JP5849264B2 - Piezoelectrically oriented ceramics and manufacturing method thereof - Google Patents
Piezoelectrically oriented ceramics and manufacturing method thereof Download PDFInfo
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- JP5849264B2 JP5849264B2 JP2013549183A JP2013549183A JP5849264B2 JP 5849264 B2 JP5849264 B2 JP 5849264B2 JP 2013549183 A JP2013549183 A JP 2013549183A JP 2013549183 A JP2013549183 A JP 2013549183A JP 5849264 B2 JP5849264 B2 JP 5849264B2
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- 239000000919 ceramic Substances 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 239000000843 powder Substances 0.000 claims description 106
- 239000000203 mixture Substances 0.000 claims description 78
- 230000004907 flux Effects 0.000 claims description 44
- 239000013078 crystal Substances 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkali metal halogen salt Chemical class 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000523 sample Substances 0.000 description 125
- 239000010936 titanium Substances 0.000 description 47
- 238000001878 scanning electron micrograph Methods 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 14
- 229910000464 lead oxide Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 229910000484 niobium oxide Inorganic materials 0.000 description 12
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
この発明は、三成分系ＰＺＴ（Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3）化合物を主成分とする圧電配向セラミックスおよびその製造方法に関する。This invention relates to a piezoelectric oriented ceramics and a manufacturing method thereof mainly containing ternary PZT (Pb ((Ti 1- x Zr x) 1-y) ((Ma a Mb b) y) O 3) compound.
従来、誘電体材料や圧電体材料として、ペロブスカイト構造を有する圧電配向セラミックスが使用されている。これらのペロブスカイト構造を有する圧電配向セラミックスにおいては、その結晶を配向させることによって、圧電配向セラミックスの電気特性が向上することが知られている。 Conventionally, piezoelectric oriented ceramics having a perovskite structure have been used as dielectric materials and piezoelectric materials. In the piezoelectric oriented ceramics having these perovskite structures, it is known that the electrical characteristics of the piezoelectric oriented ceramics are improved by orienting the crystals.
ペロブスカイト構造を有する圧電配向セラミックスの製造方法として、例えば、特許文献１に記載の技術が提案されている。特許文献１に記載された技術は、ペロブスカイト構造を有する主成分１００ｍｏｌに対して５ｍｏｌ以下（ただし０ｍｏｌを除く）の割合で含有される副成分とを含み、該副成分として、たとえば３ｄ元素を含む仮焼粉末を溶媒と混合して作製したスラリーを磁場中で成形しようとする圧電配向セラミックスの製造方法である。 As a method for producing a piezoelectric oriented ceramic having a perovskite structure, for example, a technique described in Patent Document 1 has been proposed. The technique described in Patent Document 1 includes subcomponents contained in a ratio of 5 mol or less (excluding 0 mol) with respect to 100 mol of the main component having a perovskite structure, and includes, for example, a 3d element as the subcomponent. This is a method for producing a piezoelectric oriented ceramic in which a slurry prepared by mixing calcined powder with a solvent is formed in a magnetic field.
また、ペロブスカイト構造を有する圧電配向セラミックスの製造方法として、特許文献２に記載の技術が提案されている。特許文献２に記載された技術は、チタン酸ジルコン酸鉛系化合物を主成分とする圧電原料粉末を含むスラリーを磁場中で成形することを特徴とする圧電配向セラミックスの製造方法である。 In addition, as a method for producing a piezoelectric oriented ceramic having a perovskite structure, a technique described in Patent Document 2 has been proposed. The technique described in Patent Document 2 is a method for producing a piezoelectric oriented ceramic, characterized in that a slurry containing a piezoelectric raw material powder mainly composed of a lead zirconate titanate compound is formed in a magnetic field.
しかしながら、特許文献１に記載のペロブスカイト構造を有する主成分１００ｍｏｌに対して副成分５ｍｏｌとした圧電配向セラミックスでは、配向した圧電配向セラミックスが得られるが、高い圧電ｄ定数を得ることが困難であった。 However, in the piezoelectric oriented ceramic described in Patent Document 1 with the main component having a perovskite structure of 100 mol and the subcomponent being 5 mol, an oriented piezoelectric oriented ceramic can be obtained, but it is difficult to obtain a high piezoelectric d constant. .
また、特許文献２に記載の圧電配向セラミックスの製造方法において、圧電原料粉末の仮焼温度を高めると配向度は高くなるが、圧電ｄ定数が大幅に低下することが明らかとなった。また、仮焼温度が低いと、配向度が低くなるという問題があった。 Further, in the method for producing a piezoelectric oriented ceramic described in Patent Document 2, it has been clarified that when the calcining temperature of the piezoelectric raw material powder is increased, the degree of orientation is increased, but the piezoelectric d constant is significantly reduced. Further, when the calcining temperature is low, there is a problem that the degree of orientation is low.
それゆえに、この発明の主たる目的は、三成分系ＰＺＴ化合物において、結晶配向性が高く、かつ圧電ｄ定数の高い圧電配向セラミックスおよびその製造方法を提供することである。 Therefore, a main object of the present invention is to provide a piezoelectric oriented ceramic having a high crystal orientation and a high piezoelectric d constant in a ternary PZT compound and a method for producing the same.
この発明にかかる圧電配向セラミックスは、組成式（Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3）を主成分とする圧電配向セラミックスであって、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０で、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０であり、結晶相が正方晶またはモルフォトロピック相境界であり、Ｌｏｔｇｅｒｉｎｇ法による配向度が５０％以上であり、且つ、圧電ｄ 33 定数が２３０ｐＣ／Ｎ以上であることを特徴とする、圧電配向セラミックスである。
またこの発明にかかる圧電配向セラミックスの製造方法は、組成式（Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3）を主成分とする組成物粉末を含むスラリーを磁場中で成形することを特徴とする圧電配向セラミックスの製造方法であって、組成物粉末は、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０であり、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０であり、前記組成式となるように調合された素原料粉末を含む、素原料混合スラリーを作製する工程と、素原料混合スラリーを乾燥したものを９００℃以下の温度で仮焼して仮焼粉末を作製する工程と、仮焼粉末を、アルカリ金属のハロゲン塩をフラックスとするフラックス中で熱処理する工程と、を含むことを特徴とする、圧電配向セラミックスの製造方法である。
また、この発明にかかる圧電配向セラミックスの製造方法では、アルカリ金属のハロゲン塩が、ＫＣｌまたはＮａＣｌの少なくとも一方であることが好ましい。
また、この発明にかかる圧電配向セラミックスの製造方法では、仮焼粉末を作製する工程において、８００℃以上の温度で仮焼することが好ましい。
Piezoelectric oriented ceramic according to the present invention is the piezoelectric oriented ceramics mainly the composition formula (Pb ((Ti 1-x Zr x) 1-y) ((Ma a Mb b) y) O 3), Ma is at least one of Ni, Mn, Cr, Mg, Sn, Fe, Co, Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0.40, the molar ratio of Ti to Zr (1-x) / x is 1.0 ≦ (1-x) /x≦2.0, and the crystal phase is a tetragonal or morphotropic phase boundary der is, it is the degree of orientation according
The manufacturing method of the piezoelectric oriented ceramic according to the present invention, the composition formula (Pb ((Ti 1-x Zr x) 1-y) ((Ma a Mb b) y) O 3) composition powder based on A method for producing a piezoelectric oriented ceramic characterized in that a slurry containing s is formed in a magnetic field, wherein the composition powder has at least one of Ma, Ni, Mn, Cr, Mg, Sn, Fe, Co, and Zn. Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0.40, and the molar ratio of Ti and Zr (1-x) / a step of preparing a raw material mixed slurry, wherein x is 1.0 ≦ (1-x) /x≦2.0, and the raw material mixed slurry includes the raw material powder prepared so as to have the composition formula; A step of preparing a calcined powder by calcining a dried product at a temperature of 900 ° C. or lower ; And a step of heat-treating the calcined powder in a flux using an alkali metal halide salt as a flux .
