CN104926301A - 压电器件 - Google Patents
压电器件 Download PDFInfo
- Publication number
- CN104926301A CN104926301A CN201510242147.6A CN201510242147A CN104926301A CN 104926301 A CN104926301 A CN 104926301A CN 201510242147 A CN201510242147 A CN 201510242147A CN 104926301 A CN104926301 A CN 104926301A
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- Prior art keywords
- composition
- piezoelectric
- piezoelectric ceramic
- uhligite
- piezoelectric device
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- 239000000203 mixture Substances 0.000 claims abstract description 146
- 239000000919 ceramic Substances 0.000 claims abstract description 42
- 239000004020 conductor Substances 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 238000005204 segregation Methods 0.000 description 16
- 229910052726 zirconium Inorganic materials 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 230000005684 electric field Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910001316 Ag alloy Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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Abstract
本发明提供一种适合在高温环境下的使用的压电器件和压电陶瓷组合物。该压电器件具有将包含(LilNamK1-l-m)n(Nb1-oTao)O3表示的钙钛矿组合物和Ag成分的压电陶瓷组合物烧制而得到的压电陶瓷层;和夹着该压电陶瓷层的导体层,压电陶瓷层中,在钙钛矿组合物的烧结体中的空隙偏析有Ag,在由所述钙钛矿组合物的烧结体构成的结晶颗粒的晶界或者晶界三重点存在包含Si和K的结晶或者非晶质,其中,l~o满足下列的条件,即0.04<l≤0.1,0≤m≤1,0.95≤n≤1.05,0≤o≤1。
Description
本申请是国际申请日为2012年11月27日、国际申请号为PCT/JP2012/080545、国家申请号为201280057788.9、发明名称为“压电器件和压电陶瓷组合物”的分案申请
技术领域
本发明特别涉及在高温环境下适合使用的音响元件、压电致动器(actuator)等压电器件和其使用的压电陶瓷组合物。
背景技术
作为音响元件、压电致动器等的压电器件的电气机械转换材料,使用压电陶瓷组合物。
