CN102378744B - 陶瓷、压电器件及其制备方法 - Google Patents
陶瓷、压电器件及其制备方法 Download PDFInfo
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- CN102378744B CN102378744B CN201080015258.9A CN201080015258A CN102378744B CN 102378744 B CN102378744 B CN 102378744B CN 201080015258 A CN201080015258 A CN 201080015258A CN 102378744 B CN102378744 B CN 102378744B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 127
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 230000005291 magnetic effect Effects 0.000 claims description 55
- 239000000843 powder Substances 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910002902 BiFeO3 Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 57
- 238000000034 method Methods 0.000 description 21
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 230000010287 polarization Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000005498 polishing Methods 0.000 description 11
- 229910052602 gypsum Inorganic materials 0.000 description 10
- 239000010440 gypsum Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005162 X-ray Laue diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- XYLOFRFPOPXJOQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(piperazine-1-carbonyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(Cn1cc(c(n1)C(=O)N1CCNCC1)-c1cnc(NC2Cc3ccccc3C2)nc1)N1CCc2n[nH]nc2C1 XYLOFRFPOPXJOQ-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical class [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000007775 ferroic material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/24—Complex oxides with formula AMeO3, wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. ortho ferrites
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Abstract
本发明提供压电陶瓷,其含有具有假立方型的{110}面取向的BiFeO3,其适合畴工程,该压电陶瓷包括由下述通式(1)表示的钙钛矿型金属氧化物,并且具有假立方型的{110}面取向:通式(1)xBiFeO3-(1-x)ABO3其中A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;和B表示具有3、4或5价的金属离子,条件是x在0.3≤x≤1的范围内。
Description
技术领域
本发明涉及压电陶瓷、压电器件及其制备方法,更具体地,涉及无铅压电陶瓷和使用其的压电器件以及该压电器件的制备方法。
背景技术
用于压电器件(其用于超声马达、喷墨头等)的许多压电陶瓷,是所谓的PZT的材料,并且是包括铅(Pb)、锆(Zr)和钛(Ti)的氧化物。因此,从环境问题出发,正在进行不含有铅的压电陶瓷(无铅压电陶瓷)的开发。
