JP5660947B2 - Method for producing BaTi2O5 composite oxide - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 239000002131 composite material Substances 0.000 title claims description 34
- 238000010304 firing Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
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- 229910052804 chromium Inorganic materials 0.000 claims description 5
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- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
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- 229910052758 niobium Inorganic materials 0.000 claims description 5
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Description
本発明は、ＢａＴｉ2Ｏ5系複合酸化物の製造方法に関する。 The present invention relates to a method for producing a BaTi 2 O 5 composite oxide.
ＢａＴｉ2Ｏ5は、多岐用途での強誘電性材料としての応用が期待されることから、これらを安価に提供できる簡便な製造方法の開発が嘱望されている。 Since BaTi 2 O 5 is expected to be used as a ferroelectric material for various purposes, development of a simple manufacturing method capable of providing these at low cost is desired.
従来の主なＢａＴｉ2Ｏ5は、溶融法を利用したものである。溶融法では、原料をたとえばＢａＴｉＯ3とＴｉＯ2の組成比１：１の混合物とし、これを１３８６℃以上に加熱して溶融した後に、冷却・凝固することによりＢａＴｉ2Ｏ5を単相状態で得ている（特許文献１）。 Conventional main BaTi 2 O 5 uses a melting method. In the melting method, the raw material is, for example, a mixture of BaTiO 3 and TiO 2 having a composition ratio of 1: 1, and this is heated to 1386 ° C. or higher to melt and then cooled and solidified to bring BaTi 2 O 5 into a single phase state. (Patent Document 1).
また、固相反応法を利用した方法もある。従来の固相反応法では、原料としてＢａＣＯ3とＴｉＯ2の組成比１：２の混合物を用い、固体状態のまま１０００〜１２３０℃で反応させることによりＢａＴｉ2Ｏ5を得ている。たとえば、ＢａＣＯ3とＴｉＯ2のモル比１：２の混合物をミリングした後に、９００及び１０００℃で２回仮焼し、さらに１０００〜１１５０℃または１２２０〜１２３０℃での焼成によりＢａＴｉ2Ｏ5を得た例が開示されている（非特許文献１）。 There is also a method using a solid phase reaction method. In the conventional solid phase reaction method, a mixture of BaCO 3 and TiO 2 having a composition ratio of 1: 2 is used as a raw material, and BaTi 2 O 5 is obtained by reacting at 1000 to 1230 ° C. in a solid state. For example, after milling a 1: 2 molar mixture of BaCO 3 and TiO 2 , calcined twice at 900 and 1000 ° C., and further calcined at 1000 to 1150 ° C. or 1220 to 1230 ° C. to obtain BaTi 2 O 5 . An obtained example is disclosed (Non-Patent Document 1).
溶融法を利用した従来のＢａＴｉ2Ｏ5の製造方法では、溶融温度である１３８６℃以上での加熱を実現するために、高価な超耐熱炉や坩堝を必要とするため、製造コストが著しく高くなっていた。また、溶融状態を経て冷却した試料は坩堝に強く密着するため、試料回収が困難になるという問題もあった。 In the conventional manufacturing method of BaTi 2 O 5 using the melting method, an expensive super heat-resistant furnace or crucible is required to realize heating at a melting temperature of 1386 ° C. or higher, and thus the manufacturing cost is extremely high. It was. Moreover, since the sample cooled through the molten state is closely attached to the crucible, there is a problem that the sample recovery becomes difficult.
固相反応法を利用した従来のＢａＴｉ2Ｏ5の製造方法では、９００及び１０００℃での２回の仮焼をしない場合、ＢａＴｉ2Ｏ5の生成率が低下することが記されている。つまり、ＢａＴｉ2Ｏ5を高純度で得るために仮焼を含む少なくとも２回以上の焼成操作を必要としている。 In the conventional method for producing BaTi 2 O 5 using the solid-phase reaction method, it is described that the production rate of BaTi 2 O 5 is lowered when not calcined twice at 900 and 1000 ° C. That is, in order to obtain BaTi 2 O 5 with high purity, at least two or more firing operations including calcination are required.
複数回の焼成操作は、手間となるだけでなく、操作の数だけ焼成にエネルギーを費やすため、製造コストを増大させるという問題がある。 Multiple firing operations are not only laborious, but energy is consumed for firing as many as the number of operations, which increases the manufacturing cost.
