CN110462858A - 压电组合物及压电元件 - Google Patents
压电组合物及压电元件 Download PDFInfo
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- CN110462858A CN110462858A CN201880022736.5A CN201880022736A CN110462858A CN 110462858 A CN110462858 A CN 110462858A CN 201880022736 A CN201880022736 A CN 201880022736A CN 110462858 A CN110462858 A CN 110462858A
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- 239000000203 mixture Substances 0.000 title claims abstract description 123
- 239000010955 niobium Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229910003334 KNbO3 Inorganic materials 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 description 30
- 239000000843 powder Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 16
- 230000010287 polarization Effects 0.000 description 16
- 239000002994 raw material Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000005684 electric field Effects 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
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 2
- 229910017541 Cu-K Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000004523 agglutinating effect Effects 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 bicarbonate compound Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- NVDNLVYQHRUYJA-UHFFFAOYSA-N hafnium(iv) carbide Chemical compound [Hf+]#[C-] NVDNLVYQHRUYJA-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种具有良好的电阻率的压电组合物和具备该压电组合物的压电元件,该压电组合物包含含有钾及铌的复合氧化物,复合氧化物具有:以组成式KNbO3表示的第一相;选自以组成式K4Nb6O17表示的第二相以及以组成式KNb3O8表示的第三相的一个相或两个相。
Description
技术领域
本发明涉及压电组合物、及具有该压电组合物的压电元件。
背景技术
压电组合物基于结晶内的电荷的偏移所引起的自发极化,具有通过从外部接受应力而在表面产生电荷的效果(压电效应)和通过从外部施加电场而产生形变的效果(逆压电效应)。
应用了这种能够将机械性的位移与电位移相互转换的压电组合物的压电元件在各种领域中广泛使用。例如,作为利用逆压电效应的压电元件的致动器与施加电压成比例,高精度地得到微少的位移,且响应速度快,因此,用于光学系部件的驱动用、HDD的磁头驱动用、喷墨打印机的喷头驱动用、燃料喷射阀驱动用等。
另外,也被用作利用压电效应读取微少的力或变形量的传感器。另外,压电组合物具有优异的响应性,因此,也可通过施加交流电场,激励压电组合物本身或与压电组合物处于接合关系的弹性体并引起共振,也用作压电变压器、超声波马达等。