与PZT相比,无铅压电陶瓷的压电常数低,并且不足。因此,对无铅压电陶瓷进行畴工程(domain engineering),由此改善压电性(S.Wada,Japanese Journal of Applied Physics,第46卷,No.10B,2007,第7039-7043页)。上述的畴工程,需要钙钛矿型压电陶瓷,其具有假立方型(pseudo-cubic form)的{110}面取向。
BiFeO3具有极大量的剩余极化,并且居里点也高。因此,含有BiFeO3的钙钛矿型压电材料是有前途的压电材料。例如,可例示其中将BiFeO3和BaTiO3溶解的薄膜压电材料(日本专利申请公开No.2007-287745)。但是,在含有BiFeO3的钙钛矿型压电材料中,从未提供取向并且适合畴工程的钙钛矿型压电陶瓷。原因在于,如果适当选择薄膜在其上生长的基材,容易在特定方向上获得取向,而在陶瓷的情况下,由于不设置用于支持取向的基材,因此难以获得取向。
因此,作为使陶瓷定向的方法,已知磁场取向(日本专利申请公开No.2008-037064)。日本专利申请公开No.2008-037064公开了如下方法,其包括为了使具有小磁各向异性的钙钛矿型压电材料进行利用磁场的取向,添加具有强磁各向异性的添加剂以施加磁场。但是,对 于利用磁场的取向,如果添加具有强磁各向异性的添加剂,则对电特性产生不利影响,这是不希望的。此外,日本专利申请公开No.2008-037064中记载的钙钛矿型压电材料具有假立方型的{100}面取向,其为不适合畴工程的取向。
鉴于上述情况而完成了本发明,其目的在于提供含有BiFeO3的压电陶瓷,其适合畴工程。
此外,本发明提供使用上述压电陶瓷的压电器件和该压电器件的制备方法。
发明内容
能够实现上述目的的压电陶瓷是由下述通式(1)表示的钙钛矿型金属氧化物制成的陶瓷,并且具有假立方型的{110}面取向:
通式(1)
xBiFeO3-(1-x)ABO3
其中A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;B表示具有3、4或5价的金属离子,条件是x在0.3≤x≤1的范围内。
能够实现上述目的的压电器件包括经设置以夹持该压电陶瓷的电极对。
此外,能够实现上述目的的压电器件的制备方法包括:
得到包括陶瓷粉末的陶瓷浆料(slurry)的浆料步骤,该陶瓷粉末由下述通式(1)表示的钙钛矿型金属氧化物制成;
在磁场中将该陶瓷浆料成形(form)以得到取向的陶瓷压实体(compact body)的取向步骤;
将该陶瓷压实体烧结以得到陶瓷烧结体的烧结步骤;和
形成电极对以夹持该陶瓷烧结体的电极形成步骤,其中该浆料步骤中的陶瓷粉末含有30摩尔%以上的溶解或混合的BiFeO3:
通式(1)
xBiFeO3-(1-x)ABO3
其中A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;和B表示具有3、4或5价的金属离子,条件是x在0.3≤x≤1的范围内。
根据本发明,在具有大厚度的块体陶瓷中可提供块体陶瓷,其含有具有假立方型的{110}面取向的BiFeO3,其适合畴工程陶瓷。
由以下参照附图对示例性实施方案的说明,本发明进一步的特征将变得清楚。
附图说明
图1A和1B是表示取向的烧结体和非取向的烧结体(实施例1和比较例3)的X射线衍射(XRD)的坐标图;
图2是表示根据本发明的实施例2的BiFeO3的陶瓷的取向的烧结体的XRD的坐标图,其在10T的磁场中取向;
图3A和3B是表示取向的烧结体和非取向的烧结体(比较例1和比较例8)的XRD的坐标图;
图4是0.7BiFeO3-0.3BaTiO3的煅烧粉末的SEM照片;
图5是(110)立方取向的压电陶瓷(0.7BiFeO3-0.3BaTiO3)的截面SEM照片;
图6是表示BiFeO3的极化方向和自旋方向的示意图;
图7A和7B是表示利用磁场的取向过程的示意图;和
图8是本发明的压电器件的实例和表示电极表面与本发明的烧结体的磁场方向之间的位置关系的图。
具体实施方式
以下对本发明的实施方案详细说明。
根据本发明的压电陶瓷涉及由下述通式(1)表示的钙钛矿型金属氧化物制成的陶瓷,并且具有假立方型的{110}面取向:
通式(1)
xBiFeO3-(1-x)ABO3
通式(1)中,A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;B表示具有3、4或5价的金属离子。
应指出的是,A或B由多个金属离子构成时,A是具有2的平均价数的金属离子的情况下,B为具有4的平均价数的金属离子;A是具有3的平均价数的金属离子的情况下,B为具有3的平均价数的金属离子;A为具有1的平均价数的金属离子的情况下,B为具有5的平均价数的金属离子。
