JP2012140309A - Method for producing perovskite type compound oxide powder - Google Patents

Method for producing perovskite type compound oxide powder Download PDF

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JP2012140309A
JP2012140309A JP2011000467A JP2011000467A JP2012140309A JP 2012140309 A JP2012140309 A JP 2012140309A JP 2011000467 A JP2011000467 A JP 2011000467A JP 2011000467 A JP2011000467 A JP 2011000467A JP 2012140309 A JP2012140309 A JP 2012140309A
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powder
tio
surface area
specific surface
titanium oxide
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JP5375838B2 (en
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Shinichi Kato
真一 加藤
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Murata Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently and economically producing a barium titanate-based perovskite compound oxide powder, which has a large number of lamination of dielectric layers to be suitably used as a component of a dielectric layer of a thinly layered laminated ceramic capacitor, and which is minute in size, large in specific surface area, and high in crystallinity.SOLUTION: The perovskite compound oxide is synthesized, by adding barium hydroxide to a solution containing titanium oxide powder having ≥0.38 mL/g pore volume and ≥250 m/g specific surface area and by allowing the barium hydroxide to react with the titanium oxide. A part of Ba constituting A site is substituted by Sr and/or Ca. The perovskite compound oxide that is produced in the reaction steps is subjected to heat treatment to improve crystallinity.

Description

本発明は一般式ＡＢＯ3で表されるペロブスカイト型複合酸化物の製造方法に関し、詳しくは、セラミック電子部品用のセラミック原料として好適に用いることが可能なチタン酸バリウム系のペロブスカイト型複合酸化物の製造方法に関する。 The present invention relates to a method for producing a perovskite complex oxide represented by the general formula ABO 3 , and more specifically, a barium titanate-based perovskite complex oxide that can be suitably used as a ceramic raw material for ceramic electronic components. It relates to a manufacturing method.

微粒で結晶性に優れたチタン酸バリウムなどのペロブスカイト型複合酸化物を経済的に製造するための方法として、例えば、以下に説明するような固液反応を用いたペロブスカイト型複合酸化物の方法が提案されている（特許文献１参照）。   As a method for economically producing a perovskite type complex oxide such as barium titanate having fine particles and excellent crystallinity, for example, there is a method of a perovskite type complex oxide using a solid-liquid reaction as described below. It has been proposed (see Patent Document 1).

この方法は、Ａサイト成分を構成する元素の、結晶水を含む水酸化物と、２５０ｍ2／ｇ以上の比表面積を有する酸化チタン粉末とを混合する混合処理工程を備え、この混合処理工程は、加熱処理を行うことにより結晶水の水分のみでＡサイト成分の溶解した溶解液を生成させる溶解液生成工程と、酸化チタン粉末と溶解液とを反応させて反応合成物を生成させる反応工程とを含むとともに、溶解液生成工程と反応工程とが連続的に進行するようにした複合酸化物粉末の製造方法である。
また、特許文献１には、上述のようにして得られる複合酸化物を仮焼することが開示されている。 This method includes a mixing process step of mixing a hydroxide containing crystal water of an element constituting the A site component and a titanium oxide powder having a specific surface area of 250 m 2 / g or more. A solution generating step for generating a solution in which the A-site component is dissolved only by water of crystallization water by performing heat treatment, and a reaction step for generating a reaction product by reacting the titanium oxide powder and the solution. And a manufacturing method of the composite oxide powder in which the solution generation step and the reaction step proceed continuously.
Patent Document 1 discloses that the composite oxide obtained as described above is calcined.

そして、この特許文献１の発明の方法によれば、異相が少なく、超微粒で、かつ、結晶性に優れた複合酸化物が得られ、これを仮焼処理することにより、立方晶系複合酸化物から結晶系が転移して、結晶性に優れた正方晶系の複合酸化物を製造することができるとされている。   Then, according to the method of the invention of Patent Document 1, a composite oxide with few heterogeneous phases, ultrafine particles and excellent crystallinity is obtained, and this is calcined to obtain a cubic composite oxide. It is said that a tetragonal complex oxide having excellent crystallinity can be produced by transferring the crystal system from the product.

ところで、先行技術のような固液反応によって微粒のチタン酸バリウム（ＢａＴｉＯ3）系のペロブスカイト型複合酸化物粉末を得るためには、反応を十分に進行させる見地から、水酸化バリウム（Ｂａ（ＯＨ）2）が酸化チタン（ＴｉＯ2）内部に拡散する距離を小さくすることが必要である。そのため、特許文献１の方法では、原料となる酸化チタン粉末として、比表面積（ＳＳＡ）が２５０ｍ2／ｇ以上の酸化チタン粉末（すなわち、比表面積相当径で６ｎｍ以下の酸化チタン粉末）を用いるようにしている。 By the way, in order to obtain a fine barium titanate (BaTiO 3 ) -based perovskite complex oxide powder by solid-liquid reaction as in the prior art, barium hydroxide (Ba (OH 2 ) It is necessary to reduce the distance at which 2 ) diffuses inside the titanium oxide (TiO 2 ). Therefore, in the method of Patent Document 1, titanium oxide powder having a specific surface area (SSA) of 250 m 2 / g or more (that is, titanium oxide powder having a specific surface area equivalent diameter of 6 nm or less) is used as a titanium oxide powder as a raw material. I have to.

