヒータ。
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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
CN104860677A (zh) * 2015-04-20 2015-08-26 河南师范大学 一种掺杂锆钛酸钡基铁电陶瓷材料及其制备方法
CN109761602B (zh) * 2019-02-28 2020-11-24 华中科技大学 一种低阻热敏陶瓷材料及其制备方法与应用
TWI844017B (zh) * 2022-05-10 2024-06-01 鈞成金屬股份有限公司 一體式車肩座結構改良

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EP2253602A1 (en) 2010-11-24
JP5844507B2 (ja) 2016-01-20
CN101959829A (zh) 2011-01-26
KR101545763B1 (ko) 2015-08-19
KR20110009653A (ko) 2011-01-28
JP2009227477A (ja) 2009-10-08
EP2253602A4 (en) 2015-03-25
TWI485122B (zh) 2015-05-21
US20110011848A1 (en) 2011-01-20
US8766145B2 (en) 2014-07-01
TW200940475A (en) 2009-10-01

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