JP2001302348A - Piezoelectric ceramic composition - Google Patents
Piezoelectric ceramic compositionInfo
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- JP2001302348A JP2001302348A JP2000117437A JP2000117437A JP2001302348A JP 2001302348 A JP2001302348 A JP 2001302348A JP 2000117437 A JP2000117437 A JP 2000117437A JP 2000117437 A JP2000117437 A JP 2000117437A JP 2001302348 A JP2001302348 A JP 2001302348A
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000006073 displacement reaction Methods 0.000 claims abstract description 17
- 230000005684 electric field Effects 0.000 claims abstract description 16
- 230000010287 polarization Effects 0.000 claims description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 8
- 150000002602 lanthanoids Chemical class 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 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 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011835 investigation Methods 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
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、チタン酸ジルコン
酸鉛を主成分とする圧電磁器組成物に関するものであ
り,特に高電界下での圧電変位量が大きく,且つ比誘電
率の温度変化が小さいとともに,絶縁性に優れた圧電磁
器組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition containing lead zirconate titanate as a main component, and in particular, has a large piezoelectric displacement under a high electric field and a change in relative permittivity with temperature. The present invention relates to a piezoelectric ceramic composition which is small and has excellent insulation properties.
【0002】[0002]
【従来の技術】従来、圧電磁器材料としては,PbTi
O3やPbZrO3を主成分として含む圧電セラミック
ス(以下、PZT系圧電セラミックスと呼ぶ)や,複合
ペロブスカイト類を第三,第四成分として固溶させた多
成分系PZT系圧電セラミックスが,圧電定数が大であ
るために,圧電振動子を初めとしてアクチュエータ用の
材料として広く利用されている。2. Description of the Related Art Conventionally, PbTi has been used as a piezoelectric ceramic material.
Piezoelectric ceramics containing O 3 or PbZrO 3 as a main component (hereinafter referred to as PZT-based piezoelectric ceramics) and multi-component PZT-based piezoelectric ceramics in which composite perovskites are dissolved as third and fourth components are used as piezoelectric constants. Is widely used as a material for actuators including piezoelectric vibrators.
【0003】これらの系の材料は,一般にモルフォトピ
ック相境界(MPB)近傍組成において,圧電定数(d
定数)等の圧電変位に寄与する特性が向上するため,ア
クチュエータ用材料としては,前記MPB近傍組成の圧
電磁器材料が広く実用化されている。[0003] Materials of these systems generally have a piezoelectric constant (d) at a composition near the morphotopic phase boundary (MPB).
As a material for actuators, piezoelectric ceramic materials having a composition in the vicinity of the MPB have been widely used as a material for an actuator because the characteristics contributing to piezoelectric displacement such as a constant are improved.
【0004】[0004]
【発明が解決しようとする課題】しかしながら,前記圧
電定数は一般にEMAS−6100等で示された,共振
−***振法で求められた値であり,基本的には低電界
(約数百V/m程度)印加時の圧電変位の割合を示して
いる。これに対し,実際の圧電アクチュエータにおける
駆動電界は,数百kV/m〜数千kV/mにもなり,前
記方法で求めた圧電定数が実用的な意味を持たない場合
がある。さらに,近年圧電アクチュエータ利用範囲の広
がりに伴い,広い温度範囲での特性安定性,特に静電容
量の温度安定性が求められている。例えば,自動車用部
品として圧電アクチュエータが使用される場合には,そ
の使用環境に応じて,−40℃〜170℃にもなる広い
温度範囲での特性安定性が要求される場合がある。これ
に対し,一般に前記MPB近傍組成での圧電磁器材料
は,比誘電率の温度変動が大きくなり,広い温度範囲に
おけるアクチュエータ特性の安定性,特に静電容量の安
定性に問題が生じている。However, the piezoelectric constant is a value obtained by a resonance-anti-resonance method generally shown by EMAS-6100 or the like, and is basically a low electric field (about several hundred V / (approximately m) when applied. On the other hand, the driving electric field in an actual piezoelectric actuator is several hundred kV / m to several thousand kV / m, and the piezoelectric constant obtained by the above method may not have a practical meaning. Furthermore, with the expansion of the range of use of piezoelectric actuators in recent years, there has been a demand for characteristic stability over a wide temperature range, particularly temperature stability of capacitance. For example, when a piezoelectric actuator is used as a component for an automobile, the stability of characteristics in a wide temperature range of −40 ° C. to 170 ° C. may be required depending on the use environment. On the other hand, in general, the piezoelectric ceramic material having a composition near the MPB has a large variation in the relative dielectric constant with temperature, and thus has a problem in the stability of the actuator characteristics in a wide temperature range, particularly in the stability of the capacitance.
