JP4726082B2 - Method for producing crystal-oriented ceramics - Google Patents
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本発明は、構成粒子の結晶方位を揃えた結晶配向セラミックスの製造方法に関する。 The present invention relates to a method for producing a crystallographically-oriented ceramic in which the crystal orientations of constituent particles are aligned.
結晶配向セラミックスの製造方法としてＲＴＧＧ(Ｒｅａｃｔｉｖｅ Ｔｅｍｐｌａｔｅｄ Ｇｒａｉｎ Ｇｒｏｗｔｈ)法と称される方法が知られている。このＲＴＧＧ法は従前のＴＧＧ(Ｔｅｍｐｌａｔｅｄ Ｇｒａｉｎ Ｇｒｏｗｔｈ)法の改良に当たるもので、主原料たるテンプレート粒子と補足原料とを含むスラリーを作成し、該スラリーにドクターブレード等によって応力を加えてテンプレート粒子が配列した成形体を作成し、該成形体を熱処理してテンプレート粒子と補足原料とを反応焼結させて目的物質の焼結体(結晶配向セラミックス)を得る方法である。 As a method for producing a crystallographically-oriented ceramic, a method called RTGG (Reactive Templated Grain Growth) method is known. This RTGG method is an improvement of the conventional TGG (Templated Grain Growth) method. A slurry containing template particles as a main raw material and a supplementary raw material is prepared, and stress is applied to the slurry by a doctor blade or the like to arrange the template particles. In this method, the molded body is prepared, and the molded body is heat-treated to react and sinter the template particles and the supplementary raw material to obtain a sintered body (crystal oriented ceramic) of the target substance.
また、結晶配向セラミックスの製造方法として強磁場法と称される方法も知られている。この強磁場法は、主原料たる粒子を含むスラリーを作成し、該スラリーに強磁場を印加して粒子が配向した成形体を作成し、該成形体を熱処理して焼結体(結晶配向セラミックス)を得る方法である。
前記ＲＴＧＧ法は、テンプレート粒子の成長速度の差異による異方性を結晶配向に利用しているため、配向させる結晶方位差が限定されることもあって構成粒子の結晶方位を制御し難い。一方、前記強磁場法は、強磁場を利用して配向を行っているためＲＴＧＧ法に比べて構成粒子の結晶方位を制御し易いが、より高い結晶配向度を得るには未だ改良の余地がある。 In the RTGG method, since the anisotropy due to the difference in the growth rate of the template particles is utilized for crystal orientation, the crystal orientation of the constituent particles is difficult to control because the crystal orientation difference to be oriented is limited. On the other hand, since the strong magnetic field method is oriented using a strong magnetic field, the crystal orientation of the constituent particles is easier to control than the RTGG method, but there is still room for improvement in order to obtain a higher degree of crystal orientation. is there.
本発明は前記事情に鑑みて創作されたもので、その目的とするところは、高い結晶配向度が得られる結晶配向セラミックスの製造方法を提供することにある。 The present invention was created in view of the above circumstances, and an object thereof is to provide a method for producing a crystallographically-oriented ceramic capable of obtaining a high degree of crystal orientation.
前記課題を達成するため、本発明の結晶配向セラミックスの製造方法は、強磁場印加により配向し得る第１粒子と該第１粒子への金属イオン拡散を伴う反応焼結により目的物質を生成し得る第２粒子とを含むスラリーを作成するステップと、スラリーに強磁場を印加して第１粒子が配向した成形体を作成するステップと、成形体を熱処理して第２粒子から第１粒子への金属イオン拡散により第１粒子と第２粒子を反応焼結させて目的物質の焼結体を作成するステップとを備える、ことをその特徴とする。 In order to achieve the above object, the method for producing a crystallographically-oriented ceramic of the present invention can generate a target substance by first sintering that can be oriented by applying a strong magnetic field and reactive sintering involving diffusion of metal ions into the first particle. Creating a slurry containing the second particles, applying a strong magnetic field to the slurry to create a shaped body in which the first particles are oriented, and heat-treating the shaped body from the second particles to the first particles. And a step of reacting and sintering the first particles and the second particles by metal ion diffusion to create a sintered body of the target substance.
この結晶配向セラミックスの製造方法によれば、強磁場を印加して第１粒子を配向させた後に第２粒子から第１粒子への金属イオン拡散により第１粒子と第２粒子を反応焼結させているので、配向後の第１粒子の結晶方位は反応によって変化せず、目的物質の粒子は配向後の第１粒子の結晶方位に沿って成長する。つまり、生成された目的物質の粒子の結晶方位は配向後の第１粒子の結晶方位に従うため粒成長によっても変化することはないので、作成された焼結体に高い結晶配向度を得ることができる。 According to this method for producing a crystal-oriented ceramic, after applying a strong magnetic field to orient the first particles, the first particles and the second particles are reacted and sintered by metal ion diffusion from the second particles to the first particles. Therefore, the crystal orientation of the first particles after orientation does not change by reaction, and the particles of the target substance grow along the crystal orientation of the first particles after orientation. In other words, since the crystal orientation of the produced target substance particles follows the crystal orientation of the first particles after orientation, it does not change due to grain growth, so that a high degree of crystal orientation can be obtained in the produced sintered body. it can.
本発明によれば、高い結晶配向度が得られる結晶配向セラミックスの製造方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the crystal orientation ceramics from which a high degree of crystal orientation is obtained can be provided.
本発明の前記目的とそれ以外の目的と、構成特徴と、作用効果は、以下の説明と添付図面によって明らかとなる。 The above object and other objects, structural features, and operational effects of the present invention will become apparent from the following description and the accompanying drawings.
本発明による結晶配向セラミックスの製造方法は、強磁場印加により配向し得る第１粒子と該第１粒子への金属イオン拡散を伴う反応焼結により目的物質を生成し得る第２粒子とを含むスラリーを作成するステップと、スラリーに強磁場を印加して第１粒子が配向した成形体を作成するステップと、成形体を熱処理して第２粒子から第１粒子への金属イオン拡散により第１粒子と第２粒子を反応焼結させて目的物質の焼結体を作成するステップとを備えている。 The method for producing a crystallographically-oriented ceramic according to the present invention comprises a slurry containing first particles that can be oriented by applying a strong magnetic field and second particles that can produce a target substance by reactive sintering involving diffusion of metal ions into the first particles. A step in which a strong magnetic field is applied to the slurry to form a shaped body in which the first particles are oriented, and the shaped body is heat-treated to diffuse the first particles by metal ion diffusion from the second particles to the first particles. And a step of reacting and sintering the second particles to produce a sintered body of the target substance.
前記スラリーには、第１粒子と第２粒子がそれぞれスラリー中に分散しているもの、或いは、第２粒子が表面にコーティングされた第１粒子がスラリー中に分散しているものが利用できる。前者のスラリーの場合には第１粒子と第２粒子の粒径比(第１粒子の粒径／第２粒子の粒径)が３．８以上、好ましくは３．８以上２２以下のものを用いる。後者のスラリーの場合には第１粒子の粒径と第２粒子のコーティング厚さの比(第１粒子の粒径／第２粒子のコーティング厚さ)が４．６以上、好ましくは４．６以上２７以下のものを用いる。 As the slurry, one in which the first particles and the second particles are dispersed in the slurry, or one in which the first particles coated on the surface of the second particles are dispersed in the slurry can be used. In the case of the former slurry, the particle size ratio between the first particles and the second particles (the particle size of the first particles / the particle size of the second particles) is 3.8 or more, preferably 3.8 or more and 22 or less. Use. In the case of the latter slurry, the ratio of the first particle size to the second particle coating thickness (first particle size / second particle coating thickness) is 4.6 or more, preferably 4.6. 27 or less is used.