In the manufacturing method of the piezoelectric oriented ceramic according to the present invention, the halogen salt of A alkali metal is preferably at least one of KCl or NaCl.
In the method for producing a piezoelectric oriented ceramic according to the present invention, it is preferable to calcine at a temperature of 800 ° C. or higher in the step of producing the calcined powder.
この発明にかかる圧電配向セラミックスによれば、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高く、かつ圧電ｄ定数が高い圧電配向セラミックスを得ることができる。
また、この発明にかかる圧電配向セラミックスでは、圧電配向セラミックスを構成する粒子が、形状異方性の小さい球状であるので、クラックの発生や進展を生じさせにくくすることができる。
さらに、この発明にかかる圧電配向セラミックスの製造方法によれば、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高い圧電配向セラミックスを得ることができる。
また、この発明にかかる圧電配向セラミックスの製造方法では、組成物粉末として、仮焼粉末をアルカリ金属のハロゲン塩をフラックスとするフラックス中で熱処理した粉末を用いることにより、磁場中成形による高い配向度と高い圧電ｄ定数を得ることができる。
さらに、この発明にかかる圧電配向セラミックスの製造方法では、仮焼粉末を作製する工程において、９００℃以下の温度で仮焼することにより、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高く、さらに圧電ｄ定数の高い圧電配向セラミックスを得ることができる。According to the piezoelectric oriented ceramic according to the present invention, a piezoelectric oriented ceramic having a high degree of orientation calculated by the Lottgering method and a high piezoelectric d constant can be obtained.
Moreover, in the piezoelectric oriented ceramic according to the present invention, since the particles constituting the piezoelectric oriented ceramic are spherical with a small shape anisotropy, it is possible to make it difficult for cracks to be generated and propagated.
Furthermore, according to the method for producing a piezoelectric oriented ceramic according to the present invention, a piezoelectric oriented ceramic having a high degree of orientation calculated by the Lottgering method can be obtained.
Further, in the method for producing a piezoelectric oriented ceramic according to the present invention, a powder obtained by heat-treating a calcined powder in a flux using an alkali metal halogen salt as a flux is used as a composition powder, thereby achieving a high degree of orientation by molding in a magnetic field. A high piezoelectric d constant can be obtained.
Furthermore, in the method for producing a piezoelectric oriented ceramic according to the present invention, the degree of orientation calculated by the Rotgering method is high by calcining at a temperature of 900 ° C. or lower in the step of producing the calcined powder, and the piezoelectric d constant is further reduced. High piezoelectric oriented ceramics can be obtained.
この発明の上述の目的，その他の目的，特徴および利点は、図面を参照して行う以下の発明を実施するための形態の説明から一層明らかとなろう。 The above-mentioned object, other objects, features and advantages of the present invention will become more apparent from the following description of embodiments for carrying out the invention with reference to the drawings.
本発明にかかる圧電配向セラミックスおよびその製造方法の一実施の形態について説明する。 An embodiment of a piezoelectric oriented ceramic and a method for producing the same according to the present invention will be described.
（圧電配向セラミックス）
本発明にかかる圧電配向セラミックスは、複合ペロブスカイト構造を有する圧電配向セラミックスである。この圧電配向セラミックスを構成する粒子は、三成分系ＰＺＴ化合物である組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3を主成分とする粒子を含む。また、この圧電配向セラミックスを構成する粒子は球状である。(Piezoelectric oriented ceramics)
The piezoelectric oriented ceramic according to the present invention is a piezoelectric oriented ceramic having a composite perovskite structure. The particles constituting the piezoelectric oriented ceramic are particles mainly composed of a compositional formula Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 which is a ternary PZT compound. including. Further, the particles constituting the piezoelectric oriented ceramic are spherical.
また、本発明にかかる圧電配向セラミックスは、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3を主成分とし、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０であり、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０である。Further, the piezoelectric oriented ceramic according to the present invention has a composition formula Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 as a main component, and Ma is Ni, Mn, Cr , Mg, Sn, Fe, Co, Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0.40 And the molar ratio (1-x) / x of Ti and Zr is 1.0 ≦ (1-x) /x≦2.0.
また、本発明にかかる圧電配向セラミックスは、結晶相が正方晶またはモルフォトロピック相境界である。 In the piezoelectric oriented ceramic according to the present invention, the crystal phase is a tetragonal or morphotropic phase boundary.
本発明にかかる圧電配向セラミックスにおいて、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3の組成範囲を上記の範囲とすることで、結晶相が菱面体晶からモルフォトロピック相境界を介して正方晶となるため、磁場中成形による配向化が起こりやすくなると考えられる。また、Ｍａ、Ｍｂの量をこの発明にかかる圧電配向セラミックスの組成範囲とすることで、結晶方位ごとの磁化率の差が大きくなり、磁場中成形すると配向化しやすくなり、かつＭａ、Ｍｂを加えることにより電気特性が向上すると考えられる。In the piezoelectric oriented ceramic according to the present invention, the composition range of the composition formula Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 is the above range, Since it becomes a tetragonal crystal from a rhombohedral crystal through a morphotropic phase boundary, it is considered that orientation by forming in a magnetic field is likely to occur. Further, by setting the amounts of Ma and Mb within the composition range of the piezoelectric oriented ceramic according to the present invention, the difference in magnetic susceptibility for each crystal orientation becomes large, and when formed in a magnetic field, orientation becomes easy, and Ma and Mb are added. This is thought to improve the electrical characteristics.
したがって、本発明にかかる圧電配向セラミックスによれば、この圧電配向セラミックスの所定の断面におけるＸ線回折（ＸＲＤ）パターンに基づいて、Ｌｏｔｇｅｒｉｎｇ（ロットゲーリング）法により算出した配向度が高く、かつ圧電ｄ定数が高い圧電配向セラミックスが得られる。 Therefore, according to the piezoelectric oriented ceramic according to the present invention, the degree of orientation calculated by the Lottgering method is high based on the X-ray diffraction (XRD) pattern in a predetermined cross section of the piezoelectric oriented ceramic, and the piezoelectric d Piezoelectric oriented ceramics with a high constant can be obtained.
（圧電配向セラミックスの製造方法）
次に、本発明にかかる圧電配向セラミックスの製造方法の一実施の形態について説明する。(Method of manufacturing piezoelectric oriented ceramics)
Next, an embodiment of a method for producing a piezoelectric oriented ceramic according to the present invention will be described.
本発明にかかる圧電配向セラミックスを製造するため、複合ペロブスカイト構造を有している三成分系ＰＺＴ化合物を含む組成物粉末を用意する。三成分系ＰＺＴ化合物を含む組成物粉末を用意するため、例えば、酸化鉛、酸化チタン、酸化ジルコニウム、酸化ニッケルおよび酸化ニオブなどの素原料を組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3となるように調合した上で湿式混合して素原料を混合したスラリーが得られる。このとき、Ｍａは、Ｎｉであり、Ｍｂは、Ｎｂであり、ａ＋ｂ＝１を満たし、かつ０．０６≦ｙ≦０．４０である。また、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3は、ＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０である。In order to produce the piezoelectric oriented ceramic according to the present invention, a composition powder containing a ternary PZT compound having a composite perovskite structure is prepared. In order to prepare a composition powder containing a ternary PZT compound, for example, raw materials such as lead oxide, titanium oxide, zirconium oxide, nickel oxide and niobium oxide are used as a composition formula Pb ((Ti 1-x Zr x ) 1- Y ) ((Ma a Mb b ) y ) O 3 is prepared, and then wet-mixed to obtain a slurry in which raw materials are mixed. At this time, Ma is Ni, Mb is Nb, satisfies a + b = 1, and satisfies 0.06 ≦ y ≦ 0.40. Further, the composition formula Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 indicates that the molar ratio of Ti to Zr (1-x) / x is 1.0 ≦ ( 1-x) /x≦2.0.