この問題を解決するために、より高エネルギーのミリング法の採用やミリング時間の拡大を通じて、原料粉末を均一混合化して反応性のばらつきを抑制し、かつ、原料粉末を微粒子化して反応性を高めたりすることにより、少ない焼成操作でＢａＴｉ2Ｏ5の生成率を向上させることが考えられる。しかし、ミリングの高エネルギー化や時間拡大は、却って製造コストを高くし、しかもスループットを落としてしまうという問題が生じる。 In order to solve this problem, through the adoption of a higher energy milling method and the expansion of the milling time, the raw material powder is uniformly mixed to suppress variation in reactivity, and the raw material powder is made finer to increase the reactivity. It is conceivable to improve the production rate of BaTi 2 O 5 with a small baking operation. However, increasing the energy of milling and expanding the time raise the problem of increasing the manufacturing cost and lowering the throughput.
また、従来法では、焼結を兼ねて焼成を行う場合には、仮焼が不可欠となる。もし仮焼をせずに焼結を行うと、ＢａＣＯ3とＴｉＯ2の反応で発生する二酸化炭素により、焼結体に要求される高密化ができなくなるという問題が生じる。 Further, in the conventional method, calcination is indispensable when firing is performed also for sintering. If sintering is performed without calcination, there arises a problem that the high density required for the sintered body cannot be obtained due to carbon dioxide generated by the reaction of BaCO 3 and TiO 2 .
その上、従来法では、ＢａＴｉ2Ｏ5を高純度で得るために、仮焼の後に１０００℃以上での焼成を必要とするため、さらなる工程数増加による製造コスト上昇を招く。 In addition, in the conventional method, in order to obtain BaTi 2 O 5 with high purity, baking at 1000 ° C. or higher is necessary after calcination, resulting in an increase in manufacturing cost due to further increase in the number of steps.
また、焼成温度を１０００℃以上とすると、多大なエネルギーの使用による製造コスト上昇や環境負荷に加え、高価な耐熱炉の使用や防災設備が必要となる場合も出るなどの問題が生じる。こうした事情から、ＢａＴｉ2Ｏ5を焼き固めずに粉末状態のまま得ればよい場合は、焼成を１０００℃未満で実行可能とするＢａＴｉ2Ｏ5の製造方法の開発が嘱望されている。 Further, if the firing temperature is 1000 ° C. or higher, problems such as an increase in manufacturing cost due to the use of a large amount of energy and an environmental load, as well as the use of an expensive heat-resistant furnace and the need for disaster prevention facilities arise. Under such circumstances, when it is sufficient to obtain BaTi 2 O 5 in a powdered state without baking it, development of a method for producing BaTi 2 O 5 that enables firing at less than 1000 ° C. is desired.
本発明は、固相反応による従来のＢａＴｉ2Ｏ5の製造方法が有していた課題を解決することを目的としたものであり、この発明により複数回の焼成操作を必要としない簡便な操作により製造コストを低減できる、固相反応法を利用したＢａＴｉ2Ｏ5系複合酸化物粉末の製造方法及びＢａＴｉ2Ｏ5系複合酸化物焼結体の製造方法を提供する。ここで、ＢａＴｉ2Ｏ5系複合酸化物とは、ＢａＴｉ2Ｏ5、又はＢａＴｉ2Ｏ5及びＢａＴｉ2Ｏ5のうちＢａ、Ｔｉを他元素で置換した酸化物で構成されるものをいう。 The object of the present invention is to solve the problems of the conventional method for producing BaTi 2 O 5 by solid-phase reaction, and a simple operation that does not require a plurality of firing operations according to the present invention. the manufacturing cost can be reduced, to provide a method of manufacturing a solid-phase reaction method the method of producing BaTi 2 O 5 based mixed oxide powder using and BaTi 2 O 5 based composite oxide sintered body. Here, the BaTi 2 O 5 -based composite oxide refers to an oxide composed of BaTi 2 O 5 or an oxide in which Ba and Ti are substituted with other elements in BaTi 2 O 5 and BaTi 2 O 5 .
発明者は簡便で製造コストの低い方法で高純度のＢａＴｉ2Ｏ5系複合酸化物を得るべく鋭意研究した結果、原料をＢａＴｉＯ3及びＴｉＯ2とする下記のＢａＴｉ2Ｏ5系複合酸化物の製造方法により本発明の目的を達成できた。 Inventor conveniently at a low manufacturing cost method of high purity BaTi 2 O 5 composite oxide intensive research as a result to obtain a, below which the raw material and BaTiO 3 and TiO 2 of BaTi 2 O 5 composite oxide The object of the present invention could be achieved by the production method.