例如,专利文献1中公开的,对于由Pb1-(3/2)aMa{(Ni1/3Nb2/3)1-b(Zn1/3Nb2/3)b}xTiyZrzO3(其中,M是选自La和Nd中的至少一种元素,并且x+y+z=1、a=0.005~0.03、b=0.5~0.95、x=0.1~0.4、y=0.3~0.5、z=0.2~0.5)表示的钙钛矿型固溶体,使其含有0.3~1.0重量%的MnO2而形成的强电介质性陶瓷。
近年,由于压电器件的性能的提高、低压驱动化等,层叠构造正在推进。
但是,专利文献1的强电介质性陶瓷,由于烧结温度为1130~1300℃这样的高温,所以需要大量用于烧结的热能。而且,作为与强电介质性陶瓷同时进行烧制的内部电极的材料,必须使用Pt、Pd含有率多的Ag合金,存在压电器件成本高的问题。
因此,为了压电器件的低成本化,正在进行可以低温烧制的压电陶瓷组合物的开发。
专利文献2中公开了,包括由Pba{Zrb·Tic·(Ni1/3Nb2/3)d·(Zn1/3Nb2/3)e}O3(其中,b+c+d+e=1、1.000≤a≤1.020、0.26≤b≤0.31、0.34≤c≤0.40、0.10≤d≤0.35、0.07≤e≤0.14]表示的钙钛矿组合物和该钙钛矿组合物中包含的Ag2O,并且Ag2O按0.005~0.03wt%的比例含有的压电陶瓷组合物,能够在900℃左右烧制。
现有技术文献
专利文献
专利文献1:日本特开平3-215359号公报
专利文献2:日本专利第4202657号公报
发明内容
发明要解决的课题
但是,使用专利文献2的压电陶瓷组合物的压电器件是矫顽电场(Coercive electric field)低并且难以适合于高温下的使用的装置。另外,有介电常数ε高并且压电器件的消耗电力(功耗)增加的问题。
由此,本发明的目的是提供一种适合于在高温环境下的使用的压电器件和压电陶瓷组合物。
用于解决课题的技术方案
为了达成上述目的,本发明的压电器件包括:将含有钙钛矿组合物和Ag成分的压电陶瓷组合物烧制而得到的压电陶瓷层;和夹着该压电陶瓷层的导体层,该压电器件中,上述压电陶瓷层在上述钙钛矿组合物的烧结体中的空隙偏析有Ag。
上述钙钛矿组合物优选包含锆钛酸盐类钙钛矿组合物和/或含碱铌酸盐类钙钛矿组合物。
本发明的压电器件,关于偏析在上述钙钛矿组合物的烧结体中的空隙中的上述Ag的粒径,d80%径为0.1~3μm。
本发明的压电器件的上述压电陶瓷组合物包含由下式(1)表示的锆钛酸盐类钙钛矿组合物和Ag成分,上述Ag成分按氧化物换算相对于上述锆钛酸盐类钙钛矿组合物100质量份优选含有0.05~0.3质量份。
(Pba·Rex){Zrb·Tic·(Ni1/3Nb2/3)d·(Zn1/3Nb2/3)e}O3…(1)
式中,Re是La和/或Nd,a~e、x满足下列条件。
0.95≤a≤1.05
0≤x≤0.05
0.35≤b≤0.45
0.35≤c≤0.45
0<d≤0.10
0.07≤e≤0.20
b+c+d+e=1
本发明的压电器件的上述钙钛矿组合物是由下式(2)表示的含碱铌酸盐类钙钛矿组合物,上述压电陶瓷层,优选在由上述钙钛矿组合物的烧结体构成的结晶颗粒的晶界或者晶界三重点存在包含Si和K的结晶或者非晶质。
(LilNamK1-l-m)n(Nb1-oTao)O3…(2)
式中,l~o满足下列的条件。
0.04<l≤0.1
0≤m≤1
0.95≤n≤1.05
0≤o≤1
本发明的压电器件优选上述导体层由Ag、Pd、Pt、Ni、Cu形成或者由包含它们之中的至少一种的合金形成。
另外,本发明的压电陶瓷组合物的特征在于,含有由下式(1)表示的锆钛酸盐类钙钛矿组合物和Ag成分,上述Ag成分按氧化物换算相对于上述锆钛酸盐类钙钛矿组合物100质量份含有0.05~0.3质量份。
(Pba·Rex){Zrb·Tic·(Ni1/3Nb2/3)d·(Zn1/3Nb2/3)e}O3…(1)
式中,Re为La和/或Nd,a~e、x满足下列的条件。