得られた素原料混合スラリーは、乾燥され、９００℃以下で仮焼されて、三成分系ＰＺＴ化合物の仮焼物が作製される。そして、この仮焼物を乾式粉砕して、組成物粉末として、仮焼粉末が作製される。続いて、この仮焼粉末をアルカリ金属のハロゲン塩をフラックスとするフラックス中で熱処理を行い、三成分系ＰＺＴ化合物をフラックス中で熱処理した粉末が用意される。なお、本発明にかかる圧電配向セラミックスを製造するための組成物粉末としては、フラックス中で熱処理した粉末を用いることが好ましい。なお、高配向の圧電配向セラミックスを得るため、仮焼物を作製する際の仮焼温度は、７００℃以上１１００℃以下が好ましいが、さらに、高い圧電ｄ定数の圧電配向セラミックスを得るためには、８００℃以上９００℃以下が好ましい。 The obtained raw material mixed slurry is dried and calcined at 900 ° C. or lower to prepare a calcined product of a ternary PZT compound. Then, this calcined product is dry-pulverized to produce a calcined powder as a composition powder. Subsequently, the calcined powder is heat-treated in a flux using a halogen salt of an alkali metal as a flux, and a powder obtained by heat-treating a ternary PZT compound in the flux is prepared. In addition, it is preferable to use the powder heat-processed in the flux as a composition powder for manufacturing the piezoelectric orientation ceramics concerning this invention. In order to obtain a highly oriented piezoelectric oriented ceramic, the calcining temperature at the time of producing the calcined product is preferably 700 ° C. or higher and 1100 ° C. or lower. Further, in order to obtain a piezoelectric oriented ceramic having a high piezoelectric d constant, 800 degreeC or more and 900 degrees C or less are preferable.
ここで、アルカリ金属のハロゲン塩をフラックスとする熱処理は、例えば、ＫＣｌおよびＮａＣｌの少なくとも一方が有利に用いられるが、ＫＣｌが特に好ましい。 Here, in the heat treatment using a halogen salt of an alkali metal as a flux, for example, at least one of KCl and NaCl is advantageously used, and KCl is particularly preferable.
また、三成分系ＰＺＴ化合物の組成物粉末を用意するため、Ｍａの材料のために酸化ニッケルを準備したが、Ｍａのための材料としては、酸化マンガン、酸化クロム、酸化マグネシウム、酸化スズ、酸化鉄、酸化コバルト、酸化亜鉛の少なくとも１種でもよい。また、前記組成範囲になるように調合する範囲においては、素原料として前記酸化物の一部または全部を、複合酸化物や炭酸塩や水酸化物で置き換えても良い。 In addition, in order to prepare a composition powder of a ternary PZT compound, nickel oxide was prepared for the Ma material, but as the material for Ma, manganese oxide, chromium oxide, magnesium oxide, tin oxide, oxidation It may be at least one of iron, cobalt oxide, and zinc oxide. Moreover, in the range prepared so that it may become the said composition range, you may substitute a part or all of the said oxide as a raw material with complex oxide, carbonate, and a hydroxide.
続いて、上記の方法により用意された三成分系ＰＺＴ化合物の組成物粉末を含む組成物粉末スラリーが作製される。そして、作製された組成物粉末スラリーを使用して磁場中で成形することによって成形体が得られる。このように、作製された組成物粉末スラリーを磁場中で成形することによって、成形体に含まれる結晶の結晶軸が、付与された磁場に従って、所定の方向に配向される。 Subsequently, a composition powder slurry containing the composition powder of the ternary PZT compound prepared by the above method is prepared. And a molded object is obtained by shape | molding in a magnetic field using the produced composition powder slurry. Thus, by shaping the prepared composition powder slurry in a magnetic field, the crystal axes of the crystals contained in the compact are oriented in a predetermined direction according to the applied magnetic field.
次に、上記方法により製造された成形体を焼成して、圧電配向セラミックスが得られる。 Next, the molded body manufactured by the above method is fired to obtain a piezoelectric oriented ceramic.
本発明にかかる圧電配向セラミックの製造方法によれば、圧電配向セラミックスにおいて、組成式（Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3）を主成分とする組成物粉末の組成範囲を、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０で、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０とすることで、Ｌｏｔｇｅｒｉｎｇ（ロットゲーリング）法により算出した配向度が高く、また、圧電ｄ定数の高い圧電配向セラミックスを得ることができる。According to the method for manufacturing a piezoelectric oriented ceramic according to the present invention, the compositional formula (Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 ) is mainly used in the piezoelectric oriented ceramic. The composition range of the composition powder as a component is such that Ma is at least one of Ni, Mn, Cr, Mg, Sn, Fe, Co, and Zn, Mb is Nb, a + b = 1 is satisfied, and Ma The total amount y with Mb is 0.06 ≦ y ≦ 0.40, and the molar ratio of Ti and Zr (1-x) / x is 1.0 ≦ (1-x) /x≦2.0. Thus, a piezoelectric oriented ceramic having a high degree of orientation calculated by the Lottgering method and a high piezoelectric d constant can be obtained.
また、本発明にかかる圧電配向セラミックスの製造方法によれば、仮焼粉末からフラックス中で熱処理した粉末を作製する工程において、仮焼粉末に対して、アルカリ金属のハロゲン塩をフラックスとする熱処理を行った組成物粉末を用いることにより、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高い圧電配向セラミックスを得ることができる。さらに、仮焼粉末を作製する工程において、９００℃以下の温度で仮焼することで、圧電ｄ定数の高い圧電配向セラミックスを得ることができる。 Further, according to the method for manufacturing a piezoelectric oriented ceramic according to the present invention, in the step of producing a powder heat-treated in the flux from the calcined powder, the calcined powder is subjected to a heat treatment using an alkali metal halogen salt as a flux. By using the performed composition powder, a piezoelectric oriented ceramic with a high degree of orientation calculated by the Lottgering method can be obtained. Furthermore, in the step of producing the calcined powder, by performing calcining at a temperature of 900 ° C. or lower, a piezoelectric oriented ceramic having a high piezoelectric d constant can be obtained.
次に、本発明に係る圧電配向セラミックスの製造方法およびその製造方法により作製された圧電配向セラミックスの効果を確認するために行った実験例について以下に説明する。 Next, a method for manufacturing a piezoelectric oriented ceramic according to the present invention and an experimental example performed for confirming the effect of the piezoelectric oriented ceramic produced by the manufacturing method will be described below.
１．試料の作製
（試料１〜試料１７）
試料１ないし試料１７は、以下に記載の作製方法により作製された。試料１ないし試料１７は、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3を主成分とする組成物粉末において、Ｔｉ／Ｚｒのモル比率、ＭａＭｂ量およびＭａの材料を変化させたものである。1. Sample preparation (Sample 1 to Sample 17)
Samples 1 to 17 were manufactured by the manufacturing method described below. Samples 1 to 17 are the composition powders having the composition formula Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 as the main component, and the molar ratio of Ti / Zr. The amount of MaMb and the material of Ma are changed.
試料１〜試料１０は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化ニッケルおよび酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合された。なお、ａは１／３であり、ｂは２／３であるので、ａ＋ｂ＝１である。Samples 1 to 10 are composed of lead oxide, titanium oxide, zirconium oxide, nickel oxide and niobium oxide as raw materials, and a composition formula Pb ((Ti 1-x Zr x ) 1-y (Ma 1/3 Mb 2 / 3 ) y ) O 3 . Since a is 1/3 and b is 2/3, a + b = 1.