其中,价数的平均是通过用多个金属离子的价数乘以各个金属离子的组分比例而得到的值。例如,以0.5∶0.5的比例将具有2的价数的金属离子和具有4的价数的金属离子组合在一起的情况下,价数的平均变为3。
作为A的金属离子的具体实例,在一种金属离子的情况下,如果将具有1的价数的金属离子定义为A1,则A1=Li、Na、K、Ag。同样地,如果将具有2的价数的金属离子定义为A2,则A2=Ba、Sr、Ca。同样地,如果将具有3的价数的金属离子定义为A3,则A3=Bi、La、Ce、Nd。在多个金属离子的价数的平均为1的情况下,建立起A1xA11-x(0<x<1)。同样地,在价数的平均为2的情况下,建立起A2xA21-x(0<x<1)和A11/2A31/2。在价数的平均为3的情况下,建立起A3xA31-x(0<x<1)。作为B的金属离子的具体实例,在一种金属离子的情况下,如果将具有3的价数的金属离子定义为B3,则B3=Mn、Sb、Al、Yb、In、Fe、Co、Sc、Y、Sn。同样地,如果将具有4的价数的金属离子定义为B4,则B4=Ti、Zr。同样地,如果将具有5的价数的金属离子定义为B5,则B5=Nb、Sb、Ta。多个金属离子的价数的平均为3的情况下,建立起B3xB31-x(0<x<1)和B21/2B41/2和B22/3B51/3和B23/4B61/4和B11/3B42/3和B11/2B51/2和B13/5B62/5。但是,B1是具有1的价数的金属离子,并且B1=Cu。B2是具有2的价数的金属离子,并且B2=Mg、Ni、Zn、Co、Sn、Fe、Cd、Cu、Cr。B6为具有6的价数的金属离子,并且B6=W、Te、Re。多个金属离子的价数的平均为4的情况下,建立起B4xB41-x(0<x<1)和B31/2B51/2和B32/3B61/3和B21/3B52/3和B21/2B61/2和 B11/4B53/4和B12/5B63/5。多个金属离子的价数的平均为5的情况下,建立起B5xB51-x(0<x<1)和B41/2B61/2和B31/3B62/3和B21/4B63/4和B11/5B64/5。
通式(1)中,ABO3为钙钛矿型陶瓷,并且其实例包括BaTiO3、KNbO3、NaNbO3、LiNbO3、LiTaO3、AgNbO3、BiCrO3、BiMnO3、BiCoO3、BiNiO3、(Bi0.5Na0.5)TiO3、(Bi0.5K0.5)TiO3、Bi(Zn0.5Ti0.5)O3。其中,可溶解两种以上。更优选地,可例示BaTiO3、BiCoO3、(Bi0.5K0.5)TiO3和Bi(Zn0.5Ti0.5)O3,其可与BiFeO3形成变晶相界(MPB)。
符号x在0.3≤x≤1、优选0.5≤x≤0.9的范围内。
根据本发明的压电陶瓷具有假立方型的{110}面取向。
应指出的是,以下,对于晶系假定为假立方的情形的晶体(Miller)指数,添加立方。假立方表示比立方晶系稍微扭曲的晶胞。例如,具有假立方型的{hkl}面取向表示为(hkl)立方取向。
根据本发明的包括xBiFeO3-(1-x)ABO3的压电陶瓷具有如下特征:具有(110)立方取向。其中,具有(110)立方取向意味着采用Lotgering法的假立方型的{110}面的Lotgering因子F为10%-100%,优选为15%-100%,进一步优选为50%-100%。原因在于,如果Lotgering因子F低于10%,与非取向在特性上基本上不存在差异。
Lotgering因子F的计算方法使用由目标晶体表面衍射的X射线的峰强度,并且由下式1计算。
F=(ρ-ρ0)/(1-ρ0)(式1)
其中,ρ0使用非取向样品的X射线衍射强度(I0)计算,并且在(110)立方取向的情况下,ρ0计算为{110}立方面的衍射的合计与总衍射强度的合计之比,由下式2表示。
ρ0=∑I0{110}立方/∑I0{hkl}立方(式2)
符号ρ使用取向样品的X射线衍射强度(I)计算,并且在(110)立方取向的情况下,ρ0计算为{110}立方面的衍射的合计与总衍射强度的合计之比,如上述式2中那样,由下式3表示。
ρ=∑I{110}立方/∑I{hk l}立方(式3)
为了使陶瓷经历畴工程,需要极化方向和取向方向彼此不同。BiFeO3具有菱形晶体的晶系,并且极化方向为<111>立方方向。因此,如果可以得到包括具有(110)立方取向的xBiFeO3-(1-x)ABO3的压电陶瓷,由于极化方向和取向方向彼此不同,由此适合畴工程。
此外,本发明的压电陶瓷的厚度为50μm以上,优选为100μm以上。即,该陶瓷为块体陶瓷。
根据本发明的压电器件具有如下特征:包括上述陶瓷和经设置以夹持该陶瓷的电极对。
优选与假立方型的{110}取向面平行地设置电极。
此外,根据本发明的压电器件的制备方法包括:
得到包括陶瓷粉末的陶瓷浆料的浆料步骤,该陶瓷粉末由上述通式(1)表示的钙钛矿型金属氧化物制成;
在磁场中将该陶瓷浆料成形以得到取向的陶瓷压实体的取向步骤;
将该陶瓷压实体烧结以得到陶瓷烧结体的烧结步骤;和