一般而言,压电组合物由多晶体构成,通过对烧成后的铁电体组合物实施极化处理而得到。烧成后的铁电体组合物中,各结晶中的自发极化的方向是随机的,作为铁电体组合物整体,不会产生电荷的偏移,不会呈现压电效应及逆压电效应。因此,进行通过对烧成后的铁电体组合物施加矫顽电场以上的直流电场,使自发极化的方向与一定方向一致的被称为极化处理的操作。极化处理后的铁电体组合物能够体现作为压电组合物的性质。
作为压电组合物,大多使用由锆酸铅(PbZrO3)和钛酸铅(PbTiO3)构成的铅系压电组合物。但是,铅系压电组合物含有60~70重量%程度的熔点低的氧化铅(PbO),在烧成时,氧化铅容易挥发。因此,从环境负荷的观点来看,得到无铅的压电组合物成为极其重要的技术问题。
作为无铅的环保型的压电组合物,对铌酸钾系的化合物进行着研究。已知该铌酸钾系的化合物在无铅的压电组合物中,也具有较高的居里温度,并呈现较大的压电效应及逆压电效应。例如,非专利文献1中公开有以组成式KNbO3表示的压电组合物。
现有技术文献
非专利文献
非专利文献1:S.Sato,et al,“Excess Potassium and Microstructure Controlfor Producing Dense KNbO3Ceramics”,Transactions of the Materials ReseachSociety of Japan,37[1]65-68(2012)。
发明内容
发明想要解决的技术问题
非专利文献1中记载了使用化学计量比的原料制作的KNbO3的烧结体中,存在烧成时的钾的挥发所引起的空隙且密度降低。因此,非专利文献1中,通过设为钾比化学计量比过量地含有的组成来提高密度。
但是,非专利文献1公开的方法中,虽然密度提高,但难以控制钾的挥发量,难以做成目标的组成。另外,通过设为过量地含有钾的组成,会存在如下问题,即,在烧结后的KNbO3中残留钾化合物,且呈现潮解性。
另一方面,当在晶粒间存在空隙时,存在如下问题,即,压电组合物的电阻率降低,不能充分进行极化处理,不能最大限地发挥压电组合物所具有的压电特性。
本发明是鉴于这种实际状况而完成的,其目的在于,提供一种具有良好的电阻率的压电组合物和具备该压电组合物的压电元件。
解决技术问题的手段
为了达成上述目的,本发明提供的压电组合物如下:
[1]该压电组合物是一种包含含有钾及铌的复合氧化物,其特征在于,该复合氧化物具有:
以组成式KNbO3表示的第一相;以及
选自以组成式K4Nb6O17表示的第二相及以组成式KNb3O8表示的第三相中的一个相或两个相。
[2]根据[1]所记载的压电组合物,其特征在于,
将第二相的体积相对于第一相的体积的比率及第三相的体积相对于第一相的体积的比率分别设为x%及y%时,
x及y满足0<x+y<10.0%的关系。
[3]根据[2]所记载的压电组合物,其特征在于,
x及y满足x>y的关系。
[4]根据[1]~[3]中任一项所记载的压电组合物,其特征在于,
压电组合物含有选自过渡金属元素中的一种以上。
[5]一种压电元件,其包含[1]~[4]中任一项所记载的压电组合物。
发明效果
通过本发明的压电组合物具有上述特征,能够提供具有良好的电阻率的压电组合物和具备该压电组合物的压电元件。
附图说明
图1是本实施方式的压电元件的一例的示意性的立体图;
图2是本实施方式的压电元件的其它例子的示意性的截面图;
图3(a)是本发明的实施例的试样的X射线衍射图,图3(b)是本发明的比较例的试样的X射线衍射图。
符号说明
5……压电元件;1……压电体部;2、3……电极;
50……压电元件;10……层叠体;11……压电层;12……内部电极层;
21、22……端子电极。
具体实施方式
以下,基于具体的实施方式,按照以下的顺序详细地说明本发明。
1.压电元件
1.1压电组合物
2.压电元件的制造方法
3.本实施方式的效果
4.变形例
(1.压电元件)
首先,对应用了本实施方式的压电组合物的压电元件进行说明。作为压电元件,只要是可应用本实施方式的压电组合物的元件则没有特别限制。本实施方式中,例如示例了压电变压器、薄膜传感器、压电超声波马达等。
图1所示的压电元件5具备板状的压电体部1、和形成于作为压电体部1的两个主面的一对相对面1a、1b的一对电极2、3。压电体部1由本实施方式的压电组合物构成,压电组合物的详情进行后述。另外,电极2、3中含有的导电材料没有特别限定,可以根据期望的特性、用途等任意地设定。本实施方式中,可例举金(Au)、银(Ag)及钯(Pd)等。