また、試料１１は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化マンガンおよび酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合され、試料１２は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化クロムおよび酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合され、試料１３は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化マグネシウムおよび酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合され、試料１４は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化スズおよび酸化ニオブが、組成としてＰｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合された。
さらに、試料１５は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化鉄および酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合され、試料１６は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化コバルトおよび酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合され、試料１７は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化亜鉛および酸化ニオブが、組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3となるように調合された。Sample 11 is composed of lead oxide, titanium oxide, zirconium oxide, manganese oxide and niobium oxide as raw materials, and a composition formula Pb ((Ti 1-x Zr x ) 1-y (Ma 1/3 Mb 2 / 3 ) y ) Prepared to be O 3, and sample 12 is composed of lead oxide, titanium oxide, zirconium oxide, chromium oxide and niobium oxide as raw materials, and a composition formula Pb ((Ti 1-x Zr x ) as a composition. 1-y (Ma 1/3 Mb 2/3 ) y ) O 3, and sample 13 is composed of lead oxide, titanium oxide, zirconium oxide, magnesium oxide and niobium oxide as the composition as raw materials. Formula 14 is prepared so as to be Pb ((Ti 1−x Zr x ) 1−y (Ma 1/3 Mb 2/3 ) y ) O 3. Sample 14 is composed of lead oxide, titanium oxide, zirconium oxide as raw materials. , Tin oxide and niobium oxide have the composition Pb (Ti 1-x Zr x) formulated such that 1-y (Ma 1/3 Mb 2/3 ) y) O 3.
Further,
ここで、試料１〜試料１７の各試料に対する組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3におけるＴｉとＺｒのモル比率（Ｔｉ／Ｚｒ比）を表１に示す。また、試料１〜試料１７の各試料に対する組成として組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3におけるＭａＭｂ量であるｙの値も表１に示す。Here, the composition ratio of Ti to Zr in the composition formula Pb ((Ti 1-x Zr x ) 1-y (Ma 1/3 Mb 2/3 ) y ) O 3 as the composition of each of the samples 1 to 17 (Ti / Zr ratio) is shown in Table 1. The value of y is MaMb amount in the composition formula Pb ((Ti 1-x Zr x) 1-y (Ma 1/3 Mb 2/3) y) O 3 as a composition for each sample of samples 1 17 Are also shown in Table 1.
次に、上記の記載のとおり調合されたものは、水を溶媒としてボールミルにより混合撹拌され、素原料混合スラリーが得られた。得られた素原料混合スラリーを乾燥したものは、９００℃で仮焼され、仮焼粉末が得られた。続いて、得られた仮焼粉末とＫＣｌとは、重量比で１：１となるように混合され、アルミナるつぼ中で１０００℃、１２時間熱処理して室温まで冷却した後、ＫＣｌを水洗除去して、組成物粉末として、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）y）Ｏ3のフラックス中で熱処理した粉末が得られた。Next, what was prepared as described above was mixed and stirred by a ball mill using water as a solvent to obtain a raw material mixed slurry. What dried the obtained raw material mixing slurry was calcined at 900 ° C. to obtain a calcined powder. Subsequently, the obtained calcined powder and KCl were mixed at a weight ratio of 1: 1, heat-treated in an alumina crucible at 1000 ° C. for 12 hours and cooled to room temperature, and then KCl was removed by washing with water. Te, as a composition powder the composition formula Pb ((Ti 1-x Zr x) 1-y (Ma 1/3 Mb 2/3) y) powder heat-treated at O 3 in the flux was obtained.
ここで、得られた試料１ないし試料１７のフラックス中で熱処理した粉末のうち、代表的なもののＳＥＭ像が、図１に示される。図１（ａ）は、試料１のＳＥＭ像であり、図１（ｂ）は、試料３のＳＥＭ像であり、図１（ｃ）は、試料４のＳＥＭ像であり、図１（ｄ）は、試料６のＳＥＭ像であり、図１（ｅ）は、試料７のＳＥＭ像であり、図１（ｆ）は、試料８のＳＥＭ像である。図１によると、いずれのフラックス中で熱処理した粉末も球状であることがわかる。すなわち、図１に示される各試料に係るフラックス中で熱処理した粉末は、結晶粒が等方的に成長しており、形状異方性の小さいことがわかる。 Here, an SEM image of a representative one of the powders heat-treated in the fluxes of the obtained samples 1 to 17 is shown in FIG. 1A is an SEM image of the sample 1, FIG. 1B is an SEM image of the sample 3, FIG. 1C is an SEM image of the sample 4, and FIG. Is an SEM image of sample 6, FIG. 1 (e) is an SEM image of sample 7, and FIG. 1 (f) is an SEM image of sample 8. According to FIG. 1, it can be seen that the powder heat-treated in any flux is spherical. That is, it can be seen that the powder heat-treated in the flux according to each sample shown in FIG. 1 has crystal grains growing isotropically and has a small shape anisotropy.
次に、得られたフラックス中で熱処理した粉末を２５ｇ取り出し、このフラックス中で熱処理した粉末１００重量部に対し、分散剤１．５重量部、純水４０重量部を加えて８時間ボールミル混合することにより、組成物粉末スラリーが得られた。 Next, 25 g of the powder heat-treated in the obtained flux was taken out, and 1.5 parts by weight of a dispersant and 40 parts by weight of pure water were added to 100 parts by weight of the powder heat-treated in the flux, followed by ball mill mixing for 8 hours. Thus, a composition powder slurry was obtained.
次に、得られた組成物粉末スラリーは、１２Ｔの磁場中で鋳込み成形することにより、成形体が得られた。得られた成形体は、焼成温度１１５０℃、トップ温度での保持時間３時間の条件で焼成され、試料１ないし試料１７の焼結体が得られた。 Next, the obtained composition powder slurry was cast and molded in a 12 T magnetic field to obtain a molded body. The obtained molded body was fired under conditions of a firing temperature of 1150 ° C. and a holding time of 3 hours at the top temperature, and sintered bodies of Sample 1 to Sample 17 were obtained.
続いて、試料１８ないし試料２０の作製において、仮焼粉末を得るための仮焼温度を変化させ、さらに仮焼粉末に対するフラックス中での熱処理の有無の効果についての実験例が示される。
Subsequently, in the production of Sample 18 to
（試料１８）
試料１８は、以下に記載の作製方法により作製された。なお、試料１８は、９００℃で仮焼された仮焼粉末をＫＣｌフラックス中で熱処理した組成物粉末を用いた試料である。
試料１８は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化ニッケル、酸化ニオブが、組成として組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3となるように調合された。そして、調合されたものは、水を溶媒としてボールミルにより混合撹拌され、素原料混合スラリーが得られた。得られた素原料混合スラリーを乾燥したものは、９００℃で仮焼され、仮焼粉末が得られた。得られた仮焼粉末とＫＣｌとは、重量比で１：１となるように混合され、アルミナるつぼ中で１０００℃、１２時間熱処理して室温まで冷却した後、ＫＣｌを水洗除去して、組成物粉末として、組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3のフラックス中で熱処理した粉末が得られた。ここで、得られたフラックス中で熱処理した粉末のＳＥＭ像は、図２（ａ）に示される。図２（ａ）によると、フラックス中で熱処理した粉末は球状であることがわかる。すなわち、図２（ａ）に示される各試料に係るフラックス中で熱処理した粉末は、結晶粒が等方的に成長しており、形状異方性が小さいことがわかる。(Sample 18)
Sample 18 was produced by the production method described below. In addition, the sample 18 is a sample using the composition powder which heat-processed the calcining powder calcined at 900 degreeC in KCl flux.