しかしながら、上述のような微細な酸化チタン一次粒子が強く凝集している場合、通常の撹拌では微小な凝集体を個々の一次粒子にまで分散することは困難で、液中では凝集粒子として存在することになる。   However, when the fine titanium oxide primary particles as described above are strongly agglomerated, it is difficult to disperse the fine agglomerates into the individual primary particles by ordinary stirring, and they exist as agglomerated particles in the liquid. It will be.

そのため、酸化チタン（ＴｉＯ2）と、水酸化バリウム（Ｂａ（ＯＨ）2）とを十分に反応させるためには、水酸化バリウムは酸化チタン凝集体の内部にまで拡散する必要があるが、酸化チタン粉末の密な凝集体が存在する場合には、酸化チタン凝集体の内部にまで水酸化バリウムを拡散させることが困難で、結果として酸化チタン粉末原料と水酸化バリウムとの反応が、不十分になってしまうという問題点がある。 Therefore, in order to sufficiently react titanium oxide (TiO 2 ) and barium hydroxide (Ba (OH) 2 ), barium hydroxide needs to diffuse to the inside of the titanium oxide aggregate. When there is a dense aggregate of titanium powder, it is difficult to diffuse barium hydroxide into the titanium oxide aggregate, resulting in insufficient reaction between the titanium oxide powder raw material and barium hydroxide. There is a problem of becoming.

また、近年、積層セラミックコンデンサにおいて、容量形成用の内部電極間に介在する誘電体層としてのセラミック層の厚み（素子厚み）が１μｍ未満の領域のものが実用化されるに至っており、微粒で、ｃ／ａ軸比が大きく、結晶性の高いチタン酸バリウム粉末への要求が大きくなっているが、上述の特許文献１の技術では、必ずしも上記の要求に応えることができなくなりつつあるのが実情である。   In recent years, multilayer ceramic capacitors having a ceramic layer thickness (element thickness) of less than 1 μm as a dielectric layer interposed between internal electrodes for capacitance formation have been put into practical use. Although the demand for a barium titanate powder having a large c / a axial ratio and high crystallinity is increasing, the technique of the above-mentioned Patent Document 1 is not necessarily meeting the above requirements. It is a fact.

特許第４２００４２７号公報Japanese Patent No. 4200197

本発明は、上記課題を解決するものであり、例えば、誘電体層の積層数が多く、薄層化された積層セラミックコンデンサにおける誘電体層の構成材料などとして好適に用いることが可能な、微細で、表面積が大きく、結晶性の高いチタン酸バリウム系のペロブスカイト型複合酸化物を効率よく製造するための方法を提供することを目的とする。   The present invention solves the above-described problems. For example, the dielectric layer has a large number of laminated dielectric layers, and can be suitably used as a constituent material of a dielectric layer in a thin laminated ceramic capacitor. Thus, an object of the present invention is to provide a method for efficiently producing a barium titanate-based perovskite complex oxide having a large surface area and high crystallinity.

上記課題を解決するため、発明者は、固液反応によって微粒のチタン酸バリウム（ＢａＴｉＯ3）系のペロブスカイト型複合酸化物粉末を製造することに関して、種々の検討を行い、従来は、原料である酸化チタン粉末の比表面積によって反応性を評価し、適切な比表面積を有するＴｉＯ2粉末を選択することで、必要な反応性を確保することができると考えてきたが、酸化チタン粉末を構成する粒子（ＴｉＯ2一次粒子）どうしのパッキングが密な場合には、ＴｉＯ2一次粒子が凝集した凝集体の内部へのＢａ2+の拡散が妨げられ、反応が不均一になる傾向があることを知った。 In order to solve the above-mentioned problems, the inventor has made various studies on producing fine barium titanate (BaTiO 3 ) -based perovskite complex oxide powders by solid-liquid reaction. It has been thought that the reactivity can be ensured by evaluating the reactivity based on the specific surface area of the titanium oxide powder and selecting the TiO 2 powder having an appropriate specific surface area. When the packing of the particles (TiO 2 primary particles) is dense, the diffusion of Ba 2+ into the agglomerates in which the TiO 2 primary particles are aggregated is prevented, and the reaction tends to be non-uniform. Knew.