0.95≤a≤1.05
0≤x≤0.05
0.35≤b≤0.45
0.35≤c≤0.45
0<d≤0.10
0.07≤e≤0.20
b+c+d+e=1
本发明的压电陶瓷组合物优选上述Ag成分的最大粒径为3μm以下。
发明效果
根据本发明的压电器件,压电陶瓷组合物含有钙钛矿组合物和Ag成分,因此压电陶瓷组合物的烧制温度(烧成温度)低,作为导体层能够使用Ag或Ag含量高的Ag合金。而且,压电陶瓷层在钙钛矿组合物的烧结体中的空隙中偏析有Ag,由此能够提高矫顽电场,能够实现适于在高温环境下使用的压电器件。而且,即使在作为导体层使用了Ag或者Ag合金的情况下,也能够防止导体层的Ag在压电陶瓷层中扩散而导体层缺乏,能够抑制特性的降低。
另外,如果在钙钛矿组合物的烧结体中的空隙偏析的Ag的粒径的d80%径为0.1~3μm,则能够实现压电特性良好的压电器件。
另外,含有由上式(1)表示的锆钛酸盐类钙钛矿组合物和Ag成分,并且Ag成分按氧化物换算相对于钙钛矿组合物100质量份含有0.05~0.3质量份的压电陶瓷组合物,能够形成居里温度Tc高、矫顽电场高、介电常数ε低的压电陶瓷层,进而可以进行900℃以下的低温烧制,能够将Ag或者Ag含量低的Ag合金作为导体金属材料使用。因此,能够以低成本制造消耗电力低、更适合高温环境下的使用的压电器件。
另外,在由上式(2)表示的含碱铌酸盐类钙钛矿组合物的烧结体构成的结晶颗粒的晶界或者晶界三重点,存在含有Si和K的结晶或者非晶质的压电陶瓷层,能够实现消耗电力低、适合高温环境下的使用的压电器件。
附图说明
[图1]是本发明的压电器件的截面图的示意图。
具体实施方式
如图1所示,本发明的压电器件包括:在钙钛矿组合物的烧结体中的空隙中偏析有Ag的压电陶瓷层;和夹着该压电陶瓷层的导体层。
通过使Ag偏析在钙钛矿组合物的烧结体中的空隙中,在烧结中,Ag成为氧的供给源,另外具有使液相的生成温度下降的效果。由此,抑制素体的氧、Pb的欠缺,材料的热力学方面的稳定性增加,由此形成为能够提高矫顽电场,能够实现适合在高温环境下的使用的压电器件。进而,即使在使用Ag或Ag合金作为导体层的情况下,通过使Ag偏析在钙钛矿组合物的烧结体中的空隙中,也能够防止导体层的Ag在压电陶瓷层扩散而导体层缺乏,能够抑制特性的降低。
而且,是否在钙钛矿组合物的烧结体中的空隙偏析有Ag,能够用TEM(透过型电子显微镜)、SEM(扫描型电子显微镜)观察,通过计测其尺寸分布而能够定量化。另外,偏析的Ag是否不是氧化物而是金属Ag,能够通过基于特性X线进行的组成分析来确认。
在本发明中,压电陶瓷层在钙钛矿组合物的烧结体中的空隙中偏析的上述Ag的粒径的d80%径优选为0.1~3μm。如果偏析的Ag的粒径是在上述范围,则能够使压电器件的压电特性良好。d80%径超过3μm时,以此为起点击穿电压有下降的倾向,另外压电陶瓷层的层间的Ag颗粒数减少,因此有耐圧寿命特性降低的倾向。另外,不足0.1μm时,成为Ag在烧结体中均匀地扩散的状态,有压电特性等劣化的倾向。
而且,在本发明中,通过TEM图像观察到偏析的Ag。而且,Ag的粒径是通过将从TEM图像任意选择的200个Ag颗粒的粒径进行图像的二进制化和测定判定为Ag的部分的长度而求得的,然后求得体积径累积,求出d80%径。
为了形成压电陶瓷层而使用的压电陶瓷组合物使用含有钙钛矿组合物和Ag成分的物质。
钙钛矿组合物优选锆钛酸盐类钙钛矿组合物和/或含碱铌酸盐类钙钛矿组合物。
作为锆钛酸盐类钙钛矿组合物,优选使用由下式(1)表示的组成构成的物质。
(Pba·Rex){Zrb·Tic·(Ni1/3Nb2/3)d·(Zn1/3Nb2/3)e}O3…(1)
在式(1)中,Re是La和/或Nd。