形成电极对以夹持该陶瓷烧结体的电极形成步骤,其中该浆料步骤中的陶瓷粉末含有30摩尔%以上的溶解或混合的BiFeO3,并且该取向步骤中的磁场方向与该电极形成步骤中的电极的法线方向(normal direction)相同。
以下对根据本发明的压电器件的制备方法进行说明。
首先,在浆料步骤中,得到包括陶瓷粉末的陶瓷浆料,该陶瓷粉末由xBiFeO3-(1-x)ABO3表示的钙钛矿型金属氧化物制成。
浆料步骤是如下步骤,其中,为了使陶瓷粉末进行利用磁场的取向,将陶瓷粉末分散在溶剂中以形成浆料。为了促进利用磁场的取向,陶瓷粉末的平均颗粒直径为50nm-30μm,优选100nm-10μm。利用磁场的取向中,必要的是磁场产生的取向能量大于浆料溶液的Brown运动的热能。磁场产生的取向能量与单位颗粒的质量成比例,并且热能与单位颗粒的表面积成比例。因此,如果陶瓷粉末的颗粒直径小于50nm,与表面积成比例的Brown运动的热能变为主导,因此利用磁场的取向受到抑制,这是不希望的。另一方面,如果颗粒直径变得大于30μm,烧结体的晶粒直径尺寸变大,因此其机械强度降低,这是不希望的。
陶瓷粉末的形状优选为各向同性,例如,优选球状。如果陶瓷粉末具有各向异性,则使压实体的密度降低,由此难以烧结。结果,使烧结体的密度降低,这是不希望的。
优选通过烧结使浆料用分散材料耗散以不使其电特性降低,例如,优选聚碳酸铵盐。
关于浆料用溶剂,优选水或乙醇。
浆料的固体浓度优选为30wt%-90wt%。如果浆料的固体浓度大于90wt%,作为浆料的分散状态并不好,利用磁场的取向受到抑制,这是不希望的。另一方面,如果固体浓度小于30wt%,在成形步骤中不能得到足够的压实体密度,这是不希望的。
向浆料中,除了分散材料以外,还可添加粘结剂以提高压实体的强度。此外,向浆料中,可添加用于促进烧结体的烧结的烧结助剂,例如,可例示CuO等。
接下来,通过取向步骤,在磁场下将陶瓷浆料成形,以由此得到取向的陶瓷压实体。取向步骤是使浆料步骤中的浆料经历磁场以使之成形,以由此得到取向的压实体的步骤。
通常,难以使钙钛矿型压电陶瓷进行利用磁场的取向。原因在于,要进行利用磁场的取向,磁各向异性是必要的,但通常的钙钛矿型压电陶瓷具有极小的磁各向异性。即使可利用磁场使通常的钙钛矿型压电陶瓷取向,也不可能使极化方向和取向方向彼此不同以适合畴工程。这是因为,通常的钙钛矿型压电陶瓷中,极化方向与磁各向异性的方向相同,因此如果利用磁场使通常的钙钛矿型压电陶瓷取向,在极化方向上发生取向。
参照图6和图7A和7B对利用磁场的取向的机理进行说明。
图6是表示BiFeO3的极化方向和自旋方向的示意图。BiFeO3是同时具有铁电性和反铁磁性的多铁性材料。如图6中所示,BiFeO3的极化方向4是<111>立方方向。与其相反,电子自旋的方向是,如由BiFeO3 的Fe原子的自旋方向5所示,[110]立方方向。因此,尽管BiFeO3的极化方向为<111>立方方向,但磁各向异性的方向变为[110]立方方向。结果,磁场的施加产生(110)立方取向。如上所述,在不同于通常的钙钛矿型压电陶瓷的BiFeO3中,极化方向不同于利用磁场的取向的方向。
接下来,对取向步骤进行说明。
图7A和7B是表示将BiFeO3和钙钛矿型压电陶瓷溶解或混合的情形的利用磁场的取向过程的示意图。图7A和7B中,压实粉末6含有其中溶解的BiFeO3和钙钛矿型压电陶瓷,并且附图标记7表示浆料;8表示磁场;和9表示利用磁场取向的浆料。压实体10含有其中使BiFeO3溶解取向的陶瓷粉末,并且附图标记11表示BiFeO3的陶瓷粉末;12表示钙钛矿型压电陶瓷ABO3的陶瓷粉末;和13表示其中使混合的陶瓷粉末取向的压实体。
首先,对将BiFeO3溶解在钙钛矿型压电陶瓷ABO3中的情形的取向步骤进行说明。
本发明的发明人进行了深入研究,结果发现其中含有30摩尔%以上的BiFeO3,钙钛矿型压电陶瓷,难以利用磁场取向,可具有适合畴工程的(110)立方取向。
将这种情况的利用磁场的取向过程的步骤示于7A中。
图7A是对于其中将BiFeO3和钙钛矿型压电陶瓷溶解的陶瓷粉末的利用磁场的取向过程的示意图。图7A中,对BiFeO3和钙钛矿型压电陶瓷ABO3进行煅烧,并且将溶解的陶瓷粉末6形成为浆料7。如果将磁场8施加于浆料7,如附图标记9所示,由于磁各向异性而在浆料中发生取向。保持这种状态以进行成形,由此能够得到取向的压实体10。
现在,对这种情形的取向机理进行说明。与作为典型的钙钛矿型压电陶瓷的BaTiO3相比,BiFeO3的每单位的磁各向异性的量大大约100倍。因此,将BiFeO3溶解于钙钛矿型压电陶瓷的情况下,可使磁各向异性增大,由此使利用磁场的取向发生。但是,如果使BiFeO3的含量减少到小于30摩尔%,则使磁各向异性降低。结果,与由磁场产生的 取向能量相比,Brown运动的热能变为主导,因此使取向显著降低。
接下来,对将BiFeO3与钙钛矿型压电陶瓷ABO3混合的情形的取向步骤进行说明。图7B是表示BiFeO3和钙钛矿型压电陶瓷的陶瓷粉末的情形的利用磁场的取向过程的示意图。