本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法は、原子物質量比Ｔｉ／Ｂａを１．８〜２．２の範囲内にするようにＢａＴｉＯ3とＴｉＯ2からなる原料を調合する調合工程と、前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、前記粉砕物を８５０℃以上１０００℃未満で加熱する焼成工程と、を備えていることを特徴とする。 In the method for producing a BaTi 2 O 5 composite oxide according to the present invention, a raw material composed of BaTiO 3 and TiO 2 is prepared so that the atomic mass ratio Ti / Ba is in the range of 1.8 to 2.2. A mixing step, mixing and pulverizing the raw materials to form a pulverized product having an average particle size of 10 to 650 nm, and a firing step of heating the pulverized product at 850 ° C. or more and less than 1000 ° C. It is characterized by having.
また、本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法は、原子物質量比Ｔｉ／Ｂａを１．８〜２．２の範囲内にするようにＢａＴｉＯ3とＴｉＯ2からなる原料を調合する調合工程と、前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、前記粉砕物を１０〜１０3ＭＰａの圧力で圧縮する圧縮工程と、圧縮した前記粉砕物を８５０℃以上１０００℃未満で加熱する焼成工程と、を備えていることを特徴とする。
これにより、従来の固相反応法を利用した製造方法に比べて少ない工程にすることができる。また、従来の溶融法及び固相反応法を利用した製造方法に比べ、従来に比べて安価な炉の使用や製造にかかるエネルギーやコストの低減が可能となる。
Further, in the method for producing a BaTi 2 O 5 composite oxide according to the present invention, a raw material composed of BaTiO 3 and TiO 2 is used so that the atomic mass ratio Ti / Ba is in the range of 1.8 to 2.2. A blending step for blending, a mixing and pulverizing step for mixing and atomizing the raw materials to form a pulverized product having an average particle size of 10 to 650 nm, and a compressing step for compressing the pulverized product at a pressure of 10 to 10 3 MPa. And a firing step of heating the compressed pulverized product at 850 ° C. or higher and lower than 1000 ° C.
As a result, the number of steps can be reduced as compared with the manufacturing method using the conventional solid phase reaction method. Further, compared to the conventional manufacturing method using the melting method and the solid phase reaction method, it is possible to use an inexpensive furnace and to reduce energy and cost for manufacturing compared to the conventional method.
また、本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法は、原子物質量比Ｔｉ／Ｂａを１．８〜２．２の範囲内にするようにＢａＴｉＯ3とＴｉＯ2からなる原料を調合する調合工程と、前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、前記粉砕物を１２００〜１２３０℃で加熱する焼成工程と、を備えていることを特徴とする。 Further, in the method for producing a BaTi 2 O 5 composite oxide according to the present invention, a raw material composed of BaTiO 3 and TiO 2 is used so that the atomic mass ratio Ti / Ba is in the range of 1.8 to 2.2. A blending step for blending, mixing and pulverizing the raw materials to form a pulverized product having an average particle size of 10 to 650 nm, and a firing step for heating the pulverized product at 1200 to 1230 ° C. It is characterized by having.
また、本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法は、原子物質量比Ｔｉ／Ｂａを１．８〜２．２の範囲内にするようにＢａＴｉＯ3とＴｉＯ2からなる原料を調合する調合工程と、前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、前記粉砕物を１０〜１０3ＭＰａの圧力で圧縮する圧縮工程と、圧縮した前記粉砕物を１２００〜１２３０℃で加熱する焼成工程と、を備えていることを特徴とする。
これにより、仮焼をせずにＢａＴｉ2Ｏ5系複合酸化物の高密焼結を行うことができるので、ＢａＴｉ2Ｏ5系複合酸化物の高密焼結体を安価に提供することができる。
Further, in the method for producing a BaTi 2 O 5 composite oxide according to the present invention, a raw material composed of BaTiO 3 and TiO 2 is used so that the atomic mass ratio Ti / Ba is in the range of 1.8 to 2.2. A blending step for blending, a mixing and pulverizing step for mixing and atomizing the raw materials to form a pulverized product having an average particle size of 10 to 650 nm, and a compressing step for compressing the pulverized product at a pressure of 10 to 10 3 MPa. And a firing step of heating the compressed pulverized product at 1200 to 1230 ° C.