图1中,压电体部1具有长方体形状,但压电体部1的形状没有特别的限制,可根据期望的特性、用途等任意地设定。另外,压电体部1的尺寸也没有特别限制,可根据期望的特性、用途等任意地设定。
压电体部1按照规定的方向极化。例如,图1所示的压电元件5中,沿着压电体部1的厚度方向即电极2、3相对的方向极化。在电极2、3中,例如经由未图示的电线等电连接有未图示的外部电源,经由电极2、3对压电体部1施加规定的电压。当施加电压时,在压电体部1中,通过逆压电效应,电位移转换成机械性的位移,压电体部1能够在横方向上进行横向振动。
(1.2压电组合物)
本实施方式的压电组合物含有以含有钾(K)及铌(Nb)的复合氧化物作为主成分。本实施方式中,主成分是相对于压电组合物100mol%占据90mol%以上的成分。
上述的复合氧化物具有以组成式KNbO3表示的第一相。KNbO3是具有钙钛矿结构的复合氧化物。钙钛矿结构以通式ABO3表示,由B位元素和氧构成的BO6氧八面体构成共享彼此的顶点的三维网络,通过向该网络的空隙充填A位点元素而形成。本实施方式中,A位点元素为K,B位点元素为Nb。
已知KNbO3在成型体的烧成时,作为碱金属的K容易挥发。当K挥发时,从称重时的组成来看,K变少,结果,Nb量相对于K量过量,表示A位点元素与B位点元素的摩尔比的A/B比变化,组成的平衡破坏。
在该情况下,为了维持KNbO3的组成的平衡,有时从Nb从KNbO3的组成成为过量的状态,形成Nb比KNbO3中的K与Nb的比(K:Nb=1:1)过量存在的相。
本实施方式中,上述的复合氧化物除了上述的第一相以外,还具有Nb比第一相中的K与Nb的比过量地含有的相。具体而言,上述的复合氧化物具有以组成式K4Nb6O17表示的第二相和/或以组成式KNb3O8表示的第三相。即,上述的复合氧化物也可以除了具有第一相之外,还具有第二相及第三相,也可以具有第二相及第三相中的任一方。
本实施方式中,在KNbO3中,利用由于K的挥发而变得过量的Nb形成与第一相(KNbO3)不同的相,来弥补随着K的挥发而产生的压电组合物内的空隙。即,压电组合物中存在包含上述第一相的两个相或3个相,由此,在构成第一相(KNbO3)的晶粒间存在构成第二相(K4Nb6O17)的晶粒和/或构成第三相(KNb3O8)的晶粒。其结果,容易形成于构成第一相的晶粒间的空隙被构成第二相的晶粒和/或构成第三相的晶粒充填,压电组合物的电阻率提高。
另外,优选将第二相相对于第一相的比率及第三相相对于第一相的比率设为特定的范围内。本实施方式中,将第一相的体积设为100%,且将第二相的体积设为x%,将第三相的体积设为y%时,优选“x”及“y”满足0<x+y<10.0的关系,更优选满足0.1≤x+y≤6.0的关系,进一步优选满足0.2≤x+y≤4.0的关系。
另外,优选“x”及“y”满足x>y的关系。即,优选第二相(K4Nb6O17)比第三相(KNb3O8)更多地存在。特别优选第二相以规定的比例存在,且第三相几乎不存在。即,特别优选满足0<x<10.0的关系。
通过相对于第一相的体积,将第二相的体积比率及第三相的体积比率设为上述的范围内,从而能够有效地弥补构成第一相的晶粒间的空隙,并进一步提高上述的效果。
本实施方式中,上述的第一相的体积、第二相的体积及第三相的体积根据通过压电组合物的XRD(X-ray Diffraction)测定而得到的第一相、第二相及第三相的峰值强度算出。具体而言,通过XRD测定得到的X射线衍射图中,同定第一相(KNbO3)呈现的最大峰值、第二相(K4Nb6O17)呈现的最大峰值、第三相(KNb3O8)呈现的最大峰值,并算出第一相的峰值强度I1、第二相的峰值强度I2及第三相的峰值强度I3。然后,“x”根据x=100×I2/I1算出,“y”根据y=100×I3/I1算出。在使用Cu-Kα射线作为X射线源的情况下,第一相的最大峰值出现于2θ=31~33°附近,第二相的最大峰值出现于2θ=9~11°或11~13°附近,第三相的最大峰值出现于2θ=25~27°附近。
另外,本实施方式的压电组合物优选含有选自除上述的Nb之外的过渡金属元素(长周期型周期表中的3族~11族的元素)的1个以上。具体而言,作为除稀土元素之外的过渡金属元素,可示例:铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、钨(W)、钼(Mo)等。作为稀土元素,可示例:钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)等。