また、ＴｉＯ2一次粒子のパッキングの程度は、原料となる酸化チタン粉末の細孔径分布から知ることが可能であり、この細孔径分布は、細孔容積（ＢＪＨ法）で調べることができることを知った。なお、ＢＪＨ法により細孔容積を求めると、通常は直径が１〜数十ｎｍ程度の細孔の容積が求められることになるとされている。
そして、かかる知見に基づいて、さらに実験、検討を続けて、本発明を完成するに至った。 In addition, the degree of packing of the TiO 2 primary particles can be known from the pore size distribution of the titanium oxide powder as a raw material, and this pore size distribution can be examined by the pore volume (BJH method). It was. In addition, when the pore volume is determined by the BJH method, the volume of the pore having a diameter of about 1 to several tens of nm is usually determined.
And based on this knowledge, it continued experiment and examination, and came to complete this invention.

すなわち、本発明のペロブスカイト型複合酸化物の製造方法は、
一般式ＡＢＯ3で表されるチタン酸バリウム系のペロブスカイト型複合酸化物の製造方法であって、
少なくとも酸化チタン粉末を含む溶液に、水酸化バリウムを加え、反応させる反応工程を備えているとともに、
前記酸化チタン粉末として、細孔容積が０．３８ｍＬ／ｇ以上で、比表面積が２５０ｍ2／ｇ以上の酸化チタン粉末を用いること
を特徴としている。 That is, the method for producing the perovskite complex oxide of the present invention includes:
A method for producing a barium titanate-based perovskite complex oxide represented by the general formula ABO 3 ,
It has a reaction step of adding barium hydroxide to a solution containing at least titanium oxide powder and reacting it,
As the titanium oxide powder, a titanium oxide powder having a pore volume of 0.38 mL / g or more and a specific surface area of 250 m 2 / g or more is used.

また、本発明により製造されるペロブスカイト型複合酸化物は、Ａサイトを構成するＢａの一部が、Ｓｒおよび／またはＣａにより置換されていてもよい。   In the perovskite complex oxide produced according to the present invention, a part of Ba constituting the A site may be substituted with Sr and / or Ca.

また、本発明のペロブスカイト型複合酸化物の製造方法においては、前記反応工程で生成したペロブスカイト型複合酸化物を熱処理する工程をさらに備えていることが好ましい。   Moreover, it is preferable that the method for producing a perovskite complex oxide of the present invention further includes a step of heat-treating the perovskite complex oxide generated in the reaction step.

本発明の一般式ＡＢＯ3で表されるペロブスカイト型複合酸化物の製造方法は、少なくとも酸化チタン粉末を含む溶液に、水酸化バリウムを加え、反応させる反応工程を備えているとともに、上述の酸化チタン粉末として、細孔容積が０．３８ｍＬ／ｇ以上であり、かつ、比表面積が２５０ｍ2／ｇ以上である酸化チタン粉末を用いるようにしているので、従来の固液反応により得られるペロブスカイト型複合酸化物よりも比表面積が大きい、微細なペロブスカイト型複合酸化物を得ることができる。 The method for producing a perovskite type complex oxide represented by the general formula ABO 3 of the present invention includes a reaction step of adding barium hydroxide to a solution containing at least a titanium oxide powder and reacting the solution, and the titanium oxide described above. Since a titanium oxide powder having a pore volume of 0.38 mL / g or more and a specific surface area of 250 m 2 / g or more is used as the powder, a perovskite type composite obtained by a conventional solid-liquid reaction is used. A fine perovskite complex oxide having a specific surface area larger than that of the oxide can be obtained.

すなわち、細孔容積が０．３８ｍＬ／ｇ以上で、比表面積が２５０ｍ2／ｇ以上の酸化チタン粉末を用いた場合、単に比表面積（ＳＳＡ）だけに着目して選定した酸化チタンを用いる場合に比べて、より大きい比表面積を有するペロブスカイト型複合酸化物を、特に複雑な製造工程を必要とすることなく効率よく製造することが可能になる。 That is, when a titanium oxide powder having a pore volume of 0.38 mL / g or more and a specific surface area of 250 m 2 / g or more is used, a titanium oxide selected by paying attention only to the specific surface area (SSA) is used. In comparison, it is possible to efficiently manufacture a perovskite complex oxide having a larger specific surface area without requiring a particularly complicated manufacturing process.

なお、本発明において、酸化チタン粉末について規定されている細孔容積は、ＢＪＨ法により求められる値であり、比表面積はＢＥＴ法により求められる値である。   In the present invention, the pore volume defined for the titanium oxide powder is a value obtained by the BJH method, and the specific surface area is a value obtained by the BET method.