Thus, it is possible to perform dense sintering of BaTi 2 O 5 composite oxide without calcining, it is possible to provide an inexpensive dense sintered body of BaTi 2 O 5 based complex oxide.
また、前記調合工程において、さらにＶ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｅ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔの群から選ばれる少なくとも一種類の元素を含む第一の添加物を加えることを特徴とする。また、前記第一の添加物が、二酸化物であることを特徴とする。 In the blending step, V, Cr, Mn, Fe, Co, Ni, Ge, Se, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Sn, Hf, Ta, W, Re, Os, A first additive containing at least one element selected from the group of Ir and Pt is added. Further, the first additive is a dioxide.
また、前記調合工程において、さらにＣａ、Ｒｂ、Ｓｒ、Ｃｓ、Ｐｂ、Ｆｒ、Ｒａの群の中から選ばれる少なくとも一種類の元素を含む第二の添加物を加えることを特徴とする。また、前記第二の添加物が、炭酸塩またはチタン酸塩であることを特徴とする。
この元素置換により、結晶格子を歪ませ、電子分布を変化させることにより、誘電率、圧電定数、結晶変態温度などを制御できる。
Further, in the preparation step, a second additive containing at least one element selected from the group consisting of Ca, Rb, Sr, Cs, Pb, Fr, and Ra is further added. The second additive is a carbonate or titanate.
By this element substitution, the dielectric constant, piezoelectric constant, crystal transformation temperature, and the like can be controlled by distorting the crystal lattice and changing the electron distribution.
本発明に係るＢａＴｉ2Ｏ5系複合酸化粉末の製造方法は、従来の固相反応法を利用した製造方法に比べて少ない工程にすることができる。
また、従来の溶融法及び固相反応法を利用した製造方法に比べ、従来に比べて安価な炉の使用や製造にかかるエネルギーやコストの低減が可能となる。
また、本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法により、仮焼をせずにＢａＴｉ2Ｏ5系複合酸化物の高密焼結を行うことができるので、ＢａＴｉ2Ｏ5系複合酸化物の高密焼結体を安価に提供することができる。
The manufacturing method of the BaTi 2 O 5 composite oxide powder according to the present invention can be reduced in steps compared to a manufacturing method using a conventional solid phase reaction method.
Further, compared to the conventional manufacturing method using the melting method and the solid phase reaction method, it is possible to use an inexpensive furnace and to reduce energy and cost for manufacturing compared to the conventional method.
Further, by the manufacturing method of BaTi 2 O 5 based composite oxide according to the present invention, since without the calcination can be carried out dense sintering of BaTi 2 O 5 based complex oxide, BaTi 2 O 5 composite An oxide dense sintered body can be provided at low cost.
本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法における第１の実施形態について、図１を参照しながら説明する。この製造方法は調合工程、混合・粉砕工程、および焼成工程から構成されている。 A first embodiment of the method for producing a BaTi 2 O 5 composite oxide according to the present invention will be described with reference to FIG. This manufacturing method includes a blending step, a mixing / pulverizing step, and a firing step.
調合工程では、純度９９．９％以上のＢａＴｉＯ3およびＴｉＯ2をＴｉ原子とＢａ原子の物質量比（Ｔｉ／Ｂａ）が１．８〜２．２となるように原料を秤量する。すなわち、ＢａＴｉＯ3中のＴｉとＴｉＯ2中のＴｉがおよそ１：１となるように混合される。 In the blending step, BaTiO 3 and TiO 2 having a purity of 99.9% or more are weighed so that the material ratio (Ti / Ba) between Ti atoms and Ba atoms is 1.8 to 2.2. That is, Ti in BaTiO 3 and Ti in TiO 2 are mixed so as to be approximately 1: 1.