本实施方式中,作为过渡金属元素,优选为铜(Cu)及锰(Mn)。通过含有过渡金属元素,能够提高压电组合物的烧结性。其结果,压电组合物的电阻率提高。
相对于上述的复合氧化物1摩尔(100摩尔%)的以元素换算计的过渡金属元素的含量优选为0.1摩尔%以上且3.0摩尔%以下,更优选为0.1摩尔%以上且1.0摩尔%以下。
如果过渡金属元素在上述的范围内含有,则其存在形式没有特别限制,过渡金属元素也可以固溶于构成第一相的晶粒的晶粒内,也可以存在于晶界。在存在于晶界的情况下,也可以与其它元素形成化合物,也可以固溶于构成第二相和/或第三相的晶粒内。但是,不优选作为与第一相~第三相不同的相存在。后述的压电组合物的制造工序中,通过控制添加过渡金属元素的原料的时机,能够使含有过渡金属元素的相不作为与第一相~第三相不同的相析出。
此外,本实施方式的压电组合物也可以含有作为杂质的铅(Pb),但其含量优选为1重量%以下,更优选为完全不含有Pb。这是由于,从低公害化、对环境性及生态学的观点来看,能够将烧成时的Pb的挥发,或搭载含有本实施方式的压电组合物的压电元件的电子设备在市场中流通废弃之后对环境中的Pb的释放抑制到最小限。
从压电特性的发挥、机械强度的观点来看,构成本实施方式的压电组合物的晶粒的平均结晶粒径只要进行控制即可,本实施方式中,平均结晶粒径优选为例如0.5μm~20μm。
(2.压电元件的制造方法)
接着,以下说明压电元件的制造方法的一例。
首先,准备压电组合物的初始原料。作为复合氧化物的初始原料,能够使用含有K的化合物。作为含有K的化合物,例如可示例碳酸盐、碳酸氢化合物等。作为含有Nb的化合物,例如可示例氧化物等。
本实施方式中,称量准备的复合氧化物的初始原料时,优选将ABO3中的A/B比,即K相对于Nb的摩尔比设为超过1.00且低于1.20。通过这样,处于容易形成第二相和/或第三相的倾向。
作为计算A/B比的方法,只要是公知的方法则没有特别限制,例如,也可以根据使用的原料粉的标准值和称重量计算,也可以通过XRF(X-ray Fluorescence)测定称量的原料粉的组成来计算。
在压电组合物含有过渡金属元素的情况下,准备过渡金属元素的初始原料。作为过渡金属元素的初始原料,也可以是过渡金属元素单体,也可以是含有过渡金属元素的化合物。本实施方式中,优选为含有过渡金属元素的氧化物。
将准备的复合氧化物的初始原料按照规定的比例称量后,使用球磨机等进行5~20小时混合。作为混合的方法,可以是湿式混合,也可以是干式混合。在湿式混合的情况下,干燥混合粉。接下来,将对混合粉或将混合粉成型而得到的成型体在大气中以750~1050℃、1~20小时的条件进行热处理(煅烧),得到复合氧化物的煅烧粉末。
本实施方式中,为了调整A/B比,优选相对于得到的煅烧粉末,进一步添加含有Nb的化合物。优选将添加了含有Nb的化合物之后的A/B比设为超过0.90且低于1.00。通过这样,Nb量相对于K量成为过量,处于容易形成第二相和/或第三相的倾向。
作为计算A/B比的方法,只要是公知的方法则没有特别限制,也可以通过XRF等测定煅烧粉末的组成,算出A/B比之后,以成为期望的A/B比的方式添加含有Nb的化合物,也可以通过XRF等测定添加了含有Nb的化合物的煅烧粉末的组成来计算。
在得到的煅烧粉末凝聚的情况下,优选使用球磨机等以规定时间进行煅烧粉末的粉碎,并做成粉碎粉。向调整了A/B比的煅烧粉末或粉碎粉中,根据需要添加按照规定的比例称量的过渡金属元素的初始原料,使用球磨机等进行5~20小时的混合,得到压电组合物的原料粉。作为混合的方法,可以是湿式混合,也可以是干式混合。在湿式混合的情况下,干燥混合粉,从而得到压电组合物的原料粉。
将压电组合物的原料粉成型的方法没有特别限制,根据期望的形状、尺寸等适当选择即可。在进行压制成型的情况下,向压电组合物的原料粉中添加规定的粘合剂和根据需要的添加物,成型为规定的形状而得到成型体。另外,也可以使用向压电组合物的原料粉中添加规定的粘合剂等进行造粒而得到的造粒粉来得到成型体。也可以根据需要,相对于得到的成型体,通过CIP等进一步进行加压处理。
对得到的成型体实施脱粘合剂处理。作为脱粘合剂条件,优选将保持温度设为400℃~800℃,将温度保持时间优选设为2小时~4小时。
接下来,将脱粘合剂处理后的成型体进行热处理(烧成)。作为烧成条件,优选将保持温度设为950℃~1060℃,优选将温度保持时间设为2小时~4小时,优选将升温及降温速度设为50℃/小时~300℃/小时程度,优选将气氛设为含氧气氛。