【0005】PbTiO3−PbZrO3−Pb(Ni
1/3Nb2/3)O3系(以下,PNN−PZT系と
呼ぶ)の圧電磁器組成物はd定数が大きいため,アクュ
エータ素子用の圧電磁器材料として利用されている。[0005] PbTiO 3 -PbZrO 3 -Pb (Ni
1/3 Nb 2/3) O 3 system (hereinafter, the piezoelectric ceramic composition is referred to as PNN-PZT system) has a large d constant, is utilized as a piezoelectric ceramic material for Akuyueta element.
【0006】しかし,圧電アクチュエータの応用範囲が
広がるにつれ,さらに大きなd定数を持つ材料が求めら
れている。また,この系の圧電磁器材料は電気抵抗率が
比較的小さく,積層型圧電素子のように、一層の厚みが
100μm前後の素子に使用した場合,印加できる電圧
を大きくできず,充分な特性を引き出せなかったり,使
用中に絶縁破壊してしまう等の問題点が生じている。However, as the range of application of the piezoelectric actuator is expanded, a material having a larger d constant is required. Further, the piezoelectric ceramic material of this system has a relatively small electric resistivity, and when used for an element having a thickness of about 100 μm, such as a laminated piezoelectric element, the voltage that can be applied cannot be increased, and sufficient characteristics can be obtained. There are problems such as being unable to be pulled out and causing dielectric breakdown during use.
【0007】また,前記PNN−PZT系圧電磁器材料
は,電気抵抗率の温度変動も大きいため,特に前述のよ
うな広い温度範囲で使用する場合には,さらに信頼性が
低下するなどの問題があった。Further, since the PNN-PZT piezoelectric ceramic material has a large variation in electric resistivity with temperature, there is a problem that the reliability is further lowered particularly when used in the above-mentioned wide temperature range. there were.
【0008】そこで、本発明の一技術的課題は、高電圧
印加時の圧電歪定数が大きく,かつ,比誘電率の温度変
化が小さく,高温度範囲での電気抵抗率も大きく、した
がって、広い温度範囲で安定な特性を有するとともに絶
縁性に優れた圧電磁器組成物を提供することにある。Therefore, one technical problem of the present invention is that the piezoelectric strain constant when a high voltage is applied is large, the change in relative permittivity with temperature is small, and the electric resistivity in a high temperature range is large. An object of the present invention is to provide a piezoelectric ceramic composition having stable properties in a temperature range and excellent in insulating properties.
【0009】また、本発明の特別な技術的課題は、アク
チュエータ用材料として極めて有用な圧電磁器組成物を
提供することにある。A special technical object of the present invention is to provide a piezoelectric ceramic composition which is extremely useful as a material for an actuator.