在式(1)中,a是0.95≤a≤1.05,优选1.00≤a≤1.02。a<0.95时,虽然能够得到优良的压电特性,但是即使添加Ag也不可能进行低温烧结,a>1.05时,Pb二次相大量析出,压电特性降低,成为不耐实用的状态。通过使a在上述范围,能够得到在900℃的烧制下压电特性优良的、陶瓷颗粒的粒径小的压电陶瓷组合物。
在式(1)中,x是0≤x≤0.05,优选0.003≤x≤0.007。即,式(1)的钙钛矿组合物中,Pb的一部分可以由La和/或Nd置换。通过将Pb的一部分用La和/或Nd置换,能够提高压电常数。x>0.05时,居里温度Tc变低。通过使x在上述范围,能够将居里温度Tc保持在300℃以上的高温,能够提高压电常数。
进而,优选调整为1.00≤a+x≤1.02。原因是,因为在(1)式的钙钛矿中,即使将ABO3型钙钛矿的A/B比调整为1.00~1.02,也可以保持特性。
在式(1)中,b是0.35≤b≤0.45,优选0.38≤b≤0.42。b<0.35时,居里温度Tc变低,b>0.45时,压电常数变低。通过使b在上述范围,能够将居里温度Tc保持在300℃以上的高温,能够提高压电常数。
在式(1)中,c是0.35≤c≤0.45,优选0.38≤c≤0.42。c<0.35时,居里温度Tc变低,c>0.45时,压电常数变低。通过使c在上述范围,能够将居里温度Tc保持在300℃以上的高温,能够提高压电常数。
在式(1)中,d满足0<d≤0.10,优选0.3≤d≤0.7。d=0时,居里温度Tc高,但是压电常数变低,d>0.10时,居里温度Tc变低。通过使d在上述范围,能够将Tc维持保持在300℃以上的高温,能够提高压电常数。
在式(1)中,e是0.07≤e≤0.20,优选0.13≤e≤0.17。e<0.07时,素体的晶粒成长显著,不能保持微细构造,低温烧结变得不可进行,e>0.20时,压电常数变低。通过使e在上述范围,可以进行低温烧结和压电常数的维持。
在式(1)中,b+c+d+e=1。
另外,作为含碱铌酸盐类钙钛矿组合物,优选使用由下式(2)表示的组成构成的物质。具备在由式(2)表示的含碱铌酸盐类钙钛矿组合物的烧结体构成的晶粒的晶界或者晶界三重点存在含有Si和K的结晶或者非晶质的压电陶瓷层的压电器件,消耗电力低,适合在高温环境下的使用。
(LilNamK1-l-m)n(Nb1-oTao)O3…(2)
在式(2)中,l优选0.04<l≤0.1。当l≤0.04或者l>0.1时,有在室温下的压电常数变低的倾向。
在式(2)中,m优选0≤m≤1。m>1时,有成为二次相、压电常数降低的倾向。
在式(2)中,n优选0.95≤n≤1.05。当n<0.95或者n>1.05时,有成为二次相、压电常数降低的倾向。
在式(2)中,o优选0≤o≤1。o>1时,有成为二次相、压电常数降低的倾向。
在本发明中,作为压电陶瓷组合物,优选使用含有由式(1)表示的锆钛酸盐类钙钛矿组合物和Ag成分的物质,上述Ag成分按氧化物换算相对于锆钛酸盐类钙钛矿组合物100质量份含有0.05~0.3质量份。该压电陶瓷组合物可以进行在900℃以下的低温烧制,作为导体层材料使用Ag或Ag含量高的Ag合金,能够与压电陶瓷组合物同时进行烧制来制造压电器件。另外,将该压电陶瓷组合物进行烧制得到的压电陶瓷层,居里温度Tc高达300℃以上,矫顽电场即使在120℃也高达0.8kV/mm以上,介电常数ε低至1800~2200,因此能够实现消耗电力低并且更适合于在高温环境下的使用的压电器件。而且,在本发明中,居里温度Tc、矫顽电场、介电常数ε是用在后述的实施例中记载的方法测定的值。
作为在压电陶瓷组合物中含有的Ag成分,能够举出Ag的氧化物(Ag2O)、碳酸盐(Ag2CO3)等。