また、本発明によれば、Ａサイトを構成するＢａの一部を、Ｓｒおよび／またはＣａにより置換した組成のペロブスカイト型複合酸化物を製造することも可能であり、その場合には、特性を調整して、所望の特性を有するペロブスカイト型複合酸化物を効率よく製造することができる。   In addition, according to the present invention, it is also possible to produce a perovskite type complex oxide having a composition in which a part of Ba constituting the A site is substituted with Sr and / or Ca. By adjusting, a perovskite complex oxide having desired characteristics can be produced efficiently.

なお、Ｂａと置換するＳｒおよび／またはＣａの成分原料は、酸化チタンスラリーに含ませておくことも可能であり、また、反応工程の直前に、水酸化バリウムよりも先にあるいは同時に、酸化チタンスラリーに添加することも可能である。   It should be noted that the component raw materials of Sr and / or Ca to be substituted for Ba can be contained in the titanium oxide slurry, and before or simultaneously with the barium hydroxide immediately before the reaction step, the titanium oxide. It is also possible to add to the slurry.

なお、水酸化バリウムとして、水和水を含まない水酸化バリウムを用いることにより、酸化チタン粉末などが分散したスラリーに固形の水酸化バリウムが直接に添加することが可能になるため、製造プロセスを簡略化することができる。また、水和水を含まない水酸化バリウムを固形のまま酸化チタンスラリーに添加するようにした場合、その溶解熱により温度上昇が起こり、合成反応を促進させることが可能になる。   By using barium hydroxide containing no hydration water as barium hydroxide, solid barium hydroxide can be added directly to a slurry in which titanium oxide powder or the like is dispersed. It can be simplified. Further, when barium hydroxide containing no hydration water is added to the titanium oxide slurry in a solid state, the temperature rises due to the heat of dissolution, and the synthesis reaction can be promoted.

また、本発明において、反応工程で生成したペロブスカイト型複合酸化物を熱処理することにより、ｃ／ａ軸比を高めて、結晶性の高いペロブスカイト型複合酸化物を得ることができる。   In the present invention, a perovskite complex oxide having high crystallinity can be obtained by heat-treating the perovskite complex oxide produced in the reaction step to increase the c / a axial ratio.

例えば、８００〜１０００℃の温度で熱処理することで、ｃ／ａ軸比が大きい（１を超える）正方晶のペロブスカイト型複合酸化物が得られる。また、本発明においては、細孔容積が０．３８ｍＬ／ｇ以上で、比表面積が２５０ｍ2／ｇ以上の酸化チタン粉末を用いるようにしているので、粒成長し、結晶性が向上する工程である熱処理工程を経た後においても、十分に微細で、比表面積が大きく、かつ、ｃ／ａ軸比の大きい、結晶性の高いペロブスカイト型複合酸化物を得ることができる。 For example, by performing heat treatment at a temperature of 800 to 1000 ° C., a tetragonal perovskite complex oxide having a large c / a axial ratio (greater than 1) can be obtained. In the present invention, since the titanium oxide powder having a pore volume of 0.38 mL / g or more and a specific surface area of 250 m 2 / g or more is used, the grain growth and crystallinity are improved. Even after a certain heat treatment step, it is possible to obtain a perovskite complex oxide that is sufficiently fine, has a large specific surface area, and has a high c / a axial ratio and high crystallinity.

本発明の一実施例（実施例１）においてＴｉ原料として用いた酸化チタン（ＴｉＯ2）粉末の比表面積と、反応を行わせることにより得たＢａＴｉＯ3粉末の比表面積の関係を示す図である。Is a graph showing the specific surface area of titanium oxide (TiO 2) powder was used as a Ti raw material in one embodiment (Example 1), the relationship between the specific surface area of the BaTiO 3 powder obtained by causing the reaction of the present invention . 本発明の一実施例（実施例１）においてＴｉ原料として用いた酸化チタン（ＴｉＯ2）粉末の細孔容積と、反応を行わせることにより得たＢａＴｉＯ3粉末の比表面積の関係を示す図である。A diagram showing a titanium oxide (TiO 2) powder pore volume was used as a Ti material in one embodiment (Example 1), the relationship between the specific surface area of the BaTiO 3 powder obtained by causing the reaction of the present invention is there. 表１のＮｏ．２およびＮｏ．７の酸化チタン（ＴｉＯ2）粉末を用いて作製したＢａＴｉＯ3粉末を仮焼した後のＢａＴｉＯ3粉末の比表面積と、結晶のｃ／ａ軸比との関係を示す図である。No. in Table 1 2 and no. 7 and a specific surface area of the BaTiO 3 powder after calcining BaTiO 3 powder produced by using a titanium oxide (TiO 2) powder is a diagram showing the relationship between the c / a axial ratio of the crystal.

以下に本発明の実施例を示して、本発明の特徴とするところをさらに詳しく説明する。   Examples of the present invention will be described below to describe the features of the present invention in more detail.