【0010】[0010]
【課題を解決するための手段】本発明者は,組成式aP
bTiO3+bPbZrO3+CPb(Ni1/3Nb
2/3)O3(a+b+c=100)で表される圧電磁
器組成物の圧電変位特性を種々調査した結果,その組成
範囲が所定の領域にあり、Pb量を滅少させることや,
La,Nd等のランタノイド元素およびSr等のアルカ
リ土類元素を副成分として添加する事で分極軸と同一方
向に,500kV/mの直流電界を印加したときの圧電
変位(以下,d33(500kV))が母成分のみの場
合より改善し,かつ,−40℃〜170℃の範囲におけ
る比誘電率の温度変化の劣化が少ない圧電磁器組成物を
見いだした。また,上記記載の圧電磁器材料に対して,
MnをMnOで表される酸化物に換算して,0〜0.0
5wt%(0は含まない)の割合で含有することによ
り,圧電磁器組成物の絶縁性が向上することを見出し、
本発明を為すに至ったものである。Means for Solving the Problems The present inventor has proposed a composition formula aP
bTiO 3 + bPbZrO 3 + CPb (Ni 1/3 Nb
As a result of various investigations on the piezoelectric displacement characteristics of the piezoelectric ceramic composition represented by 2/3 ) O 3 (a + b + c = 100), the composition range was within a predetermined range, and the Pb amount was reduced.
By adding a lanthanoid element such as La and Nd and an alkaline earth element such as Sr as subcomponents, a piezoelectric displacement when a DC electric field of 500 kV / m is applied in the same direction as the polarization axis (hereinafter, d33 (500 kV)) ) Has been found to be improved as compared with the case where only the base component is used, and to have less deterioration in the temperature change of the relative dielectric constant in the range of −40 ° C. to 170 ° C. In addition, for the piezoelectric ceramic material described above,
Converting Mn to an oxide represented by MnO, 0 to 0.0
It has been found that the content of 5 wt% (excluding 0) improves the insulating properties of the piezoelectric ceramic composition,
The present invention has been accomplished.
【0011】即ち、本発明によれば、組成式aPbTi
O3+bPbZrO3+cPb(Ni1/3N
b2/3)O3(a+b+c=100)で表され,その
組成範囲が,図1のI点(a=35mol%,b=30
mol%,c=35mol%)、J点(a=44mol
%,b=16mol%,c=40mol%)、K点(a
=50mol%,b=40mol%,c=10mol
%)、およびL点(a=40mol%,b=50mol
%,c=10mol%)の各組成点を結ぶ線上およびこ
の4点に囲まれた領域とする範囲を母成分とし,Pb量
を0〜3mol%(0を除く)の範囲で減少させた,分
極軸と同一方向に,500kV/mの直流電界を印加し
たときの圧電変位が,500pm/V以上を示し,か
つ,−40℃〜170℃の範囲で,比誘電率の温度変化
が300%以下であることを特徴とする圧電磁器組成物
が得られる。That is, according to the present invention, the composition formula aPbTi
O 3 + bPbZrO 3 + cPb (Ni 1/3 N
b 2/3 ) O 3 (a + b + c = 100), and its composition range is point I (a = 35 mol%, b = 30 in FIG. 1).
mol%, c = 35 mol%), J point (a = 44 mol)
%, B = 16 mol%, c = 40 mol%), point K (a
= 50 mol%, b = 40 mol%, c = 10 mol
%) And L point (a = 40 mol%, b = 50 mol)
%, C = 10 mol%), and the range defined as a region surrounded by these four points on the line connecting the respective composition points was used as a mother component, and the amount of Pb was reduced in the range of 0 to 3 mol% (excluding 0). When a DC electric field of 500 kV / m is applied in the same direction as the polarization axis, the piezoelectric displacement shows 500 pm / V or more, and the temperature change of the relative dielectric constant is 300% in the range of -40 ° C to 170 ° C. A piezoelectric ceramic composition characterized by the following is obtained.