Ag成分的最大粒径优选为3μm以下。如果Ag成分的最大粒径为3μm以下,则Ag容易偏析在钙钛矿组合物的烧结体中的空隙。当超过3μm时,Ag成分析出在烧结体表面,形成由Ag成分产生的二次相,有可能压电器件的产品寿命特性较低。将Ag成分的最大粒径调整为3μm以下的方法没有特别限定,例如能够举出在粉末状态下进行筛选的方法、在浆料状态下通过过滤器的方法等。
而且,在本发明中,Ag成分的粒径利用TEM进行测定,将任意选择的200个之中最大的粒径作为最大粒径。
Ag成分的含有量按氧化物换算,相对于钙钛矿组合物100质量份优选为0.05~0.3质量份,更优选为0.07~0.15质量份。Ag成分的含有量不足0.05质量份时,在低温下难以进行烧结,在900℃下的体积密度(烧结体真密度)变小,有耐湿特性劣化的倾向,当超过0.3质量份时,在烧结体表面析出Ag成分,而形成Ag成分产生的二次相,有可能压电器件的产品寿命特性降低。如果Ag成分的含有量在上述范围,则能够容易形成在钙钛矿组合物的烧结体中的空隙偏析有Ag的压电陶瓷层。
在本发明中,上述压电陶瓷组合物还可以含有Mn成分。通过含有Mn成分,得到的压电陶瓷层硬化,Q值上升,能够进一步降低压电器件的消耗电力。
Mn成分的含有量相对于钙钛矿组合物100质量份按氧化物换算优选为0~1质量%。另外,在本发明中,上述压电陶瓷组合物还可以含有Co成分。通过含有Co成分,能够将压电特性、电介质特性进行微调为所期望的特性。Co成分的含有量相对于钙钛矿组合物100质量份按氧化物换算优选为0~1质量%。
在本发明中,钙钛矿组合物的烧结体的粒径优选为3μm以下。这样,能够使耐圧寿命特性提高。
含有由式(1)表示的锆钛酸盐类钙钛矿组合物的压电陶瓷组合物,将Pb、La、Zr、Ti、Ni、Nb、Zn的氧化物、碳酸盐等以成为由式(1)表示的锆钛酸盐类钙钛矿组合物的化学计量比的方式进行混合,在水等湿式下混合后干燥,在大气气氛下,在820~850℃进行烧制2~4小时。由此,各金属成分相互进行固相反应,形成由上述式(1)表示的锆钛酸盐类钙钛矿组合物。形成钙钛矿组合物后,进行湿式粉碎或者干式粉碎,添加Ag成分,优选相对于钙钛矿组合物100质量份添加0.05~0.3质量份,通过干燥处理而得到。而且,Ag成分可以在形成钙钛矿组合物时与其他的原料一起添加,但是优选在形成钙钛矿组合物后添加。通过在形成钙钛矿组合物后添加Ag成分,容易使Ag偏析在钙钛矿组合物的烧结体中的空隙。
另外,含有由式(2)表示的含碱铌酸盐类钙钛矿组合物的压电陶瓷组合物,将Li、Na、K、Nb、Ta的氧化物、碳酸盐等以成为由式(2)表示的含碱铌酸盐类钙钛矿组合物的化学计量比的方式进行混合,与上述同样地进行烧制,由此各金属成分相互进行固相反应,形成由上述式(2)表示的含碱铌酸盐类钙钛矿组合物。然后,在形成钙钛矿组合物后,进行湿式粉碎或者干式粉碎,添加Ag成分,优选相对于钙钛矿组合物100质量份添加0.05~0.3质量份,通过干燥处理得到。
在本发明的压电器件中,作为构成导体层的材料没有特别限定。优选低电阻材料,更优选Ag、Pd、Pt、Ni、Cu或者含有它们之中的至少一种的合金。作为上述合金优选Ag-Pd合金、Ag-Pt合金。
本发明的压电器件,消耗电力较低,适合在高温环境下的使用,例如能够在车载用扬声器等音响元件、压电致动器、超声波电动机等的用途中特别优选使用。
上述压电器件例如能够通过以下方法制造。
在含有钙钛矿组合物和Ag成分的压电陶瓷组合物中,添加结合剂、溶剂、增塑剂等调整为浆料状,用刮刀法等方法形成为薄膜状来制造生片(green sheet)。作为结合剂,能够举出聚乙烯醇缩丁醛树脂、甲基丙烯酸树脂等。作为增塑剂,能够举出邻苯二甲酸二丁酯、邻苯二甲酸二辛酯等。作为溶剂,能够举出甲苯、甲基乙基酮等。
接着,在得到的生片上通过网版印刷法等印刷含有Ag、Ag-Pd合金、Ag-Pt合金等导体金属的导体膏,形成规定图案的未烧制内部导体层。
接着,将形成有未烧制内部导体层的各生片重叠多个,进行压接来制造未烧制层叠体。