前記目的物質には、一般式が(Ｂｉ2Ｏ2)2+(Ａm-1ＢmＯ3m+1)2-で表され、且つ、Ａが１〜３価の金属元素から成りＢが２〜６価の金属元素から成るビスマス層状化合物や、一般式が(Ａ１)4(Ａ２)2Ｃ4(Ｂ１)2(Ｂ２)8Ｏ30で表され、且つ、Ａ１及びＡ２が１〜２価の金属元素から成りＣが１価の金属元素から成りＢ１及びＢ２が５価の金属元素から成るタングステンブロンズ型化合物や、一般式が(Ａ３)(Ｂ３)Ｏ3で表され、且つ、Ａ３が１〜３価の金属元素から成りＢ３が３〜５価の金属元素から成るペロブスカイト型化合物が挙げられる。 The target substance is represented by the general formula (Bi 2 O 2 ) 2+ (A m-1 B m O 3m + 1 ) 2- , and A is composed of 1 to 3 valent metal elements. A bismuth layered compound composed of a divalent to hexavalent metal element, or a general formula represented by (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are 1 to 2 A tungsten bronze type compound composed of a valent metal element, C composed of a monovalent metal element, and B1 and B2 composed of a pentavalent metal element, or a general formula represented by (A3) (B3) O 3 , and A3 A perovskite type compound in which is composed of 1 to 3 valent metal elements and B3 is composed of 3 to 5 valent metal elements.
目的物質として前記ビスマス層状化合物を得る場合には、(１)第１粒子としてＢｉを含む１〜３価の金属元素を少なくとも１種類含み、且つ、Ｂｉを除く２〜６価の金属元素を少なくとも１種類含むビスマス層状化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いるか、(２)第１粒子としてその一般式が(Ａ１)4(Ａ２)2Ｃ4(Ｂ１)2(Ｂ２)8Ｏ30で表され、且つ、Ａ１及びＡ２が１〜２価の金属元素から成りＣが１価の金属元素から成りＢ１及びＢ２が５価の金属元素から成るタングステンブロンズ型化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いる。 In the case of obtaining the bismuth layered compound as the target substance, (1) at least one 1 to 3 valent metal element containing Bi as the first particles and at least 2 to 6 valent metal elements excluding Bi Use one kind of bismuth layered compound, and use as the second particle a material capable of diffusing metal ions necessary for producing a sintered body of the target material, or (2) the general formula of the first particle as (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of a monovalent metal element, C is composed of a monovalent metal element, and B1 and B2 are 5 A tungsten bronze-type compound composed of a valent metal element is used, and a substance capable of diffusing metal ions necessary for producing a sintered body of a target substance is used as the second particles.
前記(１)の具体例を挙げれば、目的物質としてＳｒＢｉ4Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＳｒＴｉＯ3を用い、目的物質としてＣａＢｉ4Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＣａＴｉＯ3を用い、目的物質としてＢａＢｉ4Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＢａＴｉＯ3を用い、目的物質としてＮａ0.5Ｂｉ4.5Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＢｉ0.5Ｎａ0.5ＴｉＯ3を用い、目的物質としてＫ0.5Ｂｉ4.5Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＢｉ0.5Ｋ0.5ＴｉＯ3を用い、目的物質としてＰｂＢｉ4Ｔｉ4Ｏ15を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＰｂＴｉＯ3を用い、目的物質としてＳｒ2Ｂｉ4Ｔｉ5Ｏ18を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＳｒＴｉＯ3を用い、目的物質としてＢａ2Ｂｉ4Ｔｉ5Ｏ18を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＢａＴｉＯ3を用い、目的物質としてＰｂ2Ｂｉ4Ｔｉ5Ｏ18を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子としてＰｂＴｉＯ3を用いる。 As a specific example of the above (1), when obtaining SrBi 4 Ti 4 O 15 as the target substance, Bi 4 Ti 3 O 12 is used as the first particle, SrTiO 3 is used as the second particle, and CaBi as the target substance. When obtaining 4 Ti 4 O 15 , Bi 4 Ti 3 O 12 is used as the first particles, CaTiO 3 is used as the second particles, and when BiBi 4 Ti 4 O 15 is obtained as the target substance, Bi is used as the first particles. When 4 Ti 3 O 12 is used and BaTiO 3 is used as the second particle and Na 0.5 Bi 4.5 Ti 4 O 15 is obtained as the target substance, Bi 4 Ti 3 O 12 is used as the first particle and Bi 0.5 is used as the second particle. When Na 0.5 TiO 3 is used and K 0.5 Bi 4.5 Ti 4 O 15 is obtained as the target substance, Bi 4 Ti 3 O 12 is used as the first particle, Bi 0.5 K 0.5 TiO 3 is used as the second particle, and the target substance is used. As PbBi 4 T When i 4 O 15 is obtained, Bi 4 Ti 3 O 12 is used as the first particle, PbTiO 3 is used as the second particle, and when Sr 2 Bi 4 Ti 5 O 18 is obtained as the target substance, the first particle is used. When Bi 4 Ti 3 O 12 is used and SrTiO 3 is used as the second particle and Ba 2 Bi 4 Ti 5 O 18 is obtained as the target substance, Bi 4 Ti 3 O 12 is used as the first particle and BaTiO is used as the second particle. 3 is used, Pb 2 Bi 4 Ti 5 O 18 is obtained as a target substance, Bi 4 Ti 3 O 12 is used as the first particles, and PbTiO 3 is used as the second particles.
前記(２)の具体例を挙げれば、目的物質としてＳｒＢｉ2Ｎｂ2Ｏ9を得る場合には第１粒子としてＳｒＮｂ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用い、目的物質としてＳｒＢｉ2Ｔａ2Ｏ9を得る場合には第１粒子としてＳｒＴａ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用い、目的物質としてＢａＢｉ2Ｎｂ2Ｏ9を得る場合には第１粒子としてＢａＮｂ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用い、目的物質としてＢａＢｉ2Ｔａ2Ｏ9を得る場合には第１粒子としてＢａＴａ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用い、目的物質としてＰｂＢｉ2Ｎｂ2Ｏ9を得る場合には第１粒子としてＰｂＮｂ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用い、目的物質としてＰｂＢｉ2Ｔａ2Ｏ9を得る場合には第１粒子としてＰｂＴａ2Ｏ6を用い第２粒子としてＢｉ2Ｏ3を用いる。 To give a specific example of the above (2), when obtaining SrBi 2 Nb 2 O 9 as the target substance, SrNb 2 O 6 is used as the first particle, Bi 2 O 3 is used as the second particle, and SrBi as the target substance. When 2 Ta 2 O 9 is obtained, SrTa 2 O 6 is used as the first particle, Bi 2 O 3 is used as the second particle, and when BaBi 2 Nb 2 O 9 is obtained as the target substance, BaNb is used as the first particle. When using 2 O 6 and using Bi 2 O 3 as the second particle and obtaining BaBi 2 Ta 2 O 9 as the target substance, BaTa 2 O 6 is used as the first particle and Bi 2 O 3 is used as the second particle. the Bi 2 O 3 used as the second particles with PbNb 2 O 6 as the first particles in the case of obtaining PbBi 2 Nb 2 O 9 as a target substance, in the case of obtaining a PbBi 2 Ta 2 O 9 as target substance use the PBTA 2 O 6 as the first particles Using Bi 2 O 3 as the second particles.
また、目的物質として前記タングステンブロンズ型化合物を得る場合には、(１)第１粒子としてその一般式が(Ａ１)4(Ａ２)2Ｃ4(Ｂ１)2(Ｂ２)8Ｏ30で表され、且つ、Ａ１及びＡ２が１〜２価の金属元素から成りＣが１価の金属元素から成りＢ１及びＢ２が５価の金属元素から成る目的物質よりも分子量の小さなタングステンブロンズ型化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いる。 When obtaining the tungsten bronze type compound as the target substance, (1) the general formula of the first particle is represented by (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 In addition, a tungsten bronze type compound having a molecular weight smaller than that of the target substance, in which A1 and A2 are composed of 1 to 2 metal elements, C is composed of monovalent metal elements, and B1 and B2 are pentavalent metal elements, A material capable of diffusing metal ions necessary for producing a sintered body of the target material is used as the second particles.
前記(１)の具体例を挙げれば、目的物質としてＳｒ2ＮａＮｂ5Ｏ15を得る場合には第１粒子としてＳｒＮｂ2Ｏ6を用い第２粒子としてＮａＮｂＯ3を用い、目的物質としてＢａ2ＮａＮｂ5Ｏ15を得る場合には第１粒子としてＢａＮｂ2Ｏ6を用い第２粒子としてＮａＮｂＯ3を用い、目的物質としてＫＳｒ2Ｎｂ5Ｏ15を得る場合には第１粒子としてＳｒＮｂ2Ｏ5を用い第２粒子としてＫＮｂＯ3を用い、目的物質としてＫＢａ2Ｎｂ5Ｏ15を得る場合には第１粒子としてＢａＮｂ2Ｏ5を用い第２粒子としてＫＮｂＯ3を用いる。 As a specific example of the (1), the NaNbO 3 used as the second particles with SrNb 2 O 6 as the first particles in the case of obtaining a Sr 2 NaNb 5 O 15 as a target substance, Ba 2 NaNb purpose material When obtaining 5 O 15 , BaNb 2 O 6 is used as the first particles, NaNbO 3 is used as the second particles, and when KSr 2 Nb 5 O 15 is obtained as the target substance, SrNb 2 O 5 is used as the first particles. When KNbO 3 is used as the second particle and KBa 2 Nb 5 O 15 is obtained as the target substance, BaNb 2 O 5 is used as the first particle and KNbO 3 is used as the second particle.