【0012】また、本発明によれば、前記圧電磁器組成
物において、母成分に対してLa,Nd等のランタノイ
ド元素およびSr等のアルカリ土類元素のうち少なくと
も1種を0〜7mol%(0を除く)の範囲で添加し,
かつPb量を0〜5mol%(0を除く)の範囲で滅少
させた,分極軸と同一方向に,500kV/mの直流電
界を印加したときの圧電変位が,500pm/V以上を
示し,かつ,40℃〜170℃の範囲で,比誘電率の温
度変化が300%以下であることを特徴とする圧電磁器
組成物が得られる。Further, according to the present invention, in the piezoelectric ceramic composition, at least one of a lanthanoid element such as La and Nd and an alkaline earth element such as Sr is 0 to 7 mol% (0 Excluding)
And a piezoelectric displacement of 500 pm / V or more when a DC electric field of 500 kV / m is applied in the same direction as the polarization axis with the Pb content reduced in the range of 0 to 5 mol% (excluding 0); In addition, a piezoelectric ceramic composition characterized in that the temperature change of the relative dielectric constant is 300% or less in the range of 40 ° C to 170 ° C.
【0013】また、本発明によれば、組成式aPbTi
O3+bPbZrO3+cPb(Ni1/3N
b2/3)O3(a+b+c=100)で表され,その
組成範囲が,図1のI点(a=35mol%,b=30
mol%,c=35mol%)、J点(a=44mol
%,b=16mol%,c=40mol%)、K点(a
=50mol%,b=40mol%,c=10mol
%)、およびL点(a=40mol%,b=50mol
%,c=10mol%)の各組成点を結ぶ線上およびこ
の4点に囲まれた領域とする範囲を母成分とし,La,
Nd等のランタノイド元素およびSr等のアルカリ土類
元素のうち1種類以上を0〜5mol%(0を除く)の
範囲で添加した,分極軸と同一方向に,500kV/m
の直流電界を印加したときの圧電変位が,500pm/
V以上を示し,かつ,−40℃〜170℃の範囲で,比
誘電率の温度変化が300%以下であることを特徴とす
る圧電磁器組成物が得られる。Further, according to the present invention, the composition formula aPbTi
O 3 + bPbZrO 3 + cPb (Ni 1/3 N
b 2/3 ) O 3 (a + b + c = 100), and its composition range is point I (a = 35 mol%, b = 30 in FIG. 1).
mol%, c = 35 mol%), J point (a = 44 mol)
%, B = 16 mol%, c = 40 mol%), point K (a
= 50 mol%, b = 40 mol%, c = 10 mol
%) And L point (a = 40 mol%, b = 50 mol)
%, C = 10 mol%) on the line connecting the respective composition points and a range surrounded by the four points is defined as a mother component, and La,
One or more of lanthanoid elements such as Nd and alkaline earth elements such as Sr are added in the range of 0 to 5 mol% (excluding 0).
The piezoelectric displacement when applying a DC electric field of 500 pm /
The piezoelectric ceramic composition is characterized in that the piezoelectric ceramic composition exhibits a temperature of not less than V and a temperature change of the relative dielectric constant of 300% or less in a range of -40 ° C to 170 ° C.
【0014】また、本発明によれば、前記いずれかの圧
電磁器組成物において、総量に対して,MnをMnOで
表される酸化物に換算して,0〜0.05wt%(0は
含まない)の割合で含有し,−40℃〜170℃におけ
る比抵抗が1.0×1011Ω・cm以上であることを
特徴とする圧電磁器組成物が得られる。According to the present invention, in any of the piezoelectric ceramic compositions described above, Mn is converted to an oxide represented by MnO in an amount of 0 to 0.05 wt% (0 is included) based on the total amount. And a specific resistance at −40 ° C. to 170 ° C. of 1.0 × 10 11 Ω · cm or more.
【0015】[0015]
【発明の実施の形態】まず、本発明の圧電磁器組成物に
ついて図面を参照しながら説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the piezoelectric ceramic composition of the present invention will be described with reference to the drawings.
【0016】図1は本発明の圧電磁器組成物の母成分の
組成を三角座標で示す図である。FIG. 1 is a diagram showing the composition of the mother component of the piezoelectric ceramic composition of the present invention in triangular coordinates.