Ｔｉ／Ｂａは２であることが好ましいが、これ以降の操作によりＴｉもしくはＢａが損失する虞がある場合は、１．８〜２．２の範囲で適宜調整できる。原子物質量比Ｔｉ／Ｂａが１．８より小さいとき、又は２．２より大きいときは、ＢａＴｉ2Ｏ5の原子物質量比と大きく異なってしまうため、ＢａＴｉ2Ｏ5系複合酸化物を安定して製造できない虞がある。 Ti / Ba is preferably 2. However, when there is a possibility that Ti or Ba may be lost by the subsequent operation, it can be appropriately adjusted within the range of 1.8 to 2.2. When atomic substance amount ratio Ti / Ba is less than 1.8, or 2.2 when larger, since greatly different and BaTi 2 O 5 atomic substance amount ratio, stabilize the BaTi 2 O 5 composite oxide There is a possibility that it cannot be manufactured.
混合・粉砕工程では、前記粉末の均一混合化し、原料粒子を微粒化する。具体的には、たとえば、前記粉末をメノウポットに入れ、ミリング用のジルコニアボールおよび水を加え、遊星型ボールミルで約３０時間のミリングを行う。その後、ジルコニアボールを除去し、１００℃〜１５０℃で乾燥する。 In the mixing and pulverizing step, the powder is uniformly mixed and the raw material particles are atomized. Specifically, for example, the powder is put in an agate pot, zirconia balls for milling and water are added, and milling is performed for about 30 hours with a planetary ball mill. Thereafter, the zirconia balls are removed and dried at 100 to 150 ° C.
この例では、粉砕機として遊星型ボールミルを用い、水を用いた湿式法により混合・粉砕を行ったが、粉砕機は遊星型ボールミルに限定されず、種々のボールミル、ビーズミル、コロイドミル等の粉砕機を好適に用いることができる。また、乾式・湿式混合のいずれの方法で行っても良い。 In this example, a planetary ball mill was used as a pulverizer, and mixing and pulverization were performed by a wet method using water. However, the pulverizer is not limited to a planetary ball mill, and various ball mills, bead mills, colloid mills, etc. The machine can be suitably used. Moreover, you may carry out by any method of dry type and wet mixing.
また、処理後の粉砕物の平均粒径は１０ｎｍ〜１μｍである。また、粉砕物の平均粒径は、より好ましくは１０〜６５０ｎｍである。これを実現するためにミリング時間を２０〜２００時間の間で適宜調整してもよい。また、ミリング用媒質は、原料粉末同士の固着を防ぎ、よく分散させるものであれば特に水に限定されるものではなく、水以外には、例えばエタノール、プロパノール、アセトン等の液体を好適に使用できる。 Moreover, the average particle diameter of the processed ground material is 10 nm to 1 μm. The average particle size of the pulverized product is more preferably 10 to 650 nm. In order to realize this, the milling time may be appropriately adjusted between 20 and 200 hours. Further, the milling medium is not particularly limited to water as long as it prevents the powders from adhering to each other and can be well dispersed. In addition to water, liquids such as ethanol, propanol, and acetone are preferably used. it can.
焼成工程では、前記粉末を、８５０〜１２３０℃で固相反応させる。これにより、ＢａＴｉ2Ｏ5を得ることができる。たとえば、９００℃以上で６時間の大気下常圧焼成では、ＢａＴｉ2Ｏ5を主成分とすることができ、９７５℃以上では、単相とすることができた。 In the firing step, the powder is subjected to a solid phase reaction at 850 to 1230 ° C. Thereby, BaTi 2 O 5 can be obtained. For example, in atmospheric pressure firing at 900 ° C. or higher for 6 hours, BaTi 2 O 5 can be a main component, and at 975 ° C. or higher, a single phase can be obtained.
焼成法としては、マッフル炉やカンタル炉などを使用する一般的な焼成・焼結法のほか、スパーク・プラズマ焼結法、ホットプレス法を採用してもよい。また、焼成の際の雰囲気は、常圧の空気でも、真空でも、窒素やアルゴンなどの不活性ガスでも、水蒸気雰囲気でもよい。ただし、真空または不活性ガス雰囲気で焼成を行った場合は、焼成の後に酸素を含む雰囲気で９００〜１１００でのアニーリングを行う。 As a firing method, in addition to a general firing / sintering method using a muffle furnace or a Kanthal furnace, a spark / plasma sintering method or a hot press method may be employed. The atmosphere during firing may be atmospheric pressure air, vacuum, an inert gas such as nitrogen or argon, or a water vapor atmosphere. However, when firing is performed in a vacuum or an inert gas atmosphere, annealing is performed at 900 to 1100 in an atmosphere containing oxygen after firing.