利用磁场的取向过程中,如图7B中所示,将BiFeO311和钙钛矿型压电陶瓷ABO312混合以得到浆料。然后,与将BiFeO3和钙钛矿型压电陶瓷ABO3溶解的情形同样地,使利用磁场的取向发生,以由此得到取向的压实体13。
对这种情况的取向机理进行说明。在1200℃-1500℃的高温下将通常的钙钛矿型陶瓷烧结。与其相反,BiFeO3具有容易烧结性例如在约800℃的低温下烧结。这意味着BiFeO3的晶粒生长速率显著地高于通常的钙钛矿型陶瓷。因此,在将BiFeO3和通常的钙钛矿型陶瓷混合以使利用磁场的取向发生的情况下,如图7B的压实体13中那样,只有BiFeO3进行(110)立方取向。但是,烧结中,具有比通常的钙钛矿型压电陶瓷ABO3显著高的晶粒生长速率的BiFeO3的晶粒生长成为主导,由此可得到具有(110)立方取向的烧结体。但是,如果BiFeO3的含量变得小于30摩尔%,即使BiFeO3的晶粒生长速率较高,占多数的不具有(110)立方取向的钙钛矿型压电陶瓷的影响变得极大,由此使取向的程度降低。
此外,混合时钙钛矿型压电陶瓷粉末的平均颗粒直径优选为BiFeO3的80%以下。原因在于,如果钙钛矿型压电陶瓷粉末的平均颗粒直径大于BiFeO3粉末的80%,可抑制利用磁场的BiFeO3粉末的取向,导致取向程度的降低。
在上述机理下,如果含有30摩尔%以上的BiFeO3,可通过利用磁场的取向过程得到具有(110)立方取向的压电陶瓷。
取向步骤中,作为成形方法,可采用不抑制由磁场产生的陶瓷颗粒的旋转的方法。此外,作为适合的方法,可给出刮刀(doctor blade)法、浇铸(casting)法和电泳。作为用于浇铸的模具,可以使用石膏模具和多孔氧化铝模具。
随着取向步骤中的磁场的强度尽可能强,取向能量变得越高,因此优选0.5T以上。强度更优选为1T以上,进一步更优选为10T-12T。
接下来,进行烧结陶瓷压实体以得到陶瓷烧结体的烧结步骤。
烧结步骤是用于加热取向步骤中得到的压实体以将其烧结的步骤。取决于其组成,可最佳地选择烧结温度,并且其优选的范围为700℃-1500℃。优选地,烧结体的平均晶粒直径为50μm以下。如果平均晶粒直径大于50μm,使烧结体的机械强度降低。烧结体的相对密度为80%以上,优选85%以上,进一步更优选87%以上。原因在于,如果相对密度小于80%,使烧结体的比介电常数显著降低并且也使机械强度降低。
陶瓷烧结体是本发明的压电陶瓷。
接下来,对在夹持由陶瓷烧结体构成的压电陶瓷的同时形成电极对的电极形成步骤进行说明。
电极形成步骤是包括将烧结步骤中得到的烧结体抛光(polishing)和形成电极的步骤。抛光中,可只形成具有取向步骤中磁场的方向作为法线方向的表面。例如,优选通过采用back Laue法找出取向轴来进行抛光。因此,进行抛光并且形成使取向轴找到的表面能够使取向的程度提高。浇铸中,在与石膏模具的接触表面上磁场产生的陶瓷的取向受到抑制,导致低的取向程度。因此,以50μm以上、更优选100μm以上进行抛光。抛光后,通过溅射或者通过银糊的烧结来形成电极。作为电极材料,优选银、金、铂等。在电极和压电陶瓷之间,可设置由Ti、TiO2、Cr等制成的紧密接触层。
此外,优选取向步骤中的磁场的方向与电极形成步骤中的电极的法线方向相同。参照图8,对磁场的方向与电极的法线方向之间的位置关系进行说明。优选如图8中所示那样,在烧结体14的两侧形成的电极15的法线与磁场16的方向相同。
在以下的实施例中,作为实例,将BaTiO3用作钙钛矿型压电陶瓷ABO3。
实施例1
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,其中x=0.7的压电陶瓷的制备如下所述进行。
如下所述得到BiFeO3粉末。对氧化铋和三氧化二铁粉末进行称重以得到相同的摩尔量,然后混合。Bi具有高的蒸汽压,因此担心Bi的不足。结果,优选添加与上述摩尔比相比过量的Bi。接下来,在使用电炉的氧化铝坩埚内在大气环境下在500℃-700℃的温度下对该混合物进行煅烧5小时。然后,在研钵内将煅烧粉末磨碎后,在大气环境下在500℃-700℃的温度下再次进行煅烧5小时。
作为BaTiO3粉末,使用了具有100nm的平均颗粒直径的BT01(由Sakai Chemical制造)。对上述的BiFeO3粉末和BaTiO3粉末进行称重以得到x=0.7的摩尔比。然后,将纯水、分散材料(Dispersant 5020,由Sannopco Co.制造)和Zr珠粒装入罐中,然后混合2小时以上。混合后,进行真空脱气以得到浆料。该浆料具有60wt%的粉末的固体浓度,并且调节分散剂的浓度以致相对于该固体含量,其浓度变为2wt%。