【0017】本発明の圧電磁器組成物は、組成式aPb
TiO3+bPbZrO3+cPb(Ni1/3Nb
2/3)O3(a+b+c=100)で表され,その組
成範囲が,図1のI点(a=35mol%,b=30m
ol%,c=35mol%)、J点(a=44mol
%,b=16mol%,c=40mol%)、K点(a
=50mol%,b=40mol%,c=10mol
%)、およびL点(a=40mol%,b=50mol
%,c=10mol%)の各組成点を結ぶ線上およびこ
の4点に囲まれた領域とする範囲を母成分としている。The piezoelectric ceramic composition of the present invention has a composition formula aPb
TiO 3 + bPbZrO 3 + cPb (Ni 1/3 Nb
2/3 ) O 3 (a + b + c = 100), and its composition range is point I in FIG. 1 (a = 35 mol%, b = 30 m
ol%, c = 35 mol%), J point (a = 44 mol)
%, B = 16 mol%, c = 40 mol%), point K (a
= 50 mol%, b = 40 mol%, c = 10 mol
%) And L point (a = 40 mol%, b = 50 mol)
%, C = 10 mol%) on a line connecting the respective composition points and a range surrounded by these four points is defined as a mother component.
【0018】本発明の圧電磁器組成物の一例は、この母
成分からPb量を0〜3mol%(0を除く)の範囲で
減少させることによって、分極軸と同一方向に500k
V/mの直流電界を印加したときの圧電変位が,500
pm/V以上を示し,かつ,−40℃〜170℃の範囲
で,比誘電率の温度変化が300%以下とした圧電磁器
組成物である。One example of the piezoelectric porcelain composition of the present invention is to reduce the amount of Pb in the range of 0 to 3 mol% (excluding 0) from this base component, so that 500 k in the same direction as the polarization axis.
When a DC electric field of V / m is applied, the piezoelectric displacement is 500
It is a piezoelectric ceramic composition which shows pm / V or more and has a relative dielectric constant with a temperature change of 300% or less in a range of -40 ° C to 170 ° C.
【0019】また、本発明の圧電磁器組成物のもう一つ
の例は、前記圧電磁器組成物において、母成分に対して
La,Nd等のランタノイド元素およびSr等のアルカ
リ土類元素のうち少なくとも1種を0〜7mol%(0
を除く)の範囲で添加し,かつPb量を0〜5mol%
(0を除く)の範囲で滅少させることによって、分極軸
と同一方向に,500kV/mの直流電界を印加したと
きの圧電変位が,500pm/V以上を示し,かつ,4
0℃〜170℃の範囲で,比誘電率の温度変化が300
%以下とした圧電磁器組成物である。Another example of the piezoelectric ceramic composition of the present invention is the piezoelectric ceramic composition, wherein at least one of a lanthanoid element such as La and Nd and an alkaline earth element such as Sr is used with respect to a mother component. Seed is 0-7 mol% (0
), And the Pb content is 0 to 5 mol%
(Excluding 0), the piezoelectric displacement when a DC electric field of 500 kV / m is applied in the same direction as the polarization axis shows 500 pm / V or more, and 4
In the range of 0 ° C to 170 ° C, the temperature change of the relative dielectric constant is 300
% Or less.
【0020】また、本発明の圧電磁器組成物のさらにも
う一つの例は、前記母成分に,La,Nd等のランタノ
イド元素およびSr等のアルカリ土類元素のうち1種類
以上を総量に対して0〜5mol%(0を除く)の範囲
で添加することによって、分極軸と同一方向に,500
kV/mの直流電界を印加したときの圧電変位が,50
0pm/V以上を示し,かつ,−40℃〜170℃の範
囲で,比誘電率の温度変化が300%以下である圧電磁
器組成物である。Further, still another example of the piezoelectric ceramic composition of the present invention is a piezoelectric ceramic composition according to the present invention, wherein one or more of lanthanoid elements such as La and Nd and alkaline earth elements such as Sr are contained in the mother component with respect to the total amount. By adding in the range of 0 to 5 mol% (excluding 0), 500% in the same direction as the polarization axis.