接着,对未烧制层叠体进行脱粘合剂处理,切割为规定形状,使未烧制内部导体层在未烧制层叠体的端部露出。然后,在未烧制层叠体的端面通过网版印刷法等方法印刷含有导体金属的导体膏,来形成未烧制外部电极层。
接着,将形成有未烧制基底金属的未烧制层叠体在氧气氛中在850~900℃下烧制2~3小时。通过这样做,能够制造压电陶瓷层被导体层夹着的上述本发明的压电器件。
实施例
作为原料粉末,分别准备PbO、La2O3、ZrO2、TiO2、NiO、ZnO、Nb2O5、Ag2O,筛选这些原料粉末,将最大粒径调整为3μm以下。然后,将筛选后的钙钛矿组合物的各原料粉末以表1所示的比例进行称重,与氧化锆珠、离子交换水一起放入罐磨机内,进行15小时湿式混合,将得到的悬浮液转移到桶(vat),放入干燥器内,在150℃下使其干燥。
[表1]
*:(Pba·Rex){Zrb·Tic·(Ni1/3Nb2/3)d·(Zn1/3Nb2/3)e}O3
接着,将通过该干燥而得到的混合物在大气气氛下使用电炉在850℃下烧制2小时。混合物内的各金属氧化物通过该烧制相互进行固相反应,形成钙钛矿组合物。
接着,将该钙钛矿组合物和按表1所示的比例称重的Ag2O与氧化锆珠、离子交换水一起放入罐磨机内,进行15小时湿式粉碎,将得到的悬浮液转移到桶,放入干燥器内,在150℃下使其干燥,得到压电陶瓷组合物。
接着,在各压电陶瓷组合物混合少量聚乙烯醇缩丁醛,使用加压冲压机以压力1.5MPa进行压缩成形,得到直径8mm、厚度0.5mm的圆板形的试样。
接着,将该试样放入电炉内,在大气氛围下在900℃~1050℃烧制2小时,之后将该试样从电炉中取出,在试样的两个面印刷无玻璃料Ag膏,在大气气氛下在700℃进行烧结,将其作为外部电极。
对于安装有该外部电极的圆板形试样,在40℃~400℃之间测定介电常数ε的温度依赖性,求得居里温度Tc。另外,使用TF分析器在25℃、1Hz、3kV/mm的条件下测定各试样的磁滞,计算出矫顽电场。接着,对带有该外部电极的试样在150℃下施加1.5kV/mm的电压15分钟,使试样极化。接着,测定该极化后的试样的压电常数Kr时,如表1所示。压电常数Kr的测定遵循电子信息技术产业协会规定(JEITAEM-4501),进行阻抗测定,进行计算。在表2表示结果。
[表2]
另外,使用试样1A、1B、2的压电陶瓷组合物,利用刮刀法使生片成形,在得到的生片上通过网版印刷法印刷Ag膏,形成未烧制内部导体层。
接着,将形成有未烧制内部导体层的各生片重叠11个,用相同的片上下夹着将没有印刷膏的片层叠为规定的厚度的覆盖片一并进行压接来制造未烧制层叠体。
接着,将该未烧制层叠体放入电炉内,在大气气氛下在900℃烧制2小时来制造层叠体。对于得到的层叠体拍摄TEM图像,确认是否在钙钛矿组合物的烧结体中的空隙偏析有Ag。另外,通过EDS(能量分散X线分光法)确认有无检测出氧。
试样1的压电器件,在钙钛矿组合物的烧结体中的空隙偏析有Ag。该偏析的Ag的粒径的d80%径为2.1μm。另外,从偏析的Ag,利用EDS没有检测出氧,偏析的Ag不是氧化物,是金属Ag。而且,该压电器件如表1所示,居里温度Tc高,矫顽电场高,即使在105℃以上的高温也能驱动,适合于在高温下的使用。另外,介电常数ε低,消耗电力小。而且,压电陶瓷组合物是能够在900℃以下烧制的。
另外,在Re中使用了Nd的试样1B也得到了相同的结果。试样1A、1B相当于本发明的压电陶瓷组合物。
与此相对,试样2的压电器件,Ag相对于压电陶瓷层大致均匀地分散,从空隙没有发现Ag的偏析。另外,居里温度Tc低,矫顽电场低,因此难以适合于在105℃以上的高温下的使用。而且,是介电常数ε高、消耗电力大的压电器件。