In the sample 18, lead oxide, titanium oxide, zirconium oxide, nickel oxide, and niobium oxide are used as raw materials, and the composition is the composition formula Pb (Ti 0.40 Zr 0.33 (Ni 1/3 Nb 2/3 ) 0.27 ) O 3. Was formulated. The prepared mixture was mixed and stirred by a ball mill using water as a solvent to obtain a raw material mixed slurry. What dried the obtained raw material mixing slurry was calcined at 900 ° C. to obtain a calcined powder. The obtained calcined powder and KCl were mixed at a weight ratio of 1: 1, heat-treated in an alumina crucible at 1000 ° C. for 12 hours and cooled to room temperature, and then KCl was washed away with water to obtain a composition. As a product powder, a powder heat-treated in a flux of composition formula Pb (Ti 0.40 Zr 0.33 (Ni 1/3 Nb 2/3 ) 0.27 ) O 3 was obtained. Here, the SEM image of the powder heat-processed in the obtained flux is shown by Fig.2 (a). According to FIG. 2A, it can be seen that the powder heat-treated in the flux is spherical. That is, it can be seen that the powder heat-treated in the flux according to each sample shown in FIG. 2A has isotropic crystal growth and small shape anisotropy.
次に、得られたフラックス中で熱処理した粉末を２５ｇ取り出し、このフラックス中で熱処理した粉末１００重量部に対し、分散剤１．５重量部、純水４０重量部を加えて８時間ボールミル混合することにより、組成物粉末スラリーが得られた。 Next, 25 g of the powder heat-treated in the obtained flux was taken out, and 1.5 parts by weight of a dispersant and 40 parts by weight of pure water were added to 100 parts by weight of the powder heat-treated in the flux, followed by ball mill mixing for 8 hours. Thus, a composition powder slurry was obtained.
次に、得られた組成物粉末スラリーは、１２Ｔの磁場中で鋳込み成形することにより、成形体が得られた。得られた成形体は、焼成温度１１５０℃、トップ温度での保持時間３時間の条件で焼成され、試料１８の焼結体が得られた。 Next, the obtained composition powder slurry was cast and molded in a 12 T magnetic field to obtain a molded body. The obtained compact was fired under the conditions of a firing temperature of 1150 ° C. and a holding time of 3 hours at the top temperature, and a sintered body of Sample 18 was obtained.
（試料１９）
試料１９は、以下に記載の作製方法により作製された。なお、試料１９は、仮焼粉末をＫＣｌフラックス中で熱処理されていない組成物粉末を用いた試料である。(Sample 19)
Sample 19 was produced by the production method described below. Sample 19 is a sample using a composition powder that is not heat-treated in a KCl flux.
試料１９は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化ニッケル、酸化ニオブが、組成として組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3となるように調合された。そして、調合されたものは、水を溶媒としてボールミルにより混合撹拌され、素原料混合スラリーが得られた。得られた素原料混合スラリーを乾燥したものは、９００℃で仮焼され、組成物粉末として、仮焼粉末が得られた。得られた仮焼粉末のＳＥＭ像は、図２（ｂ）に示される。図２（ｂ）によると、仮焼粉末は球状粒子として成長していないことがわかる。In the sample 19, lead oxide, titanium oxide, zirconium oxide, nickel oxide, and niobium oxide are used as raw materials, and the composition is the composition formula Pb (Ti 0.40 Zr 0.33 (Ni 1/3 Nb 2/3 ) 0.27 ) O 3. Was formulated. The prepared mixture was mixed and stirred by a ball mill using water as a solvent to obtain a raw material mixed slurry. What dried the obtained raw material mixing slurry was calcined at 900 ° C., and a calcined powder was obtained as a composition powder. An SEM image of the obtained calcined powder is shown in FIG. As can be seen from FIG. 2B, the calcined powder does not grow as spherical particles.
次に、得られた仮焼粉末を２５ｇ取り出し、この仮焼粉末１００重量部に対し、分散剤１．５重量部、純水４０重量部を加えて８時間ボールミル混合され、組成物粉末スラリーが得られた。 Next, 25 g of the obtained calcined powder was taken out, and 1.5 parts by weight of a dispersant and 40 parts by weight of pure water were added to 100 parts by weight of the calcined powder, and ball mill mixing was performed for 8 hours. Obtained.
次に、得られた組成物粉末スラリーは、１２Ｔの磁場中で鋳込み成形することにより、成形体が得られた。得られた成形体は、焼成温度１１５０℃、トップ温度での保持時間３時間の条件で焼成され、試料１９の焼結体が得られた。 Next, the obtained composition powder slurry was cast and molded in a 12 T magnetic field to obtain a molded body. The obtained molded body was fired under the conditions of a firing temperature of 1150 ° C. and a holding time of 3 hours at the top temperature, and a sintered body of Sample 19 was obtained.
（試料２０）
試料２０は、以下に記載の作製方法により作製された。なお、試料２０は、１１００℃で仮焼された仮焼粉末をＫＣｌフラックス中で熱処理した組成物粉末を用いた試料である。(Sample 20)
The
試料２０は、素原料として酸化鉛、酸化チタン、酸化ジルコニウム、酸化ニッケル、酸化ニオブが、組成として組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3となるように調合された。そして、調合されたものは、水を溶媒としてボールミルにより混合撹拌され、素原料混合スラリーが得られた。得られた素原料混合スラリーを乾燥したものは、１１００℃で仮焼され、仮焼粉末が得られた。得られた仮焼粉末とＫＣｌとは、重量比で１：１となるように混合されアルミナるつぼ中で１０００℃、１２時間熱処理し、室温まで冷却した後、ＫＣｌを水洗除去して、組成物粉末として、組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3のフラックス中で熱処理した粉末が得られた。得られたセラミック粉末のＳＥＭ像は、図２（ｃ）に示される。図２（ｃ）によると、フラックス中で熱処理した粉末は球状粒子として成長していないことがわかる。In the
次に、得られたフラックス中で熱処理した粉末を２５ｇ取り出し、このフラックス中で熱処理した粉末１００重量部に対し、分散剤１．５重量部、純水４０重量部を加えて８時間ボールミル混合され、組成物粉末スラリーが得られた。 Next, 25 g of the powder heat-treated in the obtained flux was taken out, and 100 parts by weight of the heat-treated powder in the flux was added with 1.5 parts by weight of a dispersant and 40 parts by weight of pure water, followed by ball mill mixing for 8 hours. A composition powder slurry was obtained.
次に、得られた組成物粉末スラリーは、１２Ｔの磁場中で鋳込み成形することにより、成形体を得た。得られた成形体は、焼成温度１１５０℃、トップ温度での保持時間３時間の条件で焼成され、試料２０の焼結体が得られた。
Next, the obtained composition powder slurry was cast and molded in a 12 T magnetic field to obtain a molded body. The obtained molded body was fired under the conditions of a firing temperature of 1150 ° C. and a holding time of 3 hours at the top temperature, and a sintered body of
２．評価
次に、まず、上述の作製方法により得られた各試料に係る焼結体の結晶相について調べた。各試料に係る結晶相が、Ｔｅｔｒａｇｏｎａｌ（正方晶）か、Ｒｈｏｍｂｏｈｅｄｒａｌ（菱面体晶）のいずれかについては、Ｘ線回析法により解析した。2. Evaluation Next, first, the crystal phase of the sintered body according to each sample obtained by the above-described production method was examined. Whether the crystal phase of each sample was tetragonal (tetragonal) or rhombohedral (rhombohedral) was analyzed by X-ray diffraction.