将得到的作为烧结体的压电组合物根据需要进行研磨,涂布电极膏进行烧结,形成电极。形成电极的方法没有特别限制,也可以通过蒸镀、溅射等形成电极。
将形成电极的烧结体在规定的温度的油中施加2kV/mm~5kV/mm的电场5分钟~1小时程度,进行极化处理。在进行了极化处理之后,得到自发极化与规定的方向一致的压电组合物。
将极化处理后的压电组合物根据需要加工成规定的大小,形成板状的压电体部1。接着,通过蒸镀等在该压电体部1上形成电极2、3,由此得到图1所示的压电元件。
(3.本实施方式的效果)
本实施方式的压电组合物含有包含钾(K)及铌(Nb)的复合氧化物作为主成分。该复合氧化物主要由具有钙钛矿结构的KNbO3相(第一相)构成,但本实施方式中,具有与第一相不同的相即第二相和/或第三相。
由于烧成时的K的挥发,这种第二相及第三相被形成为Nb量相对于K量比第一相过量的相。第二相由K4Nb6O17构成,第三相由KNb3O8构成。
第二相和/或第三相以填补由K的挥发所引起的压电组合物内的空隙的方式而存在。其结果,能够利用第二复合氧化物和/或第三复合氧化物填充压电组合物内的空隙,并提高压电组合物的电阻率。
对于烧成后的压电组合物,通过极化处理施加非常高的直流电压。因此,当压电组合物的电阻率较低时,漏电流增加,极化处理不充分,能够最大限地发挥该压电组合物所具有的压电特性。
本实施方式的压电组合物的电阻率充分高,因此,即使相对于极化处理时的较高的电压的施加,漏电也少,能够进行充分的极化处理。即,能够最大限地发挥压电组合物所具有的压电特性。
这种效果通过将压电组合物中的第二相的体积相对于第一相的体积的比率及第三相相对于第一相的体积比率的和设为规定的范围内,从而能够进一步提高。
另外,通过使压电组合物中含有过渡金属元素,从而压电组合物的烧结性提高,因此,能够进一步提高电阻率。
(4.变形例)
上述的实施方式中,对压电体部为单层的压电元件进行了说明,但也可以是具有重叠了压电体部的结构的压电元件。另外,也可以是具有将这些组合了的结构的压电元件。
作为具有层叠了压电体部的结构的压电元件,例如可示例图2所示的压电元件50。该压电元件50具备将由本实施方式的压电组合物构成的多个压电层11和多个内部电极12交替层叠的层叠体10。在该层叠体10的两端部形成有与在层叠体10的内部交替配置的内部电极层12分别导通的一对端子电极21、22。
压电层11的每一层的厚度(层间厚度)没有特别限定,可根据期望的特性及用途等任意地设定。通常,层间厚度优选为1μm~100μm程度。压电层11的层叠数没有特别限定,可根据期望的特性或用途等任意地设定。
作为制造图2所示的压电元件50的方法,只要使用公知的方法即可,例如,制作成为图2所示的层叠体10的生坯芯片,将其烧成得到层叠体10之后,将端子电极印刷或转印于层叠体10并进行烧成,由此进行制造。作为制造生坯芯片的方法,例如可示例使用了膏体的通常的印刷法、片材法等。印刷法及片材法中,使用混合上述的压电组合物的原料粉和将粘合剂溶解于溶剂中得到的媒介并涂料化的膏体,形成生坯芯片。
以上,对本发明的实施方式进行了说明,但本发明丝毫不限定于上述的实施方式,也可以在本发明的范围内以各种方式进行改变。
实施例
以下,使用实施例及比较例,更详细地说明本发明。但是,本发明不限定于以下的实施例。
首先,作为压电组合物的主成分即复合氧化物的初始原料,准备了碳酸氢钾(KHCO3)和氧化铌(Nb2O5)的粉末。另外,作为压电组合物中包含的作为含有成分的过渡金属元素的初始原料,准备了氧化铜(CuO)及氧化锰(MnO2)的粉末。
将准备的复合氧化物的初始原料以A/B比成为表1的A/B(1)一栏所示的值的方式进行称量,称量了过渡金属元素的初始原料。对于实施例1~17及比较例1、2、及4,将称量的KHCO3及Nb2O5的各粉末利用球磨机混合16小时后,以120℃进行干燥,得到了混合粉。另外,对于比较例3,将称量的KHCO3、Nb2O5及CuO的各粉末利用球磨机混合16小时后,以120℃进行干燥,得到了混合粉。
将得到的混合粉进行压制成型,以1000℃煅烧4小时,得到了复合氧化物的煅烧粉末。接着,向该煅烧粉末中,以A/B比成为表1的A/B(2)一栏所示的值的方式添加Nb2O5,利用球磨机粉碎16小时,得到了粉碎粉。
对于实施例1~11及比较例1~3,将得到的粉碎粉做成压电组合物的原料粉。另外,对于实施例12~17及比较例4,相对于得到的粉碎粉,添加称量的CuO及MnO2的各粉末,并利用球磨机混合3小时后,在100℃下干燥,得到了压电组合物的原料粉。