さらに、目的物質として前記ペロブスカイト型化合物を得る場合には、(１)第１粒子としてその一般式が(Ｂｉ2Ｏ2)2+(Ａm-1ＢmＯ3m+1)2-で表され、且つ、Ａが１〜３価の金属元素から成りＢが２〜６価の金属元素から成るビスマス層状化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いるか、(２)第１粒子としてその一般式が(Ａ４)4(Ｂ４)6Ｏ17で表され、且つ、Ａ４が１価の金属元素から成りＢ４が５価の金属元素から成る化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いるか、(３)第１粒子としてその一般式が(Ａ１)4(Ａ２)2Ｃ4(Ｂ１)2(Ｂ２)8Ｏ30で表され、且つ、Ａ１及びＡ２が１〜２価の金属元素から成りＣが１価の金属元素から成りＢ１及びＢ２が５価の金属元素から成るタングステンブロンズ型化合物を用い、第２粒子として目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質を用いる。 Further, when the perovskite type compound is obtained as a target substance, (1) the general formula of the first particle is (Bi 2 O 2 ) 2+ (A m-1 B m O 3m + 1 ) 2- And a bismuth layered compound in which A is composed of 1-3 valent metal elements and B is composed of 2-6 valent metal elements, and metal ion diffusion necessary for producing a sintered body of the target substance as second particles (2) The general formula of the first particles is (A4) 4 (B4) 6 O 17 , and A4 is composed of a monovalent metal element and B4 is pentavalent. A compound composed of a metal element is used, and a substance capable of diffusing metal ions necessary for producing a sintered body of the target substance is used as the second particle, or (3) the general formula is (A1) 4 as the first particle. (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of 1 to 2 valent metal elements, and C is 1 valent A tungsten bronze type compound consisting of a metal element and B1 and B2 consisting of a pentavalent metal element is used, and a substance capable of diffusing metal ions necessary for producing a sintered body of the target substance is used as the second particles.
前記(１)の具体例を挙げれば、目的物質としてＢｉ0.5Ｋ0.5ＴｉＯ3を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子として (０．２５Ｋ2O・０．６２５ＴｉＯ2)を用い、目的物質としてＢｉ0.5Ｎａ0.5ＴｉＯ3を得る場合には第１粒子としてＢｉ4Ｔｉ3Ｏ12を用い第２粒子として(０．２５Ｎａ2O・０．６２５ＴｉＯ2)を用いる。 Wherein (1) the way of specific example, Bi 0.5 K 0.5 in the case of obtaining a TiO 3 as second particles using a Bi 4 Ti 3 O 12 as the first particles (0.25K 2O · 0.625TiO purpose material 2 ), when Bi 0.5 Na 0.5 TiO 3 is obtained as the target substance, Bi 4 Ti 3 O 12 is used as the first particles and (0.25Na 2 O · 0.625 TiO 2 ) is used as the second particles.
前記(２)の具体例を挙げれば、目的物質としてＫＮｂＯ3を得る場合には第１粒子としてＫ4Ｎｂ6Ｏ17を用い第２粒子としてＫ2ＣＯ3を用い、目的物質として(Ｋ，Ｎａ)ＮｂＯ3を得る場合には第１粒子としてＫ4Ｎｂ6Ｏ17を用い第２粒子として(Ｋ，Ｎａ)2ＣＯ3を用い、目的物質として(Ｋ，Ｎａ，Ｌｉ)ＮｂＯ3を得る場合には第１粒子としてＫ4Ｎｂ6Ｏ17を用い第２粒子として(Ｋ，Ｎａ，Ｌｉ)2ＣＯ3を用いる。 As a specific example of the above (2), when obtaining KNbO 3 as the target substance, K 4 Nb 6 O 17 is used as the first particle, K 2 CO 3 is used as the second particle, and (K, When obtaining Na) NbO 3 , K 4 Nb 6 O 17 is used as the first particles, (K, Na) 2 CO 3 is used as the second particles, and (K, Na, Li) NbO 3 is obtained as the target substance. In this case, K 4 Nb 6 O 17 is used as the first particles, and (K, Na, Li) 2 CO 3 is used as the second particles.
前記(３)の具体例を挙げれば、目的物質として(Ｋ，Ｎａ，Ｓｒ)ＮｂＯ3を得る場合には第１粒子としてＳｒＮｂ2Ｏ6を用い第２粒子として(Ｋ，Ｎａ)ＮｂＯ3を用い、目的物質として(Ｋ，Ｎａ，Ｂａ)ＮｂＯ3を得る場合には第１粒子としてＢａＮｂ2Ｏ6を用い第２粒子として(Ｋ，Ｎａ)ＮｂＯ3を用い、目的物質として(Ｋ，Ｎａ，Ｌｉ，Ｓｒ)ＮｂＯ3を得る場合には第１粒子としてＳｒＮｂ2Ｏ6を用い第２粒子として(Ｋ，Ｎａ，Ｌｉ)ＮｂＯ3を用い、目的物質として(Ｋ，Ｎａ，Ｌｉ，Ｂａ)ＮｂＯ3を得る場合には第１粒子としてＢａＮｂ2Ｏ6を用い第２粒子として(Ｋ，Ｎａ，Ｌｉ)ＮｂＯ3を用い、目的物質として(Ｋ，Ｎａ，Ｌｉ)ＮｂＯ3を得る場合には第１粒子としてＫ3Ｌｉ2Ｎｂ5Ｏ15を用い第２粒子として(Ｋ，Ｎａ)ＮｂＯ3を用いる。 If the specific example of said (3) is given, when obtaining (K, Na, Sr) NbO 3 as a target substance, SrNb 2 O 6 is used as the first particle and (K, Na) NbO 3 is used as the second particle. When (K, Na, Ba) NbO 3 is used as the target substance, BaNb 2 O 6 is used as the first particle, (K, Na) NbO 3 is used as the second particle, and (K, Na) is used as the target substance. , Li, Sr) NbO 3 , SrNb 2 O 6 is used as the first particle, (K, Na, Li) NbO 3 is used as the second particle, and (K, Na, Li, Ba) is used as the target substance. When obtaining NbO 3 , BaNb 2 O 6 is used as the first particles, (K, Na, Li) NbO 3 is used as the second particles, and (K, Na, Li) NbO 3 is obtained as the target substance. as the second particle with K 3 Li 2 Nb 5 O 15 as the first particles (K, Na) NbO 3 There.
［実施例１］
以下に、ＳｒＢｉ4Ｔｉ4Ｏ15から成る結晶配向セラミックスの製法例を説明する。
[Example 1]
The following describes the preparation example of a crystal oriented ceramics composed of SrBi 4 Ti 4 O 15.
まず、Ｂｉ2Ｏ3粒子とＴｉＯ2粒子をｍｏｌ比２：３で固相反応により合成して平均粒径１μｍのＢｉ4Ｔｉ3Ｏ12粒子を作成する。 First, Bi 2 O 3 particles and TiO 2 particles mol ratio of 2: synthesized by the solid phase reaction at 3 to create the Bi 4 Ti 3 O 12 particles having an average particle diameter of 1 [mu] m.
次に、平均粒径１μｍのＢｉ4Ｔｉ3Ｏ12粒子と平均粒径０．１μｍのＳｒＴｉＯ3粒子をＳｒＢｉ4Ｔｉ4Ｏ15の化学両論組成になるようにｍｏｌ比１：１で配合し、これにイオン交換水と分散剤(中京油脂製Ｄ３０５)を固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 Next, Bi 4 Ti 3 O 12 particles having an average particle diameter of 1 μm and SrTiO 3 particles having an average particle diameter of 0.1 μm are blended at a molar ratio of 1: 1 so as to have a stoichiometric composition of SrBi 4 Ti 4 O 15 . To this, ion-exchanged water and a dispersing agent (D305, manufactured by Chukyo Yushi Co., Ltd.) are added so that the solid concentration becomes 30 vol%, and further stirred for 1 hour with a ball mill to prepare a slurry.