表１に示すような比表面積および細孔容積を有する、Ｎｏ．１〜Ｎｏ．９のアナターゼ型の酸化チタン（ＴｉＯ2）粉末を準備した。なお、各酸化チタン（ＴｉＯ2）粉末の比表面積はＢＥＴ法、細孔容積はＢＪＨ法により測定することにより得た値である。 No. 1 having a specific surface area and pore volume as shown in Table 1. 1-No. Nine anatase-type titanium oxide (TiO 2 ) powders were prepared. The specific surface area of each titanium oxide (TiO 2 ) powder is a value obtained by measuring by the BET method and the pore volume is measured by the BJH method.

それから、表１のＮｏ．１〜Ｎｏ．９の各ＴｉＯ2粉末７．４０ｋｇと、純水１９．４Ｌ（リットル）を反応器に投入し、撹拌機で撹拌してスラリーを作製した。 Then, in Table 1, No. 1-No. 9.40 kg of each TiO 2 powder of No. 9 and 19.4 L (liter) of pure water were put into a reactor and stirred with a stirrer to prepare a slurry.

次に、このスラリーを７０℃（５０℃以上であることが望ましい）まで加熱し、所定のＢａ／Ｔｉ比となるように、水和水を有しない水酸化バリウム（Ｂａ（ＯＨ）2）を固形のまま添加した後、温度が８０℃以上に保たれるように、加熱、撹拌しながら、１時間反応させることにより、チタン酸バリウム（ＢａＴｉＯ3）を合成し、得られたスラリーを乾燥してＢａＴｉＯ3粉末（ペロブスカイト型複合酸化物粉末）を得た。 Next, this slurry is heated to 70 ° C. (desirably 50 ° C. or higher), and barium hydroxide (Ba (OH) 2 ) without hydration water is added so as to have a predetermined Ba / Ti ratio. After adding as solid, the reaction is carried out for 1 hour with heating and stirring so that the temperature is maintained at 80 ° C. or higher, thereby synthesizing barium titanate (BaTiO 3 ) and drying the resulting slurry. Thus, BaTiO 3 powder (perovskite type complex oxide powder) was obtained.

それから、得られたＢａＴｉＯ3粉末の比表面積をＢＥＴ法で測定した。その結果を表１に示す。
また、得られたＢａＴｉＯ3粉末のＸ線回折を行いＢａ（ＯＨ）2の残留状況を調査した。その結果についても、表１に併せて示す。 Then, the specific surface area of the obtained BaTiO 3 powder was measured by the BET method. The results are shown in Table 1.
Further, X-ray diffraction was performed on the obtained BaTiO 3 powder to investigate the residual state of Ba (OH) 2 . The results are also shown in Table 1.

Figure 2012140309
Figure 2012140309

また、原料として用いたＴｉＯ2粉末の比表面積（ＳＳＡ）と、上述のようにして反応を行わせることにより作製（合成）したＢａＴｉＯ3粉末の比表面積（ＳＳＡ）の関係を図１に示すとともに、原料として用いたＴｉＯ2粉末の細孔容積と、作製（合成）したＢａＴｉＯ3粉末の比表面積の関係を図２に示す。図１および図２において、プロットしたデータの近傍に付した１〜９の番号は、表１のＮｏ．１〜９のＴｉＯ2粉末を示す番号である。 FIG. 1 shows the relationship between the specific surface area (SSA) of the TiO 2 powder used as a raw material and the specific surface area (SSA) of the BaTiO 3 powder prepared (synthesized) by reacting as described above. FIG. 2 shows the relationship between the pore volume of the TiO 2 powder used as a raw material and the specific surface area of the produced (synthesized) BaTiO 3 powder. 1 and 2, numbers 1 to 9 given in the vicinity of the plotted data are No. 1 in Table 1. Is a number indicating the 1-9 TiO 2 powder.

表１と、図１および図２から明らかなように、表１のＮｏ．１〜Ｎｏ．４のＴｉＯ2粉末を用いた場合、比表面積（ＳＳＡ）は３０７〜３１５ｍ2／ｇと、表１のＮｏ．５〜Ｎｏ．９のＴｉＯ2粉末と同等であるにも関わらず、得られたＢａＴｉＯ3粉末の比表面積（ＳＳＡ）は１０〜４４ｍ2／ｇと小さくなることが確認された。
また、未反応物であるＢａ（ＯＨ）2が残留していることも確認された。 As is clear from Table 1 and FIGS. 1-No. When using TiO 2 powder 4, the specific surface area (SSA) is a 307~315m 2 / g, Table 1 No. 5-No. Although it was equivalent to 9 TiO 2 powder, the specific surface area (SSA) of the obtained BaTiO 3 powder was confirmed to be as small as 10 to 44 m 2 / g.
It was also confirmed that unreacted Ba (OH) 2 remained.