对于取向步骤,使用了超导磁体(JMTD-10T180:由Japan Superconductor Technology制造)。由该超导磁体产生了10T的磁场。通过浇铸来进行该成形。对于浇铸,使用了石膏模具。作为石膏模具,使用了具有50mm×50mm的顶表面和30mm的高度的由石膏制成的长方体,其中在其顶表面垂直地设置直径24mm和深10mm的圆柱状孔。磁场中,将浆料浇铸到石膏模具的圆柱孔中,并且使石膏模具在磁场中静置直至将浆料干燥。使石膏模具静止以使石膏模具的顶表面与重力方向垂直。在与石膏模具的顶表面垂直的方向上施加磁场。如上所述,将浆料干燥以得到盘状压实体。
通过使用电炉在大气环境下在1030℃的温度下进行压实体的烧结5小时,以由此得到压电陶瓷的烧结体,其具有14mmΦ和1mm的厚度。其中,采用Archimedian法对得到的烧结体的密度进行评价。进而,优选地,例如,通过使用back Laue法确定{110}立方面,将得到的烧结体抛光。然后,在抛光的(110)立方取向的烧结体的抛光面上形 成电极时,使在压电材料的(110)立方取向方向上施加的电场矢量的分量增加,由此能够得到更令人满意的压电特性。如上所述抛光后,通过XRD进行烧结体的结构分析,并且计算{110}立方面的Lotgering因子F。
实施例2-5
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,在表1中所示的烧结温度下如实施例1中那样进行烧结体的制备。
比较例1和2
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,根据表1中所示的制备条件,如实施例1中那样得到烧结体。
比较例3-9
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,如实施例1中那样但无取向处理,根据表1中所示的制备条件得到烧结体。
实施例6
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,通过如下所述对BiFeO3和BaTiO3进行煅烧,然后溶解,然后进行取向步骤,从而进行其中x=0.7的压电陶瓷的制备。
对氧化铋和氧化铁粉末和BaTiO3进行称量以得到摩尔比x=0.7,然后混合。Bi具有高蒸汽压,因此担心Bi的不足。因此,优选添加与上述摩尔比相比过量的Bi。作为BaTiO3,使用由Sakai Chemical制造的BT01(平均颗粒直径100nm)。然后,如实施例1中那样,进行煅烧以得到煅烧粉末。图4表示该煅烧粉末的SEM照片。可以看到煅烧粉末的颗粒直径分布在300nm-6μm的范围内,并且均具有各向同性形状。如实施例1中那样将煅烧粉末分散于纯水中以得到浆料。使用该浆料并且如实施例1中那样进行取向步骤、烧结和抛光。以与实施例1中相同的方式确定{110}立方面的Lotgering因子F和密度。
实施例7-9
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,以与实施例6中相同的方式在表3中所示的烧结温度下进行烧结体的制备。
比较例10和11
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,根据表3中所示的制备条件,如实施例6中那样得到烧结体。
比较例12-17
在xBiFeO3-(1-x)BaTiO3(0≤x≤1)中,如实施例6中那样但无取向步骤,根据表3中所示的制备条件得到烧结体。
将实施例1中的取向的烧结体和比较例3中的非取向的烧结体的XRD结果示于图1A和1B中。图1A是实施例1的XRD,和图1B是比较例3的XRD。由这些XRD结果,确定实施例1中{110}立方面的Lotgering因子F。将Lotgering因子F和相对密度示于表2中。
将取向的烧结体的截面SEM照片示于图5中。观察到取向的烧结体的平均晶粒直径为6μm。
由实施例2-5中的XRD的结果并且由比较例4-7中的XRD的各结果确定实施例2-5中的{110}立方面的Lotgering因子F。将{110}立方面的这些Lotgering因子F和相对密度以及电场施加(40kV/cm)时的畸变示于表2中。
由比较例1和2中的XRD的结果并且由比较例8和9中的XRD的各结果确定比较例1和2中的{110}立方面的Lotgering因子F。将{110}立方面的这些Lotgering因子F和相对密度示于表2中。
图2表示实施例2中的XRD结果。从图2中发现,不仅包括(110)立方取向,而且包括(211)立方取向。
将比较例1和比较例8的XRD结果示于图3A和3B中。图3A是比较例1的XRD。图3B是比较例8的XRD。
在实施例1-5中的{110}面上,设置均具有100nm的厚度的金电极,以由此得到本发明的压电器件。极化后,将40kV/cm的电场施加于这些压电器件时评价畸变。将畸变的结果示于表2中。
比较例1-9中,设置100nm厚的金电极,由此得到压电器件。极化后,通过激光Doppler法在室温(25℃)下测定向这些压电器件施加40kV/cm电场时的畸变。将畸变的测定结果示于表2中。