次に、スラリーをプラスチック容器に流し込み、スラリー面が磁場に直交するように該プラスチック容器を超伝導マグネット内に静置してスラリーにそれぞれ１０Ｔの強磁場を印加し、強磁場印加中でスラリーを自然乾燥(約２日間)と温風乾燥(４０℃程度、約１日)の何れかによって乾燥して成形体を作成する。 Next, the slurry is poured into a plastic container, the plastic container is left in a superconducting magnet so that the slurry surface is orthogonal to the magnetic field, and a strong magnetic field of 10 T is applied to the slurry. A molded body is prepared by drying by either natural drying (about 2 days) or warm air drying (about 40 ° C., about 1 day).
次に、成形体をプラスチック容器から取り出し、これを大気中で１０００℃〜１２００℃で２ｈｏｕｒ熱処理してＢｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子とを反応焼結させてＳｒＢｉ4Ｔｉ4Ｏ15から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤ(Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ，Ｘ線回折)で測定したところ、ＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度は０．８８(ロットゲーリング法で算出)であり極めて高い結晶配向度が得られることが確認できた。 Next, the molded body is taken out from the plastic container, and this is heat treated in the atmosphere at 1000 ° C. to 1200 ° C. for 2 hours to cause Bi 4 Ti 3 O 12 particles and SrTiO 3 particles to react and sinter to form SrBi 4 Ti 4 O 15. A sintered body (crystal oriented ceramics) made of When the prepared sintered body was measured by XRD (X-ray diffraction, X-ray diffraction), the degree of crystal orientation of the SrBi 4 Ti 4 O 15 particles was 0.88 (calculated by the Lotgering method), which is an extremely high crystal. It was confirmed that the degree of orientation was obtained.
図１(Ａ)は前記スラリー中のＢｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子の様子を模式的に示すもので、Ｂｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子は粒径が小さなＳｒＴｉＯ3粒子がＢｉ4Ｔｉ3Ｏ12粒子の間に入り込むような状態で分散している。 1 (A) is the a state of the Bi 4 Ti 3 O 12 particles and SrTiO 3 particles in the slurry shows schematically, Bi 4 Ti 3 O 12 particles and SrTiO 3 particles particle size smaller SrTiO 3 particles Is dispersed in such a manner that it enters between the Bi 4 Ti 3 O 12 particles.
図１(Ｂ)は前記成形体中のＢｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子の様子を模式的に示すもので、ＸＲＤの測定結果によれば、Ｂｉ4Ｔｉ3Ｏ12粒子は強磁場印加によってそのａ−ｂ面が強磁場方向に向くように配向されている。一方、ＳｒＴｉＯ3粒子は強磁場を印加してもＢｉ4Ｔｉ3Ｏ12粒子のようには配向されない。 FIG. 1 (B) schematically shows the state of Bi 4 Ti 3 O 12 particles and SrTiO 3 particles in the compact. According to the XRD measurement results, Bi 4 Ti 3 O 12 particles are strong magnetic fields. By application, the ab plane is oriented so as to face the direction of the strong magnetic field. On the other hand, SrTiO 3 particles are not oriented like Bi 4 Ti 3 O 12 particles even when a strong magnetic field is applied.
図１(Ｃ)及び図１(Ｄ)は前記反応焼結途中の様子を模式的に示すもので、熱処理によってＳｒＴｉＯ3粒子からＢｉ4Ｔｉ3Ｏ12粒子にＳｒ2 +が拡散してＢｉ4Ｔｉ3Ｏ12粒子がＳｒＢｉ4Ｔｉ4Ｏ15粒子に変化する反応が生じ、生成されたＳｒＢｉ4Ｔｉ4Ｏ15粒子が配向方向に粒成長する。Ｓｒ2 +はＢｉ4Ｔｉ3Ｏ12粒子に拡散するため、配向後のＢｉ4Ｔｉ3Ｏ12粒子の結晶方位は反応によって変化せず、ＳｒＢｉ4Ｔｉ4Ｏ15粒子は配向後のＢｉ4Ｔｉ3Ｏ12粒子の結晶方位に沿って成長する。つまり、生成されたＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶方位は配向後のＢｉ4Ｔｉ3Ｏ12粒子の結晶方位に従うために粒成長によっても変化することはないので、作成された焼結体に高い結晶配向度を得ることができる。 1 (C) and 1 (D) schematically show the state during the reaction sintering, and Sr 2 + diffuses from the SrTiO 3 particles to the Bi 4 Ti 3 O 12 particles by the heat treatment, and Bi 4. A reaction occurs in which the Ti 3 O 12 particles change to SrBi 4 Ti 4 O 15 particles, and the generated SrBi 4 Ti 4 O 15 particles grow in the orientation direction. For sr 2 + is to diffuse the Bi 4 Ti 3 O 12 particles, the crystal orientation of Bi 4 Ti 3 O 12 particles after orientation is unchanged by the reaction, SrBi 4 Ti 4 O 15 particles after orientation Bi 4 Ti It grows along the crystal orientation of 3 O 12 grains. That is, since the crystal orientation of the produced SrBi 4 Ti 4 O 15 particles follows the crystal orientation of the Bi 4 Ti 3 O 12 particles after orientation, the crystal orientation does not change even with grain growth. A high degree of crystal orientation can be obtained.
ところで、熱処理時にはＢｉ4Ｔｉ3Ｏ12粒子からＢｉ3 +の拡散も生じ得るため、先に述べたような反応焼結を効果的に行うにはＢｉ3 +の拡散よりもＳｒ2 +の拡散が促進されるようにＢｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子の粒径比(Ｂｉ4Ｔｉ3Ｏ12粒子の粒径／ＳｒＴｉＯ3粒子の粒径)を考慮する必要がある。 By the way, since Bi 3 + diffusion can also occur from Bi 4 Ti 3 O 12 particles during heat treatment, Sr 2 + diffusion is more effective than Bi 3 + diffusion for effective reactive sintering as described above. It is necessary to consider the particle size ratio of Bi 4 Ti 3 O 12 particles and SrTiO 3 particles (Bi 4 Ti 3 O 12 particle size / SrTiO 3 particle size).
前記粒径比による拡散現象及び結晶配向度の違いを検証するため、０．１μｍ以外の平均粒径のＳｒＴｉＯ3粒子を使用して同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度を確認した。 In order to verify the difference in the diffusion phenomenon and the degree of crystal orientation due to the particle size ratio, several sintered bodies were prepared in the same procedure using SrTiO 3 particles having an average particle size other than 0.1 μm, The aggregate was measured by XRD to confirm the degree of crystal orientation of the SrBi 4 Ti 4 O 15 particles.
図２はその確認結果を示すもので、ＳｒＴｉＯ3粒子の粒径が小さいほどＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度は高くなること、具体的には前記粒径比が３．８以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＳｒＴｉＯ3粒子の粒径を選択することにより１．０に近い結晶配向度を得ることが確認できた。ＳｒＢｉ4Ｔｉ4Ｏ15粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＢｉ4Ｔｉ3Ｏ12粒子とＳｒＴｉＯ3粒子の粒径比(Ｂｉ4Ｔｉ3Ｏ12粒子の粒径／ＳｒＴｉＯ3粒子の粒径)は３．８以上であればよい。また、前記粒径比が２２で結晶配向度は０．９９に達するが、それ以上前記粒径比を上げても結晶配向度の上昇は僅かであり、ＳｒＴｉＯ3粒子の粒径が小さくなるが故に均一なスラリー分散状態を作ることが難しくなることから、前記粒径比は３．８〜２２が実用上で好ましい範囲となる。 FIG. 2 shows the result of the confirmation. The smaller the particle size of the SrTiO 3 particles, the higher the degree of crystal orientation of the SrBi 4 Ti 4 O 15 particles. Specifically, the particle size ratio is 3.8 or more. A crystal orientation degree of 0.6 or more can be obtained. In practice, it is difficult to set the crystal orientation degree to 1.0, but the crystal orientation degree close to 1.0 can be obtained by selecting the grain size of the SrTiO 3 particles. Could be confirmed. If a crystal orientation degree of 0.6 or more can be obtained in the SrBi 4 Ti 4 O 15 particles, electrical characteristics such as piezoelectric characteristics suitable for practical use can be obtained. Therefore, the Bi 4 Ti 3 O 12 particles and the SrTiO 3 particles described above are used. The particle size ratio (Bi 4 Ti 3 O 12 particles / SrTiO 3 particles) may be 3.8 or more. Further, when the particle size ratio is 22, the degree of crystal orientation reaches 0.99, but even if the particle size ratio is further increased, the increase in the crystal orientation degree is slight and the particle size of the SrTiO 3 particles becomes small. Therefore, since it becomes difficult to make a uniform slurry dispersion state, the particle size ratio is preferably in a practical range of 3.8 to 22.