一方、表１のＮｏ．５〜Ｎｏ．９のＴｉＯ2粉末を用いた場合、微粒で結晶性の高いＢａＴｉＯ3粉末が得られることが確認された。また、未反応物であるＢａ（ＯＨ）2が残留していないことが確認された。
これは、比表面積が、表１のＮｏ．１〜Ｎｏ．４と同等でも、細孔容積が大きい（０．３８ｍＬ／ｇ以上）のＴｉＯ2粉末を用いることにより、Ｂａ（ＯＨ）2がＴｉＯ2粒子の凝集体の内部まで拡散し、反応が十分に進んだことによるものである。 On the other hand, no. 5-No. When 9 TiO 2 powder was used, it was confirmed that a BaTiO 3 powder having fine particles and high crystallinity was obtained. It was also confirmed that no unreacted Ba (OH) 2 remained.
This is because the specific surface area is No. 1 in Table 1. 1-No. Even if it is equal to 4, TiO 2 powder having a large pore volume (0.38 mL / g or more) is used, so that Ba (OH) 2 diffuses to the inside of the aggregate of TiO 2 particles, and the reaction proceeds sufficiently. It is due to that.

最終組成が（Ｂａ0.95Ｃａ0.05）ＴｉＯ3となるように酸化チタン（ＴｉＯ2）粉末（表１のＮｏ．７のＴｉＯ2粉末）、炭酸カルシウム（ＣａＣＯ3）粉末、水酸化バリウム（Ｂａ（ＯＨ）2）粉末の各原料を秤量した。 Titanium oxide (TiO 2 ) powder (TiO 2 powder of No. 7 in Table 1), calcium carbonate (CaCO 3 ) powder, barium hydroxide (Ba (OH) so that the final composition is (Ba 0.95 Ca 0.05 ) TiO 3. 2 ) Each powder raw material was weighed.

それから、実施例１と同じようにＴｉＯ2粉末（表１のＮｏ．７のＴｉＯ2粉末）と、ＣａＣＯ3粉末と、純水とを反応器に投入し、撹拌機で撹拌しながら７０℃まで加熱した時点で、水和水を含まない水酸化バリウム（Ｂａ（ＯＨ）2）を加え、継続して攪拌を行いながら、８０℃以上で１時間反応させ、（Ｂａ，Ｃａ）ＴｉＯ3スラリーを得た。その後、スラリーを乾燥して（Ｂａ，Ｃａ）ＴｉＯ3粉末を得た。 Then, the same as TiO 2 powder as in Example 1 (TiO 2 powder shown in Table 1 of No.7), and CaCO 3 powder, and a pure water were charged to the reactor, up to 70 ° C. while stirring at a stirrer When heated, barium hydroxide containing no hydration water (Ba (OH) 2 ) was added, and the mixture was allowed to react at 80 ° C. or higher for 1 hour with continuous stirring, and the (Ba, Ca) TiO 3 slurry was Obtained. Thereafter, the slurry was dried to obtain (Ba, Ca) TiO 3 powder.

得られた（Ｂａ，Ｃａ）ＴｉＯ3粉末は、実施例１の表１のＮｏ．７のＴｉＯ2粉末を用いて作製（合成）したＢａＴｉＯ3とほぼ同じ比表面積を有し、組成が目標の（Ｂａ0.95Ｃａ0.05）ＴｉＯ3と一致する微細な粉末（（Ｂａ0.95Ｃａ0.05）ＴｉＯ3）粉末であることが確認された。
また、未反応物であるＢａ（ＯＨ）2が残留していないことが確認された。 The obtained (Ba, Ca) TiO 3 powder was obtained from No. 1 in Table 1 of Example 1. Fine powder ((Ba 0.95 Ca 0.05 ) TiO 3 having the same specific surface area as BaTiO 3 produced (synthesized) using TiO 2 powder of No. 7 and having the same composition as the target (Ba 0.95 Ca 0.05 ) TiO 3 3 ) It was confirmed to be powder.
It was also confirmed that no unreacted Ba (OH) 2 remained.

なお、この実施例２ではＣａソースとして炭酸カルシウム（ＣａＣＯ3）粉末を用いたが、ＣａソースはＣａＣＯ3粉末に限定されるものではなく、例えば、酢酸カルシウム、硝酸カルシウムなどの他の塩や、水酸化物（水酸化カルシウム）を用いることも可能である。 In Example 2, calcium carbonate (CaCO 3 ) powder was used as the Ca source. However, the Ca source is not limited to CaCO 3 powder. For example, other salts such as calcium acetate and calcium nitrate, It is also possible to use a hydroxide (calcium hydroxide).