また、上述の作製方法により得られた各試料に係る焼結体の配向度は、Ｌｏｔｇｅｒｉｎｇ（ロットゲーリング）法により、以下の数式（１）から算出された。配向度の計算では、磁場を印加しない状態で成形した成形体を焼成することにより得られた組成式Ｐｂ（Ｔｉ0.40Ｚｒ0.33（Ｎｉ1/3Ｎｂ2/3）0.27）Ｏ3の焼結体を基準試料とした。In addition, the degree of orientation of the sintered body according to each sample obtained by the above-described production method was calculated from the following formula (1) by the Lottgering method. In the calculation of the degree of orientation, a sintered body of composition formula Pb (Ti 0.40 Zr 0.33 (Ni 1/3 Nb 2/3 ) 0.27 ) O 3 obtained by firing a molded body molded without applying a magnetic field. Was used as a reference sample.
ここで、ΣＩ（ＨＫＬ）は評価対象の焼結体における特定の結晶面（ＨＫＬ）のＸ線ピーク強度の総和であり、ΣＩ（ｈｋｌ）は評価対象の焼結体の全結晶面（ｈｋｌ）のＸ線ピーク強度の総和である。また、ΣＩ0（ＨＫＬ）は基準試料における特定の結晶面（ＨＫＬ）のＸ線ピーク強度の総和であり、ΣＩ0（ｈｋｌ）は基準試料の全結晶面（ｈｋｌ）のＸ線ピーク強度の総和である。Here, ΣI (HKL) is the sum of X-ray peak intensities of specific crystal planes (HKL) in the sintered body to be evaluated, and ΣI (hkl) is the total crystal plane (hkl) of the sintered body to be evaluated. Is the sum of the X-ray peak intensities. ΣI 0 (HKL) is the sum of X-ray peak intensities of a specific crystal plane (HKL) in the reference sample, and ΣI 0 (hkl) is the sum of X-ray peak intensities of all crystal planes (hkl) of the reference sample. It is.
また、測定条件は、２θ＝２０〜６０ｄｅｇとした。また、全結晶面（ｈｋｌ）のＸ線ピークの強度として、＜１００＞、＜１１０＞、＜１１１＞、＜２００＞、＜２１０＞および＜２１１＞の各強度を使用した。特定の結晶面（ＨＫＬ）として、＜１００＞および＜２００＞の各強度を使用した。 The measurement conditions were 2θ = 20-60 deg. Moreover, each intensity | strength of <100>, <110>, <111>, <200>, <210>, and <211> was used as the intensity | strength of the X-ray peak of all the crystal planes (hkl). <100> and <200> intensities were used as specific crystal planes (HKL).
さらに、上述の作製方法により得られた各試料に係る焼結体について３ｋＶ／ｍｍで分極した上で、圧電ｄ33定数は、日本電子工業材料会標準規格「圧電セラミック振動子の電気的試験方法」ＥＭＡＳ−６１００に準拠し、インピーダンスアナライザ（ヒューレット・パッカード社製）を使用して、矩形振動子の長辺方向振動について、共振・反共振法によって測定した。Furthermore, after the sintered body according to each sample obtained by the above-described manufacturing method is polarized at 3 kV / mm, the piezoelectric d 33 constant is determined by the Japan Electronic Industry Material Association Standard “Electric Test Method for Piezoelectric Ceramic Vibrators”. In accordance with EMAS-6100, the long-side vibration of the rectangular vibrator was measured by a resonance / anti-resonance method using an impedance analyzer (manufactured by Hewlett-Packard Company).
得られた試料１ないし試料１７の焼結体の結晶系、配向度、および圧電ｄ定数の測定結果が、表１に示される。また、得られた試料１ないし試料１７のうち、代表的なものの圧電配向セラミックスの焼結体の所定の断面におけるＸＲＤチャートが、図３に示される。図３（ａ）は、試料１、試料３、試料４、試料６および試料７のＸＲＤチャートであり、図３（ｂ）は、試料８のＸＲＤチャートであり、図３（ｃ）は、試料９のＸＲＤチャートである。 Table 1 shows the measurement results of the crystal system, orientation degree, and piezoelectric d constant of the obtained sintered bodies of Sample 1 to Sample 17. In addition, an XRD chart in a predetermined cross section of a sintered body of a piezoelectric oriented ceramic of a representative one of the obtained samples 1 to 17 is shown in FIG. 3A is an XRD chart of Sample 1, Sample 3, Sample 4, Sample 6, and Sample 7, FIG. 3B is an XRD chart of Sample 8, and FIG. 3C is a sample. 9 is an XRD chart of 9;
表１における試料１ないし試料７は、Ｔｉ／Ｚｒのモル比率を変化させ、ＭａＭｂ量を０．２７に固定した場合の各試料におけるＬｏｔｇｅｒｉｎｇ法により算出した配向度および圧電ｄ33定数の測定結果を示している。Samples 1 to 7 in Table 1 show the measurement results of the degree of orientation and the piezoelectric d 33 constant calculated by the Rotgering method in each sample when the Ti / Zr molar ratio is changed and the MaMb amount is fixed to 0.27. Show.
この結果によると、表１における試料１ないし試料５に示すような、Ｔｉ／Ｚｒの比率を２．２から１．０の範囲内においては、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度において、いずれも５０％以上と高い配向度が得られた。これは、得られた各試料の結晶相が正方晶であることから、磁場中成形による配向化が起こりやすくなっているためであると考えられる。 According to this result, as shown in Sample 1 to Sample 5 in Table 1, when the Ti / Zr ratio is in the range of 2.2 to 1.0, the degree of orientation calculated by the Rotgering method is 50%. A high degree of orientation was obtained as described above. This is presumably because the crystal phase of each obtained sample is a tetragonal crystal, and orientation by forming in a magnetic field is likely to occur.
一方、試料６および試料７は、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度は、いずれも０％であった。ＰＺＴ化合物のようなペロブスカイト構造の結晶は、ビスマス層状化合物やタングステンブロンズ構造の結晶と比較して結晶の異方性が小さく、磁場による配向が難しい。また、正方晶のＰＺＴ化合物と比較して菱面体晶のＰＺＴ化合物は軸による磁化率の差が小さいと考えられる。このため、試料６および試料７の結晶相が菱面体晶のＰＺＴ化合物は、配向されないものと考えられる。 On the other hand, Sample 6 and Sample 7 both had an orientation degree calculated by the Lottgering method of 0%. Crystals having a perovskite structure such as a PZT compound have a smaller crystal anisotropy than a bismuth layered compound or a tungsten bronze structure, and are difficult to be oriented by a magnetic field. In addition, it is considered that the rhombohedral PZT compound has a smaller difference in magnetic susceptibility due to the axes than the tetragonal PZT compound. For this reason, it is considered that the rhombohedral PZT compounds of Sample 6 and Sample 7 are not oriented.
また、試料１では、Ｔｉ／Ｚｒのモル比率が２．２の場合であるが、圧電ｄ33定数は、２１５ｐＣ／Ｎであった。一方、試料２ないし試料５のように、Ｔｉ／Ｚｒのモル比率を２．０から１．０の範囲内とすることで、いずれも２３０ｐＣ／Ｎ以上の高い圧電ｄ33定数を有する焼結体が得られた。In Sample 1, the Ti / Zr molar ratio was 2.2, but the piezoelectric d 33 constant was 215 pC / N. On the other hand, as in Samples 2 to 5, by setting the molar ratio of Ti / Zr within the range of 2.0 to 1.0, all sintered bodies having a high piezoelectric d 33 constant of 230 pC / N or more was gotten.