The piezoelectric displacement when applying a DC electric field of kV / m is 50
A piezoelectric ceramic composition exhibiting 0 pm / V or more, and having a temperature change in relative dielectric constant of 300% or less in a range of -40 ° C to 170 ° C.
【0021】また、本発明の圧電磁器組成物の別の例
は、前記母成分に対して、La,Nd等のランタノイド
元素およびSr等のアルカリ土類元素のうち少なくとも
1種を総量に対して0〜7mol%(0を除く)の範囲
で添加するとともに、Pb量を0〜5mol%(0を除
く)の範囲で滅少させることによって、分極軸と同一方
向に,500kV/mの直流電界を印加したときの圧電
変位が,500pm/V以上を示し,かつ,40℃〜1
70℃の範囲で,比誘電率の温度変化が300%以下で
ある圧電磁器組成物である。Further, another example of the piezoelectric ceramic composition of the present invention is that a lanthanoid element such as La and Nd and an alkaline earth element such as Sr are used with respect to the mother component. A DC electric field of 500 kV / m in the same direction as the polarization axis by adding Pb in the range of 0 to 7 mol% (except 0) and decreasing the amount of Pb in the range of 0 to 5 mol% (except 0). Is greater than 500 pm / V, and 40 ° C. to 1
The piezoelectric ceramic composition has a relative dielectric constant with a temperature change of 300% or less in a temperature range of 70 ° C.
【0022】また、本発明の圧電磁器組成物の他の例
は、前記いずれかの圧電磁器組成物において、総量に対
して,MnをMnOで表される酸化物に換算して,0〜
0.05wt%(0は含まない)の割合で含有させたも
のであり、−40℃〜170℃における比抵抗が1.0
×1011Ω・cm以上である圧電磁器組成物である。Further, another example of the piezoelectric ceramic composition of the present invention is the piezoelectric ceramic composition of any of the above-described piezoelectric ceramic compositions, wherein Mn is converted to an oxide represented by MnO with respect to a total amount of 0 to 0.
It is contained at a rate of 0.05 wt% (excluding 0), and has a specific resistance of 1.0 at -40 ° C to 170 ° C.
It is a piezoelectric ceramic composition having × 10 11 Ω · cm or more.
【0023】それでは、本発明の実施の形態について説
明する。Next, an embodiment of the present invention will be described.
【0024】(第1の実施の形態)酸化チタン(TiO
2),酸化ジルコニウム(ZrO2),酸化ニッケル
(NiO),酸化ニオブ(Nb2O5)の原料とPb量
減少させた酸化鉛(PbO)を目標組成となるように秤
量し,これらの原料粉をジルコニアボールとともにアク
リルポット中に入れ,20時間湿式混合した。(First Embodiment) Titanium oxide (TiO)
2 ), raw materials of zirconium oxide (ZrO 2 ), nickel oxide (NiO), niobium oxide (Nb 2 O 5 ) and lead oxide (PbO) with a reduced Pb content are weighed so as to have a target composition, and these raw materials are weighed. The powder was placed in an acrylic pot together with zirconia balls and wet mixed for 20 hours.
【0025】次に,これらの混合粉を脱水乾燥後,アル
ミナこう鉢中で予焼を行ってから,各予焼粉をアクリル
ポット中ジルコニアボールにて15時間湿式粉砕した。
引き続き,脱水乾燥して得られた予焼粉砕粉にバインダ
を混合して加圧し,直径(φ)20×厚み(T)3mm
に成形した。この成形体を1100℃〜1300℃で2
時間焼成し,各焼結体を1mmの厚さに加工した後,両
面に銀ペーストを塗布して450℃で焼き付けて電極を
形成することにより,それぞれ組成の異なる試料とし
た。このようにして得られた各試料を3kV/mm,で
分極処理をし,HP4194Aと恒温槽を使用して,1
kHzの比誘電率εrの温度特性を測定した。温度特性
は,−40℃〜400℃の範囲で5℃〜10℃毎に30
分保持したのち,各温度での1KHzのεrを測定し
た。また,d33(500kV)は,中心点で支持した
前記試料に,等速,2秒間でOV→500V→0Vの電
圧を印加し,試料厚さ方向の変位をフリンジカウンタ式
レーザ変位計を使用して測定して算出した。Next, after dehydrating and drying these mixed powders, they were pre-fired in an alumina mortar, and each pre-fired powder was wet-pulverized with zirconia balls in an acrylic pot for 15 hours.