ＢａＴｉ2Ｏ5は１１５０〜１２００℃で分解することが知られているが、この温度範囲でも、焼成時間を短くし、たとえば１分〜２時間とすれば、分解を抑制できる。よって、本発明に係るＢａＴｉ2Ｏ5複合酸化物の製造方法における焼成工程の焼成温度は１２３０℃まで適用することが可能である。ただし、ＢａＴｉ2Ｏ5複合酸化物を粉末として得るためには、分解の回避が容易である１１５０℃までとすることがより好ましく、さらには製造コストを低減できる１０００℃未満とすることが最も好ましい。 BaTi 2 O 5 is known to decompose at 1150 to 1200 ° C. Even in this temperature range, the decomposition can be suppressed by shortening the firing time, for example, 1 minute to 2 hours. Therefore, the firing temperature in the firing step in the method for producing a BaTi 2 O 5 composite oxide according to the present invention can be applied up to 1230 ° C. However, in order to obtain a BaTi 2 O 5 composite oxide as a powder, it is more preferable to set the temperature to 1150 ° C., which is easy to avoid decomposition, and most preferable to be less than 1000 ° C., which can reduce the manufacturing cost. .
また、焼成工程でＢａＴｉ2Ｏ5系複合酸化物の焼結を兼ねて焼成を行う場合、焼成温度を１２００〜１２３０℃、より好ましくは分解の回避が容易な１２２０〜１２３０℃とする。これにより、ＢａＴｉ2Ｏ5系複合酸化物焼結体が形成できる。また、焼結密度を上げるために、焼成工程の直前に焼結助剤を添加することもできる。焼結助剤として、たとえばポリビニルアルコールを使用できる。 Further, in the case where the firing is performed while also sintering the BaTi 2 O 5 composite oxide in the firing step, the firing temperature is set to 1200 to 1230 ° C., more preferably 1220 to 1230 ° C., which facilitates avoiding decomposition. Thereby, a BaTi 2 O 5 composite oxide sintered body can be formed. Further, in order to increase the sintering density, a sintering aid can be added immediately before the firing step. For example, polyvinyl alcohol can be used as a sintering aid.
また、調合工程で、たとえば第一の添加物としてＺｒＯ2、第二の添加物としてＣａＣＯ3またはＳｒＣＯ3を原料に添加することにより、焼成工程後の最終生成物として、ＴｉをＺｒ、ＢａをＣａまたはＳｒにより置換したＢａＴｉ2Ｏ5系複合酸化物をそれぞれ作製することもできる。 Further, in the preparation step, for example, ZrO 2 as the first additive and CaCO 3 or SrCO 3 as the second additive are added to the raw material, so that Ti is Zr and Ba as the final product after the firing step. BaTi 2 O 5 -based composite oxides substituted with Ca or Sr can also be produced.
この例では、置換元素としてＺｒ、Ｃａ、Ｓｒを用いたが、一般に元素置換は互いに価数及びイオン半径及び配位数が同じであれば行うことができる。たとえば、ＢａＴｉ2Ｏ5中のＴｉと価数及びイオン半径及び配位数が近くなりうる元素としてＶ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｅ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔがある。 In this example, Zr, Ca, and Sr are used as substitution elements, but generally element substitution can be performed if the valence, ion radius, and coordination number are the same. For example, V, Cr, Mn, Fe, Co, Ni, Ge, Se, Zr, Nb, Mo, Tc, Ru can be used as elements that can be close to valence, ion radius, and coordination number of Ti in BaTi 2 O 5. , Rh, Pd, Sn, Hf, Ta, W, Re, Os, Ir, and Pt.
Ｔｉに対する置換元素を含む第一の添加物としては、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｅ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔが４価である化合物を使用すればよい。より好ましくは、第一の添加物は、原料と同種の化合物、すなわち、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｅ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔの二酸化物を使用する。第一の添加物をＴｉＯ2と同じ二酸化物で構成することで効率的に置換を行うことができる。 As the first additive containing a substitution element for Ti, V, Cr, Mn, Fe, Co, Ni, Ge, Se, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Sn, Hf, Ta, A compound in which W, Re, Os, Ir, and Pt are tetravalent may be used. More preferably, the first additive is a compound of the same type as the raw material, that is, V, Cr, Mn, Fe, Co, Ni, Ge, Se, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Sn. , Hf, Ta, W, Re, Os, Ir, and Pt dioxide are used. By constituting the first additive with the same dioxide as TiO 2 , substitution can be performed efficiently.