以与实施例1中相同的方式得到根据实施例6-9的{110}立方面的Lotgering因子F、相对密度和畸变。将结果示于表4中。
以与比较例1中相同的方式得到根据比较例10-17的{110}立方面的Lotgering因子F、相对密度和畸变。将结果示于表4中。
表1
X | 烧结温度(℃) | 取向处理 | |
实施例1 | 0.7 | 1030 | 有 |
实施例2 | 1 | 800 | 有 |
实施例3 | 0.3 | 1140 | 有 |
实施例4 | 0.9 | 970 | 有 |
实施例5 | 0.5 | 1085 | 有 |
比较例1 | 0.2 | 1170 | 有 |
比较例2 | 0.1 | 1200 | 有 |
比较例3 | 0.7 | 1030 | 无 |
比较例4 | 1 | 800 | 无 |
比较例5 | 0.3 | 1140 | 无 |
比较例6 | 0.9 | 970 | 无 |
比较例7 | 0.5 | 1085 | 无 |
比较例8 | 0.2 | 1170 | 无 |
比较例9 | 0.1 | 1200 | 无 |
表2
X | F[%] | 相对密度[%] | 畸变[%] | |
实施例1 | 0.7 | 74 | 94 | 0.037 |
实施例2 | 1 | 73 | 85 | 0.022 |
实施例3 | 0.3 | 17 | 97 | 0.033 |
实施例4 | 0.9 | 67 | 87 | 0.037 |
实施例5 | 0.5 | 53 | 90 | 0.036 |
比较例1 | 0.2 | -16 | 97 | 0.013 |
比较例2 | 0.1 | 0.4 | 95 | 0.011 |
比较例3 | 0.7 | 无取向 | 93 | 0.026 |
比较例4 | 1 | 无取向 | 86 | 0.018 |
比较例5 | 0.3 | 无取向 | 95 | 0.026 |
比较例6 | 0.9 | 无取向 | 85 | 0.025 |
比较例7 | 0.5 | 无取向 | 91 | 0.026 |
比较例8 | 0.2 | 无取向 | 92 | 0.014 |
比较例9 | 0.1 | 无取向 | 90 | 0.010 |
表3
X | 烧结温度(℃) | 取向处理 | |
实施例6 | 0.7 | 1030 | 有 |
实施例7 | 0.3 | 1140 | 有 |
实施例8 | 0.9 | 970 | 有 |
实施例9 | 0.5 | 1085 | 有 |
比较例10 | 0.2 | 1170 | 有 |
比较例11 | 0.1 | 1200 | 有 |
比较例12 | 0.7 | 1030 | 无 |
比较例13 | 0.3 | 1140 | 无 |
比较例14 | 0.9 | 970 | 无 |
比较例15 | 0.5 | 1085 | 无 |
比较例16 | 0.2 | 1170 | 无 |
比较例17 | 0.1 | 1200 | 无 |
表4
X | F[%] | 相对密度[%] | 畸变[%] | |
实施例6 | 0.7 | 96 | 95 | 0.041 |
实施例7 | 0.3 | 34 | 98 | 0.034 |
实施例8 | 0.9 | 76 | 89 | 0.039 |
实施例9 | 0.5 | 69 | 92 | 0.037 |
比较例10 | 0.2 | -14 | 96 | 0.011 |
比较例11 | 0.1 | 0.3 | 96 | 0.011 |
比较例12 | 0.7 | 无取向 | 92 | 0.025 |
比较例13 | 0.3 | 无取向 | 96 | 0.027 |
比较例14 | 0.9 | 无取向 | 80 | 0.025 |
比较例15 | 0.5 | 无取向 | 91 | 0.025 |
比较例16 | 0.2 | 无取向 | 91 | 0.013 |
比较例17 | 0.1 | 无取向 | 90 | 0.010 |
如上所述,由表2观察到,{110}立方面的Lotgering因子F在0.3≤x≤1的范围内,并且实施例1-5中{110}立方面的Lotgering因子F超过10%,并且相对密度超过85%。由上述结果可以观察到,x的优选范围在0.3≤x≤1的范围内。
由表2可知,通过分别将实施例1-5与比较例3-7进行比较,观察到20%以上的畸变的增加。特别地,x=0.5-0.9时畸变的增加率为30%以上。因此,可以看到这样的效果:通过(110)立方取向使根据本发明的压电陶瓷的压电性质改善。比较例中得到的烧结体是不具有特定取向的多晶材料。
由表4可以看到,即使对BiFeO3和BaTiO3进行煅烧后进行取向步骤的情况下,如实施例1-5中那样,实施例6-9中{110}立方面的Lotgering因子F在0.3≤x≤1的范围内超过10%,并且相对密度超过85%。由上述的结果可以看到,x的优选范围在0.3≤x≤1的范围内。