另外,使用不含Ag成分的压电陶瓷组合物的试样3的压电器件,需要1100℃以上的烧制温度,不能与Ag或Ag含有量高的Ag合金同时进行烧制。另外,由于需要提高烧制温度,所以烧制能量增加,制造成本增加。
另外,使用了含有比本发明中规定的优选的范围多的Ag成分的压电陶瓷组合物的试样4,Ag在压电陶瓷层的表面析出,产品的寿命特性容易下降。
另外,关于Pb,使a>1.05的试样5由于Pb二次相的析出而没能进行特性的评价。
另外,关于Pb,使a<0.95的试样6不能低温烧结。
另外,关于Re,使x>0.05的试样7,Tc下降,矫顽电场降低。
另外,关于Zr,使b>0.45的试样8,压电常数降低。
另外,关于Ti,使c>0.45的试样9,压电常数降低。
另外,关于(Ni1/3Nb2/3),使d>0.10的试样10,Tc下降,矫顽电场降低。
另外,关于(Ni1/3Nb2/3),使d=0的试样11,压电常数降低。
另外,关于(Zn1/3Nb2/3),使e>0.20的试样12,压电常数降低。
另外,关于(Zn1/3Nb2/3),使e<0.07的试样13,压电常数降低。
Claims (3)
1.一种压电器件,其特征在于,包括:
将包含下式(2)表示的含碱铌酸盐类钙钛矿组合物和Ag成分的压电陶瓷组合物烧制而得到的压电陶瓷层;和
夹着该压电陶瓷层的导体层,
所述压电陶瓷层中,Ag偏析在所述钙钛矿组合物的烧结体中的空隙中,
所述压电陶瓷层,在由所述钙钛矿组合物的烧结体构成的结晶颗粒的晶界或者晶界三重点存在包含Si和K的结晶或者非晶质,
(LilNamK1-l-m)n(Nb1-oTao)O3…(2)
式中,l~o满足下列的条件:
0.04<l≤0.1
0≤m≤1
0.95≤n≤1.05
0≤o≤1。
2.如权利要求1所述的压电器件,其特征在于:
偏析在所述钙钛矿组合物的烧结体中的空隙中的所述Ag的粒径,其D80径为0.1~3μm。
3.如权利要求1或2所述的压电器件,其特征在于:
所述导体层由Ag、Pd、Pt、Ni、Cu或者包含它们中的至少一种的合金形成。
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CN103958439B (zh) | 2011-12-20 | 2016-10-26 | 太阳诱电株式会社 | 压电器件和压电陶瓷组合物 |
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JP5940561B2 (ja) | 2016-06-29 |
US20160104832A1 (en) | 2016-04-14 |
CN103958439A (zh) | 2014-07-30 |
US20140368090A1 (en) | 2014-12-18 |
JP6039762B2 (ja) | 2016-12-07 |
CN104926301B (zh) | 2017-11-17 |
CN103958439B (zh) | 2016-10-26 |
JP2016175824A (ja) | 2016-10-06 |
WO2013094368A1 (ja) | 2013-06-27 |
US20160293830A1 (en) | 2016-10-06 |
US9406866B2 (en) | 2016-08-02 |
JPWO2013094368A1 (ja) | 2015-04-27 |
JP6175528B2 (ja) | 2017-08-02 |
US9614142B2 (en) | 2017-04-04 |
JP2016000689A (ja) | 2016-01-07 |
US9755137B2 (en) | 2017-09-05 |
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