Subsequently, a binder was mixed with the pre-fired pulverized powder obtained by dehydration and drying, and the mixture was pressurized to give a diameter (φ) of 20 × thickness (T) of 3 mm.
Molded. This molded body is heated at 1100 ° C. to 1300 ° C. for 2 hours.
After firing for a time, each sintered body was processed to a thickness of 1 mm, silver paste was applied to both surfaces and baked at 450 ° C. to form electrodes, thereby obtaining samples having different compositions. Each sample obtained in this way was polarized at 3 kV / mm, and was subjected to a 1
Temperature characteristics of relative permittivity εr of kHz were measured. The temperature characteristics are in the range of -40 ° C to 400 ° C.
After holding for one minute, εr at 1 KHz at each temperature was measured. For d33 (500 kV), a voltage of OV → 500 V → 0 V is applied to the sample supported at the center point at a constant speed for 2 seconds, and the displacement in the sample thickness direction is measured using a fringe counter type laser displacement meter. Was measured and calculated.
【0026】図2は,d33(500kV)の測定例を
示す図である。図2に示すように,厚さ1mmの測定試
料に,500Vの直流電圧印加時(電界強度500kV
/m)の変位量からd33(500kV)を算出した。FIG. 2 is a diagram showing an example of measurement of d33 (500 kV). As shown in FIG. 2, when a DC voltage of 500 V was applied to a measurement sample having a thickness of 1 mm (electric field strength of 500 kV
/ M) was calculated as d33 (500 kV).
【0027】また、下記表1、2の試料1〜26に母成
分とPb減少材料のd33(500kV)と−40℃〜
170℃でのεrの温度変化率を示す。表中、*のつい
た試料No.は,本発明の範囲外を示している。Samples 1 to 26 in Tables 1 and 2 below show the parent component and the d33 (500 kV) of the Pb-reducing material at -40 ° C.
The temperature change rate of εr at 170 ° C. is shown. In the table, sample Nos. Indicates outside the scope of the present invention.
【0028】上記表1より,以下の事が読み取れる。す
なわち,Pb量を減少することで温度特性を維持しつつ
d33(500kV)の向上が認められる。d33(5
00kV)の向上はPb減少量が1.5mol%程度を
ピークとして徐々に低下する。Pb減少量が過剰になる
と試料の焼結性が低下しはじめ,焼結温度の高温化,試
料の特性劣化が生じ好ましくない。試料No.25,2
6は,それぞれd33(500kV)の値が,500p
m/V未満となるため,本発明の範囲に含まれない。こ
れらの結果から,本発明の目標とする特性は,Pb減少
量が0〜3mol%(0は除く)の範囲で達成されるこ
とがわかる。From Table 1 above, the following can be read. That is, an improvement in d33 (500 kV) is observed while maintaining the temperature characteristics by reducing the amount of Pb. d33 (5
The improvement of 00 kV) gradually decreases with the peak amount of Pb decreasing at about 1.5 mol%. If the amount of Pb reduction is excessive, the sinterability of the sample starts to decrease, the sintering temperature increases, and the characteristics of the sample deteriorate, which is not preferable. Sample No. 25,2
6 means that the value of d33 (500 kV) is 500p
Since it is less than m / V, it is not included in the scope of the present invention. From these results, it can be seen that the target characteristics of the present invention are achieved when the Pb reduction amount is in the range of 0 to 3 mol% (excluding 0).