［実施例２］
以下に、ＳｒＢｉ4Ｔｉ4Ｏ15から成る結晶配向セラミックスの他の製法例を説明する。
[Example 2]
Hereinafter, another example of a method for producing a crystallographically-oriented ceramic made of SrBi 4 Ti 4 O 15 will be described.
まず、平均粒径１μｍのＢｉ4Ｔｉ3Ｏ12粒子と平均粒径０．２μｍのＳｒＴｉＯ3粒子をＳｒＢｉ4Ｔｉ4Ｏ15の化学両論組成になるように配合して乾式摩砕し、ＳｒＴｉＯ3粒子が厚さ０．０７μｍで表面にコーティングされたＢｉ4Ｔｉ3Ｏ12粒子を作成する。 First, Bi 4 Ti 3 O 12 particles having an average particle diameter of 1 μm and SrTiO 3 particles having an average particle diameter of 0.2 μm are blended so as to have a stoichiometric composition of SrBi 4 Ti 4 O 15 , dry-milled, and SrTiO 3. Bi 4 Ti 3 O 12 particles are prepared with particles coated on the surface with a thickness of 0.07 μm.
次に、ＳｒＴｉＯ3粒子が表面にコーティングされたＢｉ4Ｔｉ3Ｏ12粒子にイオン交換水と分散剤(中京油脂製Ｄ３０５)を固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 Next, ion exchange water and a dispersing agent (D305 made by Chukyo Yushi) were added to Bi 4 Ti 3 O 12 particles coated with SrTiO 3 particles on the surface so that the solid concentration was 30 vol%, and further 1 hour by a ball mill. Stir to make a slurry.
以後は実施例１と同様の手順でＳｒＢｉ4Ｔｉ4Ｏ15から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤで測定したところ、ＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度は０．９２であり極めて高い結晶配向度が得られることが確認できた。 Thereafter, a sintered body (crystal oriented ceramics) made of SrBi 4 Ti 4 O 15 is prepared in the same procedure as in Example 1. When the prepared sintered body was measured by XRD, the crystal orientation of the SrBi 4 Ti 4 O 15 particles was 0.92, and it was confirmed that an extremely high crystal orientation was obtained.
実施例１と同様に反応焼結を効果的に行うにはＢｉ4Ｔｉ3Ｏ12粒子の粒径とＳｒＴｉＯ3粒子のコーティング厚さの比(Ｂｉ4Ｔｉ3Ｏ12粒子の粒径／ＳｒＴｉＯ3粒子のコーティング厚さ)を考慮する必要がある。 Example 1 Bi 4 is effectively carry out the reaction sintering in the same manner as Ti 3 O 12 ratio of coating thickness of the particle size and SrTiO 3 particles having a particle (Bi 4 Ti 3 O 12 particle size / SrTiO 3 particles It is necessary to consider the coating thickness of the particles.
前記比による拡散現象及び結晶配向度の違いを検証するため、０．２μｍ以外の平均粒径のＳｒＴｉＯ3粒子を使用しコーティング厚さを０．０７μｍ以外にしたＢｉ4Ｔｉ3Ｏ12粒子を用いて同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度を確認した。 To verify the difference in the diffusion phenomenon and the degree of crystal orientation by the ratio, using a Bi 4 Ti 3 O 12 particles other than 0.07μm coating thickness using SrTiO 3 particles having an average particle diameter other than 0.2μm Then, several sintered bodies were prepared in the same procedure, and each sintered body was measured by XRD to confirm the degree of crystal orientation of the SrBi 4 Ti 4 O 15 particles.
図３はその確認結果を示すもので、ＳｒＴｉＯ3粒子のコーティング厚さが小さいほどＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度は高くなること、具体的には前記比が４．６以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＳｒＴｉＯ3粒子のコーティング厚さを選択することにより１．０に近い結晶配向度を得ることが確認できた。ＳｒＢｉ4Ｔｉ4Ｏ15粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＢｉ4Ｔｉ3Ｏ12粒子の粒径とＳｒＴｉＯ3粒子のコーティング厚さの比(Ｂｉ4Ｔｉ3Ｏ12粒子の粒径／ＳｒＴｉＯ3粒子のコーティング厚さ)は４．６以上であればよい。また、前記比が２７で結晶配向度は０．９９に達するが、それ以上前記比を上げても結晶配向度の上昇は僅かであり、ＳｒＴｉＯ3粒子の厚さが薄くなるが故に均一なコーティング状態を作ることが難しくなることから、前記比は４．６〜２７が実用上で好ましい範囲となる。 FIG. 3 shows the result of confirmation. The smaller the coating thickness of the SrTiO 3 particles, the higher the crystal orientation of the SrBi 4 Ti 4 O 15 particles. Specifically, when the ratio is 4.6 or more, 0 is obtained. A crystal orientation degree of .6 or more can be obtained, and in practice, it is difficult to make the crystal orientation degree 1.0, but the crystal orientation degree close to 1.0 can be obtained by selecting the coating thickness of the SrTiO 3 particles. Could be confirmed. Since electrical characteristics such as piezoelectric characteristics suitable for practical use can be obtained if a crystal orientation degree of 0.6 or more is obtained in the SrBi 4 Ti 4 O 15 particles, the particle size of the Bi 4 Ti 3 O 12 particles described above can be obtained. The ratio of coating thickness of SrTiO 3 particles (Bi 4 Ti 3 O 12 particle diameter / SrTiO 3 particle coating thickness) may be 4.6 or more. Further, when the ratio is 27 and the degree of crystal orientation reaches 0.99, even if the ratio is further increased, the increase in the degree of crystal orientation is slight and the thickness of the SrTiO 3 particles is reduced, so that the uniform coating is achieved. Since it becomes difficult to make a state, 4.6 to 27 is a practically preferable range for the ratio.
［実施例３］
以下に、ＫＳｒ2Ｎｂ5Ｏ15から成る結晶配向セラミックスの製法例を説明する。
[Example 3]
The following describes the preparation example of a crystal-oriented ceramic comprising a KSr 2 Nb 5 O 15.
まず、平均粒径２．５μｍのＳｒＮｂ2Ｏ6粒子と平均粒径０．３μｍのＫＮｂＯ3粒子をＫＳｒ2Ｎｂ5Ｏ15の化学両論組成になるように配合し、これにイオン交換水と分散剤(中京油脂製Ｄ３０５)を固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 First, SrNb 2 O 6 particles having an average particle diameter of 2.5 μm and KNbO 3 particles having an average particle diameter of 0.3 μm are blended so as to have a stoichiometric composition of KSr 2 Nb 5 O 15 , and ion-exchanged water and dispersed therein An agent (D305, manufactured by Chukyo Yushi Co., Ltd.) is added so that the solid content concentration is 30 vol%, and the slurry is further stirred by a ball mill for 1 hour.
以後は実施例１と同様の手順でＫＳｒ2Ｎｂ5Ｏ15から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤで測定したところ、ＫＳｒ2Ｎｂ5Ｏ15粒子の結晶配向度は０．８５であり極めて高い結晶配向度が得られることが確認できた。 Thereafter, a sintered body (crystal oriented ceramics) made of KSr 2 Nb 5 O 15 is prepared in the same procedure as in Example 1. When the prepared sintered body was measured by XRD, the degree of crystal orientation of the KSr 2 Nb 5 O 15 particles was 0.85, and it was confirmed that an extremely high degree of crystal orientation was obtained.
実施例１と同様に反応焼結を効果的に行うにはＳｒＮｂ2Ｏ6粒子とＫＮｂＯ3粒子の粒径比(ＳｒＮｂ2Ｏ6粒子の粒径／ＫＮｂＯ3粒子の粒径)を考慮する必要がある。 In order to perform reactive sintering effectively as in Example 1, it is necessary to consider the particle size ratio of SrNb 2 O 6 particles to KNbO 3 particles (particle size of SrNb 2 O 6 particles / particle size of KNbO 3 particles). There is.