次に、表１における試料８ないし試料１０は、Ｔｉ／Ｚｒのモル比率を１．２で固定し、ＭａＭｂ量を０．４０から０．０５まで変化させた場合の各試料における配向度および圧電ｄ33定数の測定結果を示している。Next, Sample 8 to Sample 10 in Table 1 have the Ti / Zr molar ratio fixed at 1.2 and the degree of orientation and piezoelectricity in each sample when the amount of MaMb is changed from 0.40 to 0.05. The measurement result of d33 constant is shown.
この結果によると、試料８および試料９では、ＭａＭｂ量がそれぞれ０．４０および０．０７と高いことから、磁化率の異方性が高まる可能性があるため、その結果、高い配向度が得られた。一方、試料１０は、ＭａＭｂ量が０．０５と低いため、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が５０％より低くなった。 According to this result, in Sample 8 and Sample 9, since the MaMb amount is as high as 0.40 and 0.07, respectively, the anisotropy of the magnetic susceptibility may be increased. As a result, a high degree of orientation is obtained. It was. On the other hand, since the amount of MaMb of Sample 10 was as low as 0.05, the degree of orientation calculated by the Lottgering method was lower than 50%.
次に、表１における試料１１ないし試料１４は、それぞれＭａの材料をＮｉではなくＭｎ、Ｃｒ、ＭｇおよびＳｎとし、ＭａＭｂ量は０．０６で固定した場合の各試料における配向度および圧電ｄ33定数の測定結果を示している。なお、Ｔｉ／Ｚｒのモル比率は、試料１１および試料１２は１．０とし、試料１３および試料１４は１．１であり、いずれの結晶相も正方晶としている。
また、表１における試料１５ないし試料１７は、Ｍａの材料をＮｉではなく、Ｆｅ、ＣｏおよびＺｎとし、ＭａＭｂ量は０．２０で固定した場合の各試料における配向度および圧電ｄ33定数の測定結果を示している。なお、Ｔｉ／Ｚｒのモル比率は、１．３とし、いずれの結晶相も正方晶としている。Next, Sample 11 to Sample 14 in Table 1 are not limited to Ni but to Mn, Cr, Mg and Sn, respectively, and the degree of orientation and piezoelectric d 33 in each sample when the MaMb amount is fixed at 0.06. The constant measurement results are shown. The molar ratio of Ti / Zr is 1.0 for sample 11 and sample 12, and 1.1 for sample 13 and sample 14. Both crystal phases are tetragonal.
この結果によると、各試料におけるＬｏｔｇｅｒｉｎｇ法により算出した配向度は、いずれも５０％以上の高配向度が得られた。また、各試料における圧電ｄ33定数は、いずれも２３０ｐＣ／Ｎ以上の高い圧電ｄ33定数が得られた。According to this result, the orientation degree calculated by the Lottgering method for each sample was 50% or higher. Further, the piezoelectric d 33 constant of each sample was a high piezoelectric d 33 constant of 230 pC / N or more.
従って、以上の結果より、組成式Ｐｂ（（Ｔｉ1-xＺｒx）1-y（Ｍａ1/3Ｍｂ2/3）ｙ）Ｏ3を主成分とする圧電配向セラミックスは、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０で、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０とし、さらに、結晶相を正方晶とすることで、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度および圧電ｄ33定数が、いずれも高い焼結体を得られることが明らかとなった。Therefore, from the above results, the piezoelectric oriented ceramics whose main component is the composition formula Pb ((Ti 1−x Zr x ) 1−y (Ma 1/3 Mb 2/3 ) y) O 3 has Ma as Ni, It is at least one of Mn, Cr, Mg, Sn, Fe, Co, and Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0. 40, and the molar ratio of Ti to Zr (1-x) / x is 1.0 ≦ (1-x) /x≦2.0, and the crystal phase is tetragonal. It was revealed that a sintered body having a high degree of orientation and piezoelectric d 33 constant can be obtained.
なお、以上の結果を得た理由としては、以下のように考えることができる。すなわち、正方晶は、結晶方位（＜１００＞，＜１１０＞，＜１１１＞）ごとの磁化率の差が大きい可能性があり、このため磁場中成形で高い配向度が得られたと考えられる。これに対し、試料６および試料７のような菱面体晶では、結晶方位ごとの磁化率の差が小さいと考えられ、そのため圧電配向セラミックスが得られなかったと考えられる。また、Ｍａは、チタン酸ジルコン酸鉛の結晶の磁化率の異方性を高めている可能性があり、このためＭａＭｂ量が多い場合に、高い配向度が得られたと考えられる。 The reason for obtaining the above results can be considered as follows. That is, tetragonal crystals may have a large difference in magnetic susceptibility for each crystal orientation (<100>, <110>, <111>), and it is considered that a high degree of orientation was obtained by molding in a magnetic field. On the other hand, in the rhombohedral crystals such as Sample 6 and Sample 7, it is considered that the difference in magnetic susceptibility for each crystal orientation is small, so that it is considered that a piezoelectric oriented ceramic could not be obtained. Further, Ma may increase the anisotropy of the magnetic susceptibility of the lead zirconate titanate crystal. Therefore, it is considered that a high degree of orientation was obtained when the amount of MaMb was large.
続いて、得られた試料１８ないし試料２０の焼結体の結晶相、配向度、および圧電ｄ定数の測定結果が、表２に示される。得られた試料１８ないし試料２０の圧電配向セラミックスの焼結体の所定の断面におけるＸＲＤチャートが、図４に示される。図４（ａ）は、試料１８のＸＲＤチャートであり、図４（ｂ）は、試料１９のＸＲＤチャートであり、図４（ｃ）は、試料２０のＸＲＤチャートである。
Subsequently, Table 2 shows the measurement results of the crystal phase, orientation degree, and piezoelectric d constant of the obtained sintered bodies of Sample 18 to
表２における試料１８ないし試料２０は、Ｔｉ／Ｚｒのモル比率は１．２であり、ＭａＭｂ量は０．２７である。なお、試料１８の作製工程においては、仮焼粉末を得るための仮焼温度を９００℃とし、得られた仮焼粉末に対して、ＫＣｌフラックス中での熱処理を行っている。また、試料１９の作製工程においては、仮焼粉末を得るための仮焼温度を９００℃としたが、その後得られた仮焼粉末に対しては、ＫＣｌフラックス中での熱処理は行っていない。さらに、試料２０の作製工程においては、仮焼粉末を得るための仮焼温度を１１００℃とし、得られた仮焼粉末に対して、ＫＣｌフラックス中での熱処理を行っている。
Sample 18 to
この結果によると、試料１８に対して、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度は５０％以上の高い配向度であり、圧電ｄ33定数についても６０３ｐＣ／Ｎと高い結果が得られた。According to this result, the orientation degree calculated by the Lottgering method with respect to the sample 18 was a high orientation degree of 50% or more, and the piezoelectric d 33 constant was as high as 603 pC / N.