由表4可知,通过分别将实施例6-9与比较例12-15进行比较,观察到20%以上的畸变的增加。特别地,x=0.5-0.9时畸变的增加率为30%以上。因此,可以看到存在如下效果:通过(110)立方取向使根据本发明的压电陶瓷的压电性改善。用于比较的烧结体是不具有特定取向的多晶材料。
由表2和表4,可以说更优选在对BiFeO3和BaTiO3进行煅烧后进 行取向过程,原因在于可获得较高的Lotgering因子F、较高的相对密度和较高的畸变。
在x=0.5以上的组成中,甚至在将磁场从10T降低到1T的情况下,也能够获得类似的(110)立方取向的压电陶瓷和压电器件。
实施例10
在xBiFeO3-(1-x)AgNbO3(0≤x≤1)中,如下进行其中x=0.8的压电陶瓷的制备。
以与实施例1中相同的方式,得到了BiFeO3的烧结粉末。
如下得到了AgNbO3的煅烧粉末。对氧化银(I)和五氧化铌进行称重以使银和铌变为相同的摩尔量,然后混合。接下来,在使用电炉的氧化铝坩埚内在大气环境下在900℃-1000℃的温度下对该混合物进行煅烧4小时。然后,在研钵内将煅烧粉末磨碎后,使用电炉在大气环境下在900℃-1000℃的温度下再次进行煅烧7小时。对上述的BiFeO3煅烧粉末和AgNbO3煅烧粉末进行称重以获得x=0.8的摩尔比,并且如实施例1中那样得到浆料。如实施例1中那样对该浆料进行取向步骤以得到压实体。如实施例1中那样将得到的压实体烧结,由此得到烧结体。烧结温度为1000℃。以与实施例1中相同的方式采用XRD进行烧结体的结构分析,并且观察到(110)立方取向。{110}立方面的Lotgering因子F为66%。
实施例11
xBiFeO3-(1-x)BiCoO3(0≤x≤1)中,如下进行其中x=0.9的压电陶瓷的制备。
对氧化铋、氧化铁粉末和四氧化三钴进行称重以得到x=0.9的摩尔比,并且混合。Bi具有高蒸汽压,因此担心Bi的不足。结果,优选添加与上述摩尔比相比过量的Bi。然后,如实施例1中那样进行煅烧,以由此得到煅烧粉末。烧结温度为600℃-800℃。如实施例1中那样将煅烧粉末分散在纯水中,以由此得到浆料。如实施例1中那样使用该浆料进行取向步骤,并且烧结。烧结温度为850℃。以与实施例1中相同的方式采用XRD进行烧结体的结构分析,并且观察到(110) 立方取向。{110}立方面的Lotgering因子F为71%。
由实施例11和12,作为通式(1)所示的钙钛矿型压电陶瓷ABO3,甚至在使用BaTiO3以外的上述材料的情况下,同样地,也能够制备(110)立方压电陶瓷。
作为通式(1)所示的钙钛矿型压电陶瓷ABO3,甚至在使用BaTiO3以外的上述材料的情况下,同样地,也能够制备(110)立方取向的压电陶瓷。
由于本发明的压电陶瓷含有具有假立方型的{110}面取向的BiFeO3,其适合畴工程,因此该压电陶瓷可应用于压电器件和压电传感器。
尽管已参照示例性实施方案对本发明进行了说明,但应理解本发明并不限于所公开的示例性实施方案。下述权利要求的范围应给予最宽泛的解释以包括所有这样的变形以及等同的结构和功能。
本申请要求于2009年3月31日提交的日本专利申请No.2009-087240的权益,由此将其全文并入本文作为参考。
Claims (5)
1.具有假立方型的{110}面取向的块体陶瓷,其包括由下述通式(1)表示的钙钛矿型金属氧化物:
通式(1)
xBiFeO3-(1-x)ABO3
其中A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;和B表示具有3、4或5价的金属离子,条件是x在0.3≤x≤1的范围内,
其中该陶瓷的{110}取向部具有50μm以上的厚度,
其中该陶瓷是在磁场中通过取向步骤而制备的。
2.根据权利要求1的块体陶瓷,其中假立方型的{110}面的Lotgering因子F为10%-100%。
3.压电器件,其包括根据权利要求1的块体陶瓷和经设置以夹持该陶瓷的电极对。
4.根据权利要求3的压电器件,其中与假立方型的{110}取向面平行地设置该电极。
5.压电器件的制备方法,包括:
得到包括陶瓷粉末的陶瓷浆料的浆料步骤,该陶瓷粉末包括由下述通式(1)表示的钙钛矿型金属氧化物;
在磁场中将该陶瓷浆料成形以得到取向的陶瓷压实体的取向步骤;
将该陶瓷压实体烧结以得到陶瓷烧结体的烧结步骤;和
形成电极对以夹持该陶瓷烧结体的电极形成步骤,
其中浆料步骤中的陶瓷粉末含有30摩尔%以上的BiFeO3:
通式(1)
xBiFeO3-(1-x)ABO3
其中A和B均表示一种或多种金属离子;A表示具有1、2或3价的金属离子;和B表示具有3、4或5价的金属离子,条件是x在0.3≤x≤1的范围内。
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