前記粒径比による拡散現象及び結晶配向度の違いを検証するため、０．３μｍ以外の平均粒径のＫＮｂＯ3粒子を使用して同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＫＳｒ2Ｎｂ5Ｏ15粒子の結晶配向度を確認した。 In order to verify the difference in the diffusion phenomenon and the degree of crystal orientation due to the particle size ratio, several sintered bodies were prepared in the same procedure using KNbO 3 particles having an average particle size other than 0.3 μm. The aggregate was measured by XRD, and the degree of crystal orientation of the KSr 2 Nb 5 O 15 particles was confirmed.
図２の確認結果と同様に、ＫＮｂＯ3粒子の粒径が小さいほどＫＳｒ2Ｎｂ5Ｏ15粒子の結晶配向度は高くなること、具体的には前記粒径比が３．８以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＳｒＴｉＯ3粒子の粒径を選択することにより１．０に近い結晶配向度を得ることが確認できた。ＫＳｒ2Ｎｂ5Ｏ15粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＳｒＮｂ2Ｏ6粒子とＫＮｂＯ3粒子の粒径比(ＳｒＮｂ2Ｏ6粒子の粒径／ＫＮｂＯ3粒子の粒径)は３．８以上であればよい。また、前記粒径比が２２で結晶配向度は０．９９に達するが、それ以上前記粒径比を上げても結晶配向度の上昇は僅かであり、ＫＮｂＯ3粒子の粒径が小さくなるが故に均一なスラリー分散状態を作ることが難しくなることから、前記粒径比は３．８〜２２が実用上で好ましい範囲となる。 As in the confirmation result of FIG. 2, the smaller the particle size of the KNbO 3 particles, the higher the degree of crystal orientation of the KSr 2 Nb 5 O 15 particles. Although it is difficult to obtain a crystal orientation degree of 6 or more, and in practice it is difficult to make the crystal orientation degree 1.0, a crystal orientation degree close to 1.0 is obtained by selecting the grain size of the SrTiO 3 particles. I was able to confirm. If the KSr 2 Nb 5 O 15 particles have a crystal orientation degree of 0.6 or more, electrical characteristics such as piezoelectric properties suitable for practical use can be obtained. Therefore, the SrNb 2 O 6 particles and the KNbO 3 particles described above are used. The diameter ratio (SrNb 2 O 6 particle diameter / KNbO 3 particle diameter) may be 3.8 or more. Further, when the particle size ratio is 22, the degree of crystal orientation reaches 0.99, but even if the particle size ratio is further increased, the increase in the crystal orientation degree is slight and the particle size of the KNbO 3 particles becomes small. Therefore, since it becomes difficult to make a uniform slurry dispersion state, the particle size ratio is preferably in a practical range of 3.8 to 22.
［実施例４］
以下に、ＫＳｒ2Ｎｂ5Ｏ15から成る結晶配向セラミックスの他の製法例を説明する。
[Example 4]
Hereinafter, another example of a method for producing a crystallographically-oriented ceramic made of KSr 2 Nb 5 O 15 will be described.
まず、平均粒径２．５μｍのＳｒＮｂ2Ｏ6粒子と平均粒径０．４μｍのＫＮｂＯ3粒子をＫＳｒ2Ｎｂ5Ｏ15の化学両論組成になるように配合して乾式摩砕し、ＫＮｂＯ3粒子が厚さ０．２μｍで表面にコーティングされたＳｒＮｂ2Ｏ6粒子を作成する。 First, SrNb 2 O 6 particles having an average particle diameter of 2.5 μm and KNbO 3 particles having an average particle diameter of 0.4 μm are blended so as to have a stoichiometric composition of KSr 2 Nb 5 O 15 , dry-milled, and KNbO 3 SrNb 2 O 6 particles having a thickness of 0.2 μm and coated on the surface are prepared.
次に、ＫＮｂＯ3粒子が表面にコーティングされたＳｒＮｂ2Ｏ6粒子にイオン交換水と分散剤(中京油脂製Ｄ３０５)を固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 Next, ion-exchanged water and a dispersant (D305 manufactured by Chukyo Yushi Co., Ltd.) are added to the SrNb 2 O 6 particles coated on the surface with KNbO 3 particles so that the solid concentration is 30 vol%, and further stirred for 1 hour with a ball mill. To make a slurry.
以後は実施例１と同様の手順でＫＳｒ2Ｎｂ5Ｏ15から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤで測定したところ、ＫＳｒＢｉ4Ｔｉ4Ｏ15粒子の結晶配向度は０．９であり極めて高い結晶配向度が得られることが確認できた。 Thereafter, a sintered body (crystal oriented ceramics) made of KSr 2 Nb 5 O 15 is prepared in the same procedure as in Example 1. When the produced sintered body was measured by XRD, the crystal orientation degree of the KSrBi 4 Ti 4 O 15 particles was 0.9, and it was confirmed that an extremely high crystal orientation degree was obtained.
実施例１と同様に反応焼結を効果的に行うにはＳｒＮｂ2Ｏ6粒子の粒径とＫＮｂＯ3粒子のコーティング厚さの比(ＳｒＮｂ2Ｏ6粒子の粒径／ＫＮｂＯ3粒子のコーティング厚さ)を考慮する必要がある。 The coating thickness of the particle size / KNbO 3 particles of the coating thickness ratio (SrNb 2 O 6 particles having a particle size and KNbO 3 particles SrNb 2 O 6 particles effectively carry out the reaction sintering in the same manner as in Example 1 It is necessary to consider.
前記比による拡散現象及び結晶配向度の違いを検証するため、０．４μｍ以外の平均粒径のＫＮｂＯ3粒子を使用しコーティング厚さを０．２μｍ以外にしたＳｒＮｂ2Ｏ6粒子を用いて同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＫＳｒ2Ｎｂ5Ｏ15粒子の結晶配向度を確認した。 In order to verify the difference in the diffusion phenomenon and the degree of crystal orientation due to the above ratio, the same applies to the SrNb 2 O 6 particles using KNbO 3 particles having an average particle diameter other than 0.4 μm and having a coating thickness other than 0.2 μm. Several sintered bodies were prepared by the procedure described above, and each sintered body was measured by XRD to confirm the degree of crystal orientation of the KSr 2 Nb 5 O 15 particles.
図３の確認結果と同様に、ＫＮｂＯ3粒子のコーティング厚さが小さいほどＫＳｒ2Ｎｂ5Ｏ15粒子の結晶配向度は高くなること、具体的には前記比が４．６以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＫＮｂＯ3粒子のコーティング厚さを選択することにより１．０に近い結晶配向度を得ることが確認できた。ＫＳｒ2Ｎｂ5Ｏ15粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＳｒＮｂ2Ｏ6粒子の粒径とＫＮｂＯ3粒子のコーティング厚さの比(ＳｒＮｂ2Ｏ6粒子の粒径／ＫＮｂＯ3粒子のコーティング厚さ)は４．６以上であればよい。また、前記比が２７で結晶配向度は０．９９に達するが、それ以上前記比を上げても結晶配向度の上昇は僅かであり、ＳｒＴｉＯ3粒子の厚さが薄くなるが故に均一なコーティング状態を作ることが難しくなることから、前記比は４．６〜２７が実用上で好ましい範囲となる。 Similar to the confirmation results in FIG. 3, the smaller the coating thickness of the KNbO 3 particles, the higher the degree of crystal orientation of the KSr 2 Nb 5 O 15 particles. Specifically, the ratio is 0.6 or more and 0.6. Although it is difficult to obtain the above crystal orientation degree and in practice it is difficult to set the crystal orientation degree to 1.0, a crystal orientation degree close to 1.0 is obtained by selecting the coating thickness of the KNbO 3 particles. I was able to confirm. If a crystal orientation degree of 0.6 or more is obtained in the KSr 2 Nb 5 O 15 particles, electric characteristics such as piezoelectric characteristics suitable for practical use can be obtained. Therefore, the particle size of the SrNb 2 O 6 particles described above and the KNbO 3 The ratio of the coating thickness of the particles (SrNb 2 O 6 particle diameter / KNbO 3 particle coating thickness) may be 4.6 or more. Further, when the ratio is 27 and the degree of crystal orientation reaches 0.99, even if the ratio is further increased, the increase in the degree of crystal orientation is slight and the thickness of the SrTiO 3 particles is reduced, so that the uniform coating is achieved. Since it becomes difficult to make a state, 4.6 to 27 is a practically preferable range for the ratio.