最終組成が（Ｂａ0.95Ｓｒ0.05）ＴｉＯ3となるようにＴｉＯ2粉末（表１のＮｏ．７のＴｉＯ2粉末）、炭酸ストロンチウム（ＳｒＣＯ3）粉末、水酸化バリウム（Ｂａ（ＯＨ）2）粉末の各原料を秤量した。 TiO 2 powder (No. 7 TiO 2 powder in Table 1), strontium carbonate (SrCO 3 ) powder, barium hydroxide (Ba (OH) 2 ) powder so that the final composition is (Ba 0.95 Sr 0.05 ) TiO 3 Each raw material was weighed.

それから、実施例１と同じようにＴｉＯ2粉末（表１のＮｏ．７のＴｉＯ2粉末）と、ＳｒＣＯ3粉末と、純水とを反応器に投入し、撹拌機で撹拌しながら７０℃まで加熱した時点で、水和水を含まない水酸化バリウム（Ｂａ（ＯＨ）2）を加え、継続して攪拌を行いながら、８０℃以上で１時間反応させ、（Ｂａ，Ｓｒ）ＴｉＯ3スラリーを得た。その後、スラリーを乾燥して（Ｂａ，Ｓｒ）ＴｉＯ3粉末を得た。 Then, the same as TiO 2 powder as in Example 1 (TiO 2 powder shown in Table 1 of No.7), a SrCO 3 powder, the pure water were charged to the reactor, up to 70 ° C. while stirring at a stirrer When heated, barium hydroxide containing no hydration water (Ba (OH) 2 ) was added, and the mixture was allowed to react at 80 ° C. or higher for 1 hour with continuous stirring, and the (Ba, Sr) TiO 3 slurry was Obtained. Thereafter, the slurry was dried to obtain (Ba, Sr) TiO 3 powder.

得られた（Ｂａ，Ｓｒ）ＴｉＯ3粉末は、実施例１の表１のＮｏ．７のＴｉＯ2粉末を用いて作製（合成）したＢａＴｉＯ3とほぼ同じ比表面積を有し、組成が目標の（Ｂａ0.95Ｃａ0.05）ＴｉＯ3と一致する微細な粉末（（Ｂａ0.95Ｓｒ0.05）ＴｉＯ3）粉末であることが確認された。
また、未反応物であるＢａ（ＯＨ）2が残留していないことが確認された。 The obtained (Ba, Sr) TiO 3 powder was obtained from No. 1 in Table 1 of Example 1. Fine powder ((Ba 0.95 Sr 0.05 ) TiO 3 having the same specific surface area as BaTiO 3 produced (synthesized) using TiO 2 powder of No. 7 and having a composition consistent with the target (Ba 0.95 Ca 0.05 ) TiO 3 3 ) It was confirmed to be powder.
It was also confirmed that no unreacted Ba (OH) 2 remained.

なお、この実施例３ではＳｒソースとして炭酸ストロンチウム（ＳｒＣＯ3）粉末を用いたが、Ｓｒソースは炭酸ストロンチウム（ＳｒＣＯ3）粉末に限定されるものではなく、例えば、硝酸ストロンチウムなどの他の塩や、水酸化物（水酸化ストロンチウム）などを用いることも可能である。 In Example 3, strontium carbonate (SrCO 3 ) powder was used as the Sr source. However, the Sr source is not limited to strontium carbonate (SrCO 3 ) powder, and other salts such as strontium nitrate, It is also possible to use hydroxide (strontium hydroxide) or the like.

実施例１の表１のＮｏ．２のＴｉＯ2粉末（本発明の要件を満たさない、細孔容積が０．２２ｍＬ／ｇのＴｉＯ2粉末）を用いて作製したＢａＴｉＯ3粉末と、Ｎｏ．７のＴｉＯ2粉末（本発明の要件を満たす、細孔容積が０．４８ｍＬ／ｇのＴｉＯ2粉末）を用いて作製したＢａＴｉＯ3粉末を、熱処理炉を用いて、温度条件を８００〜１０００℃の範囲で異ならせて熱処理（仮焼）を行った。 No. 1 in Table 1 of Example 1 2 of TiO 2 powder (does not meet the requirements of the present invention, a pore volume of TiO 2 powder 0.22 mL / g) and BaTiO 3 powder produced by using, No. 7 (satisfying the requirements of the present invention, a pore volume of TiO 2 powder 0.48 mL / g) TiO 2 powder of BaTiO 3 powder produced by using a using a heat treatment furnace, a temperature 800 to 1000 ° C. The heat treatment (calcination) was performed in a different range.