一方、試料１９に対して、圧電ｄ33定数は４５４ｐＣ／Ｎと高いものの、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度は、０％であった。また、試料２０に対して、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度は５０％以上と高いものの、圧電ｄ33定数は１４１と低い結果が得られた。On the other hand, although the piezoelectric d 33 constant was as high as 454 pC / N with respect to Sample 19, the degree of orientation calculated by the Lottgering method was 0%. Further, although the degree of orientation calculated by the Lottgering method was as high as 50% or more with respect to the
以上の表２における試料１８ないし試料２０の結果から、各試料の作製工程において、仮焼粉末を得るための仮焼温度を９００℃とし、さらに、得られた仮焼粉末に対して、ＫＣｌのフラックス中で熱処理を行うことで、配向度および圧電ｄ33定数といずれも高い焼結体を得ることができることが明らかとなった。From the results of Sample 18 to
なお、以上の結果を得た理由としては、以下のように考えることができる。すなわち、高い温度で仮焼した三成分系ＰＺＴ化合物の仮焼粉末は、固相反応による粒成長が進んでおり、また、未反応の酸化鉛なども少なくなっているため、焼結性が低下し、圧電ｄ定数が低下しているものと考えられる。一方、低い温度で仮焼した三成分系ＰＺＴ化合物の仮焼粉末は、ＰｂＯなどの未反応成分が多く残っているため焼結性が高く、圧電ｄ定数の低下は小さいが、粒子同士の凝集が強いため、磁場中成形しても配向化しなかったと考えられる。 The reason for obtaining the above results can be considered as follows. That is, the calcination powder of the ternary PZT compound calcined at a high temperature has progressed in grain growth due to a solid-phase reaction, and the amount of unreacted lead oxide is reduced, so that the sinterability is lowered. It is considered that the piezoelectric d constant is lowered. On the other hand, the calcination powder of the ternary PZT compound calcined at a low temperature has high sinterability because a large amount of unreacted components such as PbO remain, and the decrease in the piezoelectric d constant is small. Therefore, it is considered that the film was not oriented even when molded in a magnetic field.
また、低い温度で仮焼した後に、フラックス中で熱処理することにより得られたフラックス中で熱処理した粉末は、高い温度で熱処理を受けていないために焼結性が低下せず、他方、フラックス中で熱処理しているために、粒子同士が分散した状態で結晶性が高まり、このようにして得られたフラックス中で熱処理した粉末を使用することによって磁場中成形による高い配向度と高い圧電ｄ定数が得られたものと考えられる。 In addition, the powder heat-treated in the flux obtained by heat-treating in the flux after calcining at a low temperature does not deteriorate the sinterability because it has not been heat-treated at a high temperature. Since the crystallinity is increased in a state where the particles are dispersed, the degree of orientation due to molding in a magnetic field and the high piezoelectric d constant are obtained by using the powder heat-treated in the flux thus obtained. Is considered to have been obtained.
この発明にかかる圧電配向セラミックスでは、組成式（Ｐｂ（（Ｔｉ1-xＺｒx）1-y）（（ＭａaＭｂb）y）Ｏ3）を主成分とする組成物粉末の組成範囲を、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０で、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０とすることで、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高く、また、圧電ｄ定数の高い圧電配向セラミックスを得ることができる。In the piezoelectric oriented ceramics according to the present invention, the composition range of the composition powder whose main component is the composition formula (Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 ) , Ma is at least one of Ni, Mn, Cr, Mg, Sn, Fe, Co, Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0.40 and the molar ratio (1-x) / x of Ti and Zr is 1.0 ≦ (1-x) /x≦2.0, and the degree of orientation calculated by the Rotgering method In addition, a piezoelectric oriented ceramic having a high piezoelectric d constant can be obtained.
本発明にかかる圧電配向セラミックスの製造方法によれば、仮焼粉末からフラックス中で熱処理した粉末を作製する工程において、仮焼粉末に対して、アルカリ金属のハロゲン塩をフラックスとする熱処理により、Ｌｏｔｇｅｒｉｎｇ法により算出した配向度が高い圧電配向セラミックスを得ることができる。また、この発明にかかる圧電配向セラミックスの製造方法によれば、組成物粉末として、仮焼粉末をアルカリ金属のハロゲン塩をフラックスとするフラックス中で熱処理した粉末を用いることにより、磁場中成形による高い配向度と高い圧電ｄ定数を得ることができる。さらに、本発明にかかる圧電配向セラミックスの製造方法によれば、仮焼粉末を作製する工程において、仮焼温度を９００℃以下の温度で仮焼することで、圧電ｄ定数の高い圧電配向セラミックスを得ることができる。 According to the method for manufacturing a piezoelectric oriented ceramic according to the present invention, in the step of producing a powder heat-treated in a flux from a calcined powder, the calcined powder is subjected to a heat treatment using an alkali metal halide as a flux. Piezoelectric oriented ceramics having a high degree of orientation calculated by the method can be obtained. In addition, according to the method for producing a piezoelectric oriented ceramic according to the present invention, a powder obtained by heat-treating a calcined powder in a flux using a halogen salt of an alkali metal as a flux is used as a composition powder. An orientation degree and a high piezoelectric d constant can be obtained. Furthermore, according to the method for producing a piezoelectric oriented ceramic according to the present invention, in the step of producing the calcined powder, the calcined temperature is calcined at a temperature of 900 ° C. or lower to obtain a piezoelectric oriented ceramic having a high piezoelectric d constant. Can be obtained.
Claims (5)
ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０で、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０であり、結晶相が正方晶またはモルフォトロピック相境界であり、Ｌｏｔｇｅｒｉｎｇ法による配向度が５０％以上であり、且つ、圧電ｄ 33 定数が２３０ｐＣ／Ｎ以上であることを特徴とする、圧電配向セラミックス。 A piezoelectric oriented ceramic whose main component is the composition formula (Pb ((Ti 1−x Zr x ) 1−y ) ((Ma a Mb b ) y ) O 3 ),
Ma is at least one of Ni, Mn, Cr, Mg, Sn, Fe, Co, Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount y of Ma and Mb is 0.06 ≦ y ≦ 0.40, the molar ratio of Ti to Zr (1-x) / x is 1.0 ≦ (1-x) /x≦2.0, and the crystal phase is a tetragonal or morphotropic phase boundary der is, it is the degree of orientation according Lotgering method 50% or more and a piezoelectric constant d 33 is characterized in der Rukoto more 230PC / N, the piezoelectric oriented ceramics.
前記組成物粉末は、ＭａがＮｉ、Ｍｎ、Ｃｒ、Ｍｇ、Ｓｎ、Ｆｅ、Ｃｏ、Ｚｎの少なくとも１種であり、ＭｂがＮｂであり、ａ＋ｂ＝１を満たし、かつＭａとＭｂとの合計量ｙが０．０６≦ｙ≦０．４０であり、かつＴｉとＺｒのモル比率（１−ｘ）／ｘが１．０≦（１−ｘ）／ｘ≦２．０であり、
前記組成式となるように調合された素原料粉末を含む、素原料混合スラリーを作製する工程と、
前記素原料混合スラリーを乾燥したものを９００℃以下の温度で仮焼して仮焼粉末を作製する工程と、
前記仮焼粉末を、アルカリ金属のハロゲン塩をフラックスとするフラックス中で熱処理する工程と、
を含むことを特徴とする、圧電配向セラミックスの製造方法。 And characterized in that the molding composition formula (Pb ((Ti 1-x Zr x) 1-y) ((Ma a Mb b) y) O 3) slurry containing the composition powder based on in a magnetic field A method for producing a piezoelectric oriented ceramic comprising:
In the composition powder, Ma is at least one of Ni, Mn, Cr, Mg, Sn, Fe, Co, and Zn, Mb is Nb, a + b = 1 is satisfied, and the total amount of Ma and Mb y is 0.06 ≦ y ≦ 0.40, and the molar ratio of Ti and Zr (1-x) / x is 1.0 ≦ (1-x) /x≦2.0,
A step of preparing a raw material mixed slurry containing the raw material powder prepared so as to have the composition formula;
A step of calcining the dried raw material mixture slurry at a temperature of 900 ° C. or lower to produce a calcined powder;
Heat-treating the calcined powder in a flux using an alkali metal halogen salt as a flux;
A method for producing a piezoelectric oriented ceramic, comprising:
８００℃以上の温度で仮焼することを特徴とする、請求項３または請求項４に記載の圧電配向セラミックスの製造方法。 In the step of producing the calcined powder,
The method for producing a piezoelectric oriented ceramic according to claim 3 or 4 , wherein calcining is performed at a temperature of 800 ° C or higher .
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