また、ＢａＴｉ2Ｏ5中のＢａと価数及びイオン半径及び配位数が近くなりうる元素としてＣａ、Ｒｂ、Ｓｒ、Ｃｓ、Ｐｂ、Ｆｒ、Ｒａがある。 Examples of elements that can be close to Ba in BaTi 2 O 5 in terms of valence, ion radius, and coordination number include Ca, Rb, Sr, Cs, Pb, Fr, and Ra.
Ｂａに対する置換元素を含む第二の添加物としては、Ｃａ、Ｒｂ、Ｓｒ、Ｃｓ、Ｐｂ、Ｆｒ、Ｒａが２価である化合物を使用すればよい。より好ましくは、第二の添加物は原料と同種の化合物、すなわち、Ｃａ、Ｒｂ、Ｓｒ、Ｃｓ、Ｐｂ、Ｆｒ、Ｒａの炭酸塩またはチタン酸塩を使用する。特に、第二の添加物をＢａＴｉＯ3と同じ二チタン酸塩で構成することで効率的に置換を行うことができる。 As the second additive containing a substitution element for Ba, a compound in which Ca, Rb, Sr, Cs, Pb, Fr, and Ra are divalent may be used. More preferably, the second additive uses the same compound as the raw material, that is, a carbonate or titanate of Ca, Rb, Sr, Cs, Pb, Fr, and Ra. In particular, substitution can be performed efficiently by constituting the second additive with the same dititanate as BaTiO 3 .
また、元素置換は、Ｂａ2+サイトとＴｉ4+サイトの両方をそれぞれの置換元素で同時に置換してもよいし、別々に置換してもよい。元素置換により、結晶格子を歪ませ、電子分布を変化させることにより、誘電率、圧電定数、結晶変態温度などを制御できる。なお、同時に置換した場合は、工程時間の短縮化を図れる。
これにより、ＢａＴｉ2Ｏ5及びＢａＴｉ2Ｏ5のうちＢａ、Ｔｉを置換した酸化物で構成されるＢａＴｉ2Ｏ5系複合酸化物を形成することができる。
In addition, the element substitution may be performed by simultaneously substituting both the Ba 2+ site and the Ti 4+ site with the respective substitution elements or separately. By substituting the crystal lattice and changing the electron distribution by element substitution, the dielectric constant, piezoelectric constant, crystal transformation temperature, and the like can be controlled. In addition, when it replaces simultaneously, process time can be shortened.
As a result, it is possible to form a BaTi 2 O 5 composite oxide composed of an oxide in which Ba and Ti are substituted among BaTi 2 O 5 and BaTi 2 O 5 .
次に、本発明に係るＢａＴｉ2Ｏ5系複合酸化物の製造方法における第２の実施形態を、図２を参照しながら説明する。
調合工程および混合・粉砕工程は前記実施例と同じ条件で行う。なお、元素置換は、第１の実施形態と同様に行うことができる。
Next, a second embodiment of the method for producing a BaTi 2 O 5 composite oxide according to the present invention will be described with reference to FIG.
The blending step and the mixing / pulverizing step are performed under the same conditions as in the previous examples. Element replacement can be performed in the same manner as in the first embodiment.
圧縮工程では、調合工程で作製した粉末を型に詰め、これを冷間等方加圧（以下、ＣＩＰと略記）により約３００ＭＰａで圧縮し、高密成形体を作製する。
この例では、ＣＩＰ装置を用いた圧力を約３００ＭＰａでの圧縮法を採用したが、原料粒子を高密化でれば圧縮装置や圧力は限定されない。また、圧力は１０〜１０3ＭＰａとすればよい。
焼成工程は第１の実施形態と同じ条件で行う。
In the compression step, the powder produced in the blending step is packed in a mold and compressed at about 300 MPa by cold isostatic pressing (hereinafter abbreviated as CIP) to produce a high-density molded body.
In this example, a compression method using a pressure of about 300 MPa using a CIP device is adopted, but the compression device and pressure are not limited as long as the raw material particles are made dense. The pressure may be 10 to 10 3 MPa.
The firing step is performed under the same conditions as in the first embodiment.