そして、熱処理後（仮焼後）のＢａＴｉＯ3粉末について、ＢＥＴ法にて比表面積を測定した。また、Ｘ線回折法（ＸＲＤ）を用いて格子定数を測定し、ｃ／ａ軸比を算出した。
熱処理後（仮焼後）のＢａＴｉＯ3粉末の比表面積（ＳＳＡ）と、結晶のｃ／ａ軸比との関係を図３に示す。 Then, the BaTiO 3 powder after heat treatment (after calcination) were measured specific surface area by the BET method. Moreover, the lattice constant was measured using the X-ray diffraction method (XRD), and c / a axial ratio was computed.
FIG. 3 shows the relationship between the specific surface area (SSA) of the BaTiO 3 powder after heat treatment (after calcination) and the c / a axial ratio of the crystals.

図３から明らかなように、細孔容積が０．３８ｍＬ／ｇ以上（０．４８ｍＬ）で、本発明の要件を満たすＴｉＯ2粉末（Ｎｏ．７のＴｉＯ2粉末）を用いて作製（合成）し、熱処理（仮焼）したＢａＴｉＯ3粉末は、細孔容積が０．２２ｍＬ／ｇで、本発明の要件を満たさないＴｉＯ2粉末（Ｎｏ．２のＴｉＯ2粉末）を用いて作製（合成）し、熱処理（仮焼）したＢａＴｉＯ3粉末に比べてｃ／ａ軸比が大きく、結晶性が高くなることが確認された。
なお、図３からは、粒成長する（比表面積が低下する）のに伴って、ｃ／ａ軸比が大きくなり、結晶性が向上する傾向があることがわかる。 As is apparent from FIG. 3, it was produced using a TiO 2 powder (No. 7 TiO 2 powder) having a pore volume of 0.38 mL / g or more (0.48 mL) and satisfying the requirements of the present invention (synthesis). The BaTiO 3 powder that was heat-treated (calcined) was prepared using a TiO 2 powder (No. 2 TiO 2 powder) that has a pore volume of 0.22 mL / g and does not satisfy the requirements of the present invention (synthesis). As a result, it was confirmed that the c / a axial ratio was larger and the crystallinity was higher than that of the BaTiO 3 powder subjected to heat treatment (calcination).
From FIG. 3, it can be seen that as the grain grows (the specific surface area decreases), the c / a axial ratio increases and the crystallinity tends to improve.

なお、本発明は上記実施例に限定されるものではなく、反応に供する酸化チタン（ＴｉＯ2）粉末を含むスラリーの固形分濃度、スラリーに水酸化バリウムを添加して反応させる際の反応温度や反応時間などの条件、原料である酸化チタン粉末の比表面積の範囲および細孔容積、Ａサイトの一部をＳｒおよび／またはＣａで置換する際の置換割合、反応工程で生成したチタン酸バリウムを熱処理する際の条件などに関し、発明の範囲内において種々の応用、変形を加えることが可能である。 The present invention is not limited to the above embodiments, the solid concentration of the slurry containing titanium oxide (TiO 2) powder used for the reaction, the reaction temperature when the slurry with the addition of barium hydroxide reaction Ya Conditions such as reaction time, range of specific surface area and pore volume of titanium oxide powder as a raw material, substitution ratio when a part of A site is substituted with Sr and / or Ca, barium titanate produced in the reaction step Various applications and modifications can be made within the scope of the invention with respect to conditions for heat treatment.

Claims (3)

一般式ＡＢＯ3で表されるチタン酸バリウム系のペロブスカイト型複合酸化物の製造方法であって、
少なくとも酸化チタン粉末を含む溶液に、水酸化バリウムを加え、反応させる反応工程を備えているとともに、
前記酸化チタン粉末として、細孔容積が０．３８ｍＬ／ｇ以上で、比表面積が２５０ｍ2／ｇ以上の酸化チタン粉末を用いること
を特徴とするペロブスカイト型複合酸化物の製造方法。 A method for producing a barium titanate-based perovskite complex oxide represented by the general formula ABO 3 ,
It has a reaction step of adding barium hydroxide to a solution containing at least titanium oxide powder and reacting it,
A titanium oxide powder having a pore volume of 0.38 mL / g or more and a specific surface area of 250 m 2 / g or more is used. A method for producing a perovskite complex oxide. Ａサイトを構成するＢａの一部が、Ｓｒおよび／またはＣａにより置換されていることを特徴とする請求項１記載のペロブスカイト型複合酸化物の製造方法。   The method for producing a perovskite complex oxide according to claim 1, wherein a part of Ba constituting the A site is substituted with Sr and / or Ca. 前記反応工程で生成したペロブスカイト型複合酸化物を熱処理する工程をさらに備えていることを特徴とする請求項１または２記載のペロブスカイト型複合酸化物の製造方法。   The method for producing a perovskite complex oxide according to claim 1 or 2, further comprising a step of heat-treating the perovskite complex oxide generated in the reaction step.
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