向得到的压电组合物的原料粉中添加作为粘合剂的PVA,通过公知的方法进行造粒。接下来,将得到的造粒粉利用压制成型机施加5.0MPa的负载进行压制成型,得到了平板状的成型体。
对这样得到的平板状的成型体以550℃、3小时的条件实施脱粘合剂处理。将脱粘合剂处理后的成型体在大气气氛下以1050℃、3小时的条件进行烧成,得到了压电组合物(烧结体)。
对得到的烧结体进行研磨,设为厚度1.0mm的平行平板状,向该平行平板状的烧结体的两面印刷银膏后,以600℃实施烧结,并设置相对银电极,从而得到极化处理前的压电组合物的试样(实施例1~17及比较例1~4)。
对于得到的试样,如以下方式测定第二相相对于第一相的体积比和第三相相对于第一相的体积比、以及试样的电阻率。
第二相相对于第一相的体积比及第三相相对于第一相的体积比是通过对试样进行XRD测定,并根据观察的第一相、第二相及第三相的峰值强度进行计算。XRD测定使用作为X射线源使用的Cu-Kα射线的X射线衍射装置(Rigaku株式会社制造的SmartLab),测定条件在电压45kV、电流200mA且2θ=0~40°的范围内以扫描速度40deg/min进行。
根据通过测定得到的X射线衍射图,同定归属于第一相(KNbO3)的峰值中的最大的峰值、归属于第二相(K4Nb6O17)的峰值中的最大的峰值、以及归属于第三相(KNb3O8)的峰值中最大的峰值,并算出各自的最大峰值强度(I1、I2、I3)。各峰值强度通过从测定值减去背景的值而算出。将实施例5及比较例1的试样的X射线衍射图表示于图3中。根据图3(a)能够确认到,实施例5的试样中,不仅存在第一相,还存在第二相。与之相对能够确认到,与图3(b)相比,比较例1的试样中,仅存在第一相。
根据计算的强度,使用下述所示的式子,将第二相的最大峰值强度相对于第一相的最大峰值强度的比率设为第二相的体积相对于第一相的体积的比率(x),将第三相的最大峰值强度相对于第一相的最大峰值强度的比率设为第三相的体积相对于第一相的体积的比率(y)进行计算。将结果表示于表1中。
x(%)=100I2/I1
y(%)=100I3/I1
另外,就电阻率而言,使用超高电阻计(ADVANTEST制,ULTRA HIGH RESISTANCEMETER R8340),测定对形成电极的烧结体施加了50V直流电压时得到的绝缘电阻值,并根据得到的绝缘电阻值进行计算。此外,绝缘电阻值设为施加直流电压后10秒后测定的值。根据得到的绝缘电阻值,使用下述的式子,计算电阻率ρ(Ω·cm)。
ρ=RS/l
在此,R是绝缘电阻(Ω),S是电极面积(cm2),l是电极间距离(cm)。本实施例中,将电阻率为1.00×108Ω·cm以上的试样判断为良好。将结果表示于表1中。此外,表1的“电阻率ρ”的栏中的“aE+b”的记载表示“a×10b”。
【表1】
“电阻率ρ”栏中的“aE+b”的表述表示“a×10b”。
根据表1能够确认到,通过存在第二相和/或第三相,可得到良好的电阻率。另外,能够确认到通过将第二相的体积相对于第一相的体积的比率以及第三相的体积相对于第一相的体积的比率的和设为上述的范围内,能得到更高的电阻率。
另外能够确认到,通过使压电组合物含有过渡金属元素(Cu及Mn),可以得到非常高的电阻率。
产业上的可利用性
本发明的压电组合物具有较高的电阻率,因此,能够充分进行极化处理,能够适用于各种领域中的压电元件。
Claims (5)
1.一种压电组合物,其特征在于,
该压电组合物包含含有钾及铌的复合氧化物,
所述复合氧化物具有:
以组成式KNbO3表示的第一相;以及
选自以组成式K4Nb6O17表示的第二相及以组成式KNb3O8表示的第三相中的一个相或两个相。
2.根据权利要求1所述的压电组合物,其特征在于,
将所述第二相的体积相对于所述第一相的体积的比率及所述第三相的体积相对于所述第一相的体积的比率分别设为x%及y%时,
所述x及所述y满足0<x+y<10.0%的关系。
3.根据权利要求2所述的压电组合物,其特征在于,
所述x及所述y满足x>y的关系。
4.根据权利要求1~3中任一项所述的压电组合物,其特征在于,
所述压电组合物含有选自过渡金属元素中的一种以上。
5.一种压电元件,其含有权利要求1~4中任一项所述的压电组合物。
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