また、本発明のＢａＴｉ2Ｏ5系複合酸化物は、コンデンサに適用が可能である。また、本発明のＢａＴｉ2Ｏ5を強誘電体メモリ（ＦＲＡＭ）にも適用できる。また、本発明のＢａＴｉ2Ｏ5系複合酸化物は、アクチュエーター等の圧電性素子としても適用可能である。また、本発明のＢａＴｉ2Ｏ5粉末は、高い結晶性を有する粒子から成るため、これを粒成長法に適用し、高度に配向した配向膜などの配向誘電体を作製することができる。
Further, the BaTi 2 O 5 composite oxide of the present invention can be applied to a capacitor. Also, the BaTi 2 O 5 of the present invention can be applied to a ferroelectric memory (FRAM). Further, the BaTi 2 O 5 complex oxide of the present invention can also be applied as a piezoelectric element such as an actuator. In addition, since the BaTi 2 O 5 powder of the present invention is composed of particles having high crystallinity, it can be applied to a grain growth method to produce an alignment dielectric such as a highly aligned alignment film.
Claims (8)
調合した前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、
前記粉砕物を９００℃以上１０００℃未満で加熱する焼成工程と、
を備えており、焼成生成物の主成分がＢａＴｉ 2 Ｏ 5 系複合酸化物であることを特徴とするＢａＴｉ2Ｏ5系複合酸化物の製造方法。 Preparing a raw material composed of BaTiO 3 and TiO 2, and making the atomic mass ratio Ti / Ba of the raw material within a range of 1.8 to 2.2;
Mixing and pulverizing the mixed raw materials to form a pulverized product having an average particle size of 10 to 650 nm;
A firing step of heating the pulverized product at 900 ° C. or more and less than 1000 ° C .;
It includes a method of BaTi 2 O 5 based composite oxide, wherein the main component of the sintered product is BaTi 2 O 5 based complex oxide.
調合した前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、
前記粉砕物を１０〜１０3ＭＰａの圧力で圧縮する圧縮工程と、
圧縮した前記粉砕物を９００℃以上１０００℃未満で加熱する焼成工程と、
を備えており、焼成生成物の主成分がＢａＴｉ 2 Ｏ 5 系複合酸化物であることを特徴とするＢａＴｉ2Ｏ5系複合酸化物の製造方法。 Preparing a raw material composed of BaTiO 3 and TiO 2, and making the atomic mass ratio Ti / Ba of the raw material within a range of 1.8 to 2.2;
Mixing and pulverizing the mixed raw materials to form a pulverized product having an average particle size of 10 to 650 nm;
A compression step of compressing the pulverized product at a pressure of 10 to 10 3 MPa;
A firing step of heating the compressed pulverized product at 900 ° C. or more and less than 1000 ° C .;
It includes a method of BaTi 2 O 5 based composite oxide, wherein the main component of the sintered product is BaTi 2 O 5 based complex oxide.
調合した前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、
前記粉砕物を１２００〜１２３０℃で加熱する焼成工程と、
を備えていることを特徴とするＢａＴｉ2Ｏ5系複合酸化物の製造方法。 Preparing a raw material composed of BaTiO 3 and TiO 2, and making the atomic mass ratio Ti / Ba of the raw material within a range of 1.8 to 2.2;
Mixing and pulverizing the mixed raw materials to form a pulverized product having an average particle size of 10 to 650 nm;
A firing step of heating the pulverized product at 1200 to 1230 ° C;
A method for producing a BaTi 2 O 5 composite oxide, comprising:
調合した前記原料の混合及び微粒化を行い、平均粒径１０〜６５０ｎｍの粉砕物を形成する混合・粉砕工程と、
前記粉砕物を１０〜１０3ＭＰａの圧力で圧縮する圧縮工程と、
圧縮した前記粉砕物を１２００〜１２３０℃で加熱する焼成工程と、
を備えていることを特徴とするＢａＴｉ2Ｏ5系複合酸化物の製造方法。 Preparing a raw material composed of BaTiO 3 and TiO 2, and making the atomic mass ratio Ti / Ba of the raw material within a range of 1.8 to 2.2;
Mixing and pulverizing the mixed raw materials to form a pulverized product having an average particle size of 10 to 650 nm;
A compression step of compressing the pulverized product at a pressure of 10 to 10 3 MPa;
A baking step of heating the compressed pulverized product at 1200 to 1230 ° C;
A method for producing a BaTi 2 O 5 composite oxide, comprising:
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