［実施例５］
以下に、ＫＮｂＯ3から成る結晶配向セラミックスの製法例を説明する。
[Example 5]
The following describes the preparation example of a crystal oriented ceramics composed of KNbO 3.
まず、平均粒径２μｍのＫ4Ｎｂ6Ｏ17粒子と乾燥雰囲気中で粉砕して粒度を調節した平均粒径０．４μｍのＫ2ＣＯ3粒子をＫＮｂＯ3の化学両論組成になるように配合し、これに無水エタノールを固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 First, K 4 Nb 6 O 17 particles having an average particle diameter of 2 μm and K 2 CO 3 particles having an average particle diameter of 0.4 μm, which are pulverized in a dry atmosphere and adjusted in particle size, are mixed so as to have a stoichiometric composition of KNbO 3. Then, absolute ethanol is added to this so that the solid content concentration becomes 30 vol%, and further stirred with a ball mill for 1 hour to prepare a slurry.
以後は実施例１と同様の手順でＫＮｂＯ3から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤで測定したところ、ＫＮｂＯ3粒子の結晶配向度は０．７であり極めて高い結晶配向度が得られることが確認できた。 Thereafter, a sintered body (crystal oriented ceramics) made of KNbO 3 is prepared in the same procedure as in Example 1. When the prepared sintered body was measured by XRD, the crystal orientation degree of the KNbO 3 particles was 0.7, and it was confirmed that an extremely high crystal orientation degree was obtained.
実施例１と同様に反応焼結を効果的に行うにはＫ4Ｎｂ6Ｏ17粒子とＫ2ＣＯ3粒子の粒径比(Ｋ4Ｎｂ6Ｏ17粒子の粒径／Ｋ2ＣＯ3粒子の粒径)を考慮する必要がある。 In order to effectively carry out reactive sintering as in Example 1, the particle size ratio of K 4 Nb 6 O 17 particles to K 2 CO 3 particles (particle size of K 4 Nb 6 O 17 particles / K 2 CO 3 particles The particle size of the particle).
前記粒径比による拡散現象及び結晶配向度の違いを検証するため、０．４μｍ以外の平均粒径のＫ2ＣＯ3粒子を使用して同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＫＮｂＯ3粒子の結晶配向度を確認した。 In order to verify the difference in the diffusion phenomenon and the degree of crystal orientation due to the particle size ratio, several sintered bodies were prepared in the same procedure using K 2 CO 3 particles having an average particle size other than 0.4 μm, Each sintered body was measured by XRD to confirm the degree of crystal orientation of the KNbO 3 particles.
図２の確認結果と同様に、Ｋ2ＣＯ3粒子の粒径が小さいほどＫＮｂＯ3粒子の結晶配向度は高くなること、具体的には前記粒径比が３．８以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＫ2ＣＯ3粒子の粒径を選択することにより１．０に近い結晶配向度を得ることが確認できた。ＫＮｂＯ3粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＫ4Ｎｂ6Ｏ17粒子とＫ2ＣＯ3粒子の粒径比(Ｋ4Ｎｂ6Ｏ17粒子の粒径／Ｋ2ＣＯ3粒子の粒径)は３．８以上であればよい。また、前記粒径比が２２で結晶配向度は０．９９に達するが、それ以上前記粒径比を上げても結晶配向度の上昇は僅かであり、Ｋ2ＣＯ3粒子の粒径が小さくなるが故に均一なスラリー分散状態を作ることが難しくなることから、前記粒径比は３．８〜２２が実用上で好ましい範囲となる。 As in the confirmation result of FIG. 2, the smaller the particle size of the K 2 CO 3 particles, the higher the degree of crystal orientation of the KNbO 3 particles. Specifically, the particle size ratio is 3.8 or more and 0.6 or more. It is difficult to obtain a crystal orientation degree of 1.0, but in practice it is difficult to make the crystal orientation degree 1.0, but by selecting the grain size of K 2 CO 3 particles, a crystal orientation degree close to 1.0 is obtained. I was able to confirm. If KNbO 3 particles have a crystal orientation degree of 0.6 or more, electrical properties such as piezoelectric properties suitable for practical use can be obtained. Therefore, the above-mentioned grains of K 4 Nb 6 O 17 particles and K 2 CO 3 particles The diameter ratio (the particle diameter of K 4 Nb 6 O 17 particles / the particle diameter of K 2 CO 3 particles) may be 3.8 or more. Further, when the particle size ratio is 22, the degree of crystal orientation reaches 0.99, but even if the particle size ratio is further increased, the increase in crystal orientation is slight, and the particle size of the K 2 CO 3 particles is small. Therefore, since it becomes difficult to make a uniform slurry dispersion state, the particle size ratio is preferably in a practical range of 3.8 to 22.
［実施例６］
以下に、ＫＮｂＯ3から成る結晶配向セラミックスの他の製法例を説明する。
[Example 6]
Hereinafter, another example of the method for producing a crystallographically-oriented ceramic made of KNbO 3 will be described.
まず、平均粒径２μｍのＫ4Ｎｂ6Ｏ17粒子と乾燥雰囲気中で粉砕して粒度を調節した平均粒径０．４μｍのＫ2ＣＯ3粒子をＫＮｂＯ3の化学両論組成になるように配合して乾式摩砕し、Ｋ2ＣＯ3粒子が厚さ０．２４μｍで表面にコーティングされたＫ4Ｎｂ6Ｏ17粒子を作成する。 First, K 4 Nb 6 O 17 particles having an average particle diameter of 2 μm and K 2 CO 3 particles having an average particle diameter of 0.4 μm, which are pulverized in a dry atmosphere and adjusted in particle size, are mixed so as to have a stoichiometric composition of KNbO 3. Then, dry grinding is performed to prepare K 4 Nb 6 O 17 particles having a surface coated with K 2 CO 3 particles having a thickness of 0.24 μm.
次に、Ｋ2ＣＯ3粒子が表面にコーティングされたＫ4Ｎｂ6Ｏ17粒子に無水エタノールを固形分濃度が３０ｖｏｌ％となるように添加してさらにボールミルで１ｈｏｕｒ撹拌してスラリーを作成する。 Next, absolute ethanol is added to the K 4 Nb 6 O 17 particles whose surfaces are coated with K 2 CO 3 particles so that the solid content concentration is 30 vol%, and further stirred for 1 hour with a ball mill to prepare a slurry.
以後は実施例１と同様の手順でＫＮｂＯ3から成る焼結体(結晶配向セラミックス)を作成する。作成された焼結体をＸＲＤで測定したところ、ＫＮｂＯ3粒子の結晶配向度は０．８５であり極めて高い結晶配向度が得られることが確認できた。 Thereafter, a sintered body (crystal oriented ceramics) made of KNbO 3 is prepared in the same procedure as in Example 1. When the prepared sintered body was measured by XRD, the crystal orientation degree of the KNbO 3 particles was 0.85, and it was confirmed that an extremely high crystal orientation degree was obtained.
実施例１と同様に反応焼結を効果的に行うにはＫ4Ｎｂ6Ｏ17粒子の粒径とＫ2ＣＯ3粒子のコーティング厚さの比(Ｋ4Ｎｂ6Ｏ17粒子の粒径／Ｋ2ＣＯ3粒子のコーティング厚さ)を考慮する必要がある。 The particle size of the coating thickness ratio (K 4 Nb 6 O 17 particles having a particle size and K 2 CO 3 particles K 4 Nb 6 O 17 particles to effectively carry out the reaction sintering in the same manner as in Example 1 / It is necessary to consider the coating thickness of the K 2 CO 3 particles.
前記比による拡散現象及び結晶配向度の違いを検証するため、０．４μｍ以外の平均粒径のＫ2ＣＯ3粒子を使用しコーティング厚さを０．２４μｍ以外にしたＫＮｂＯ3粒子を用いて同様の手順で焼結体を幾つか作成して、各焼結体をＸＲＤで測定してＫＮｂＯ3粒子の結晶配向度を確認した。 In order to verify the difference in the diffusion phenomenon and the degree of crystal orientation due to the above ratio, the same applies to KNbO 3 particles using K 2 CO 3 particles having an average particle size other than 0.4 μm and having a coating thickness other than 0.24 μm. Several sintered bodies were prepared by the above procedure, and each sintered body was measured by XRD to confirm the degree of crystal orientation of the KNbO 3 particles.
図３の確認結果と同様に、Ｋ2ＣＯ3粒子のコーティング厚さが小さいほどＫＮｂＯ3粒子の結晶配向度は高くなること、具体的には前記比が４．６以上で０．６以上の結晶配向度が得られること、また、実際上では結晶配向度を１．０にすることは難しいがＫ2ＣＯ3粒子のコーティング厚さを選択することにより１．０に近い結晶配向度を得ることが確認できた。ＫＮｂＯ3粒子に０．６以上の結晶配向度が得られれば実用に適した圧電特性等の電気特性が得られるため、先に述べたＫ4Ｎｂ6Ｏ17粒子の粒径とＫ2ＣＯ3粒子のコーティング厚さの比(Ｋ4Ｎｂ6Ｏ17粒子の粒径／Ｋ2ＣＯ3粒子のコーティング厚さ)は４．６以上であればよい。また、前記比が２７で結晶配向度は０．９９に達するが、それ以上前記比を上げても結晶配向度の上昇は僅かであり、Ｋ2ＣＯ3粒子の厚さが薄くなるが故に均一なコーティング状態を作ることが難しくなることから、前記比は４．６〜２７が実用上で好ましい範囲となる。 Similar to the confirmation results of FIG. 3, the smaller the coating thickness of the K 2 CO 3 particles, the higher the crystal orientation of the KNbO 3 particles. Specifically, the ratio is 4.6 or more and 0.6 or more. Although crystal orientation can be obtained, and in practice it is difficult to make the crystal orientation 1.0, it is possible to obtain crystal orientation close to 1.0 by selecting the coating thickness of the K 2 CO 3 particles I was able to confirm. Since electrical characteristics such as piezoelectric characteristics suitable for practical use can be obtained if a crystal orientation degree of 0.6 or more is obtained in the KNbO 3 particles, the particle size of the K 4 Nb 6 O 17 particles and the K 2 CO 3 described above are obtained. The ratio of the coating thickness of the particles (the particle diameter of K 4 Nb 6 O 17 particles / the coating thickness of K 2 CO 3 particles) may be 4.6 or more. Further, when the ratio is 27, the degree of crystal orientation reaches 0.99, but even if the ratio is further increased, the increase in the degree of crystal orientation is slight and uniform because the thickness of the K 2 CO 3 particles is reduced. Since it becomes difficult to make a simple coating state, the ratio is 4.6 to 27 in a practically preferable range.
Claims (11)
スラリーに強磁場を印加して第１粒子が配向した成形体を作成するステップと、
成形体を熱処理して第２粒子から第１粒子への金属イオン拡散により第１粒子と第２粒子を反応焼結させて目的物質の焼結体を作成するステップとを備え、
前記スラリーは第１粒子と第２粒子がそれぞれ該スラリー中に分散していて、第１粒子と第２粒子の粒径比(第１粒子の粒径／第２粒子の粒径)は３．８以上２２以下である、
ことを特徴とする結晶配向セラミックスの製造方法。 Creating a slurry containing first particles that can be oriented by applying a strong magnetic field and second particles that can produce a target substance by reactive sintering accompanied by metal ion diffusion to the first particles;
Applying a strong magnetic field to the slurry to create a shaped body in which the first particles are oriented;
E Bei and creating a sintered body of the first particle and the target substance of the second particles are reaction sintering by the metal ions diffuse from the second particles by heat-treating the molded body to the first particles,
In the slurry, the first particles and the second particles are dispersed in the slurry, respectively, and the particle size ratio of the first particles to the second particles (the particle size of the first particles / the particle size of the second particles) is 3. 8 or more and 22 or less,
A method for producing a crystallographically-oriented ceramic.
スラリーに強磁場を印加して第１粒子が配向した成形体を作成するステップと、
成形体を熱処理して第２粒子から第１粒子への金属イオン拡散により第１粒子と第２粒子を反応焼結させて目的物質の焼結体を作成するステップとを備え、
前記スラリーは第２粒子が表面にコーティングされた第１粒子が該スラリー中に分散していて、第１粒子の粒径と第２粒子のコーティング厚さの比(第１粒子の粒径／第２粒子のコーティング厚さ)は４．６以上２７以下である、
ことを特徴とする結晶配向セラミックスの製造方法。 Creating a slurry containing first particles that can be oriented by applying a strong magnetic field and second particles that can produce a target substance by reactive sintering accompanied by metal ion diffusion to the first particles;
Applying a strong magnetic field to the slurry to create a shaped body in which the first particles are oriented;
Heat-treating the formed body to react and sinter the first particles and the second particles by metal ion diffusion from the second particles to the first particles, thereby creating a sintered body of the target substance,
In the slurry, the first particles having the second particles coated on the surface are dispersed in the slurry, and the ratio of the particle size of the first particles to the coating thickness of the second particles (the particle size of the first particles / the first particle). The coating thickness of 2 particles) is 4.6 or more and 27 or less ,
Method for producing a crystal-oriented ceramic you wherein a.
ことを特徴とする請求項１または２に記載の結晶配向セラミックスの製造方法。 The target substance is represented by the general formula (Bi 2 O 2 ) 2+ (A m-1 B m O 3m + 1 ) 2- , and A is composed of a 1-3 valent metal element and B is 2 to 2. A bismuth layered compound composed of a hexavalent metal element,
The method for producing a crystallographically-oriented ceramic according to claim 1 or 2 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項３に記載の結晶配向セラミックスの製造方法。 The first particle is a bismuth layered compound containing at least one kind of 1-3 valent metal element containing Bi and at least one kind of 2-6 valent metal element excluding Bi,
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
The method for producing a crystallographically-oriented ceramic according to claim 3 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項３に記載の結晶配向セラミックスの製造方法。 The first particles are represented by the general formula (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of a divalent metal element and C is 1 A tungsten bronze type compound consisting of a valent metal element and B1 and B2 consisting of a pentavalent metal element,
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
The method for producing a crystallographically-oriented ceramic according to claim 3 .
ことを特徴とする請求項１または２に記載の結晶配向セラミックスの製造方法。 The target substance is represented by the general formula (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of 1 to 2 metal elements, and C is monovalent. A tungsten bronze type compound in which B1 and B2 are composed of pentavalent metal elements
The method for producing a crystallographically-oriented ceramic according to claim 1 or 2 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項６に記載の結晶配向セラミックスの製造方法。 The first particles are represented by the general formula (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of a divalent metal element and C is 1 A tungsten bronze-type compound having a molecular weight smaller than that of a target substance consisting of a valent metal element and B1 and B2 being a pentavalent metal element,
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
The method for producing a crystal-oriented ceramic according to claim 6.
ことを特徴とする請求項１または２に記載の結晶配向セラミックスの製造方法。 The target substance is a perovskite type compound whose general formula is represented by (A3) (B3) O 3 , A3 is composed of 1 to 3 metal elements, and B3 is composed of 3 to 5 metal elements.
The method for producing a crystallographically-oriented ceramic according to claim 1 or 2 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項８に記載の結晶配向セラミックスの製造方法。 The first particles are represented by the general formula (Bi 2 O 2 ) 2+ (A m-1 B m O 3m + 1 ) 2- , and A is composed of 1 to 3 metal elements, and B is 2 A bismuth layered compound composed of a hexavalent metal element,
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
A method for producing a crystallographically-oriented ceramic according to claim 8 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項８に記載の結晶配向セラミックスの製造方法。 The first particle is a compound represented by the general formula (A4) 4 (B4) 6 O 17 , A4 is composed of a monovalent metal element, and B4 is composed of a pentavalent metal element.
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
A method for producing a crystallographically-oriented ceramic according to claim 8 .
第２粒子は目的物質の焼結体の作成に必要な金属イオン拡散を可能とした物質である、
ことを特徴とする請求項８に記載の結晶配向セラミックスの製造方法。
The first particles are represented by the general formula (A1) 4 (A2) 2 C 4 (B1) 2 (B2) 8 O 30 , and A1 and A2 are composed of a divalent metal element and C is 1 A tungsten bronze type compound consisting of a valent metal element and B1 and B2 consisting of a pentavalent metal element,
The second particle is a substance that enables metal ion diffusion necessary for producing a sintered body of the target substance.
A method for producing a crystallographically-oriented ceramic according to claim 8 .
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