【0029】(第2の実施の形態)酸化鉛(PbO),
酸化チタン(TiO2),酸化ジルコニウム(Zr
O2),酸化ニッケル(NiO),酸化ニオブ(Nb2
O5)の母成分原料と添加物元素として酸化ランタン
(La2O3),酸化ネオジウム(Nd2O3),炭酸
ストロンチウム(SrCO3)を目的組成となるように
秤量し,第1の実施の形態と同様に試料を作成,諸特性
の評価を行った。(Second Embodiment) Lead oxide (PbO),
Titanium oxide (TiO 2 ), zirconium oxide (Zr
O 2 ), nickel oxide (NiO), niobium oxide (Nb 2
O 5) mother ingredient material and additive element as a lanthanum oxide (La 2 O 3) of neodymium oxide (Nd 2 O 3), strontium carbonate (SrCO 3) was weighed so as to target composition, the first embodiment Samples were prepared and various characteristics were evaluated in the same manner as in the above embodiment.
【0030】下記表1及び表2の試料No.27〜39
に,添加物試料のd33(500kV)と,−40℃〜
170℃でのεrの温度変化率を示す。下記表1及び表
2中*のついた試料No.は,本発明の範囲外を示して
いる。下記表1より,以下の事が読み取れる。すなわ
ち,各元素共に添加物量の増加に従いd33(500k
V)の向上が認められると共に,Δεrの値が劣化す
る。過剰にSrを添加した試料No.30はΔεrが3
00%を超えているため本請求範囲より除外される。ま
た,試料No.39は試料作成中に破損し測定できなか
った。Sample Nos. In Tables 1 and 2 below 27-39
In addition, d33 (500 kV) of the additive sample and -40 ° C
The temperature change rate of εr at 170 ° C. is shown. Sample No. marked with * in Tables 1 and 2 below. Indicates outside the scope of the present invention. The following can be read from Table 1 below. In other words, d33 (500 k
V), and the value of Δεr deteriorates. Sample No. to which Sr was excessively added. 30 is Δεr 3
Since it exceeds 00%, it is excluded from the claims. The sample No. Sample No. 39 was damaged during sample preparation and could not be measured.
【0031】(第3の実施の形態)酸化鉛(PbO),
酸化チタン(ZrO2),酸化ジルコニウム(Zr
O2),酸化ニッケル(NiO),酸化ニオブ(Nb2
O5)の母成分原料と添加物元素として酸化ランタン
(La2O3),酸化ネオジウム(Nd2O3),炭酸
ストロンチウム(SrCO3)を目的組成となるように
秤量し第1の実施の形態と同様に試料を作成,諸特性の
評価を行った。下記表2の試料No.40〜64に,試
料のd33(500kV)と,−40℃〜170℃での
εrの温度変化率を示す。表2中*のついた試料No.
は,本発明の範囲外を示している。下記表2より,以下
の事が読み取れる。添加物の添加と共にPb量を減少す
ることで,単純に添加した場合よりも多量の添加物を添
加でき,Δεrの劣化が少ない。また,Pb減少量と添
加量を加算して0.99mol程度のバランスがとれて
いる試料No.42,47,54等では添加量が比較的
少なくても良好なd33(500kV)を示す。(Third Embodiment) Lead oxide (PbO),
Titanium oxide (ZrO 2 ), zirconium oxide (Zr
O 2 ), nickel oxide (NiO), niobium oxide (Nb 2
First, lanthanum oxide (La 2 O 3 ), neodymium oxide (Nd 2 O 3 ), and strontium carbonate (SrCO 3 ) were weighed to obtain the target composition and the additive element of O 5 ). Samples were prepared in the same manner as in the form, and various characteristics were evaluated. Sample No. in Table 2 below. 40 to 64 show d33 (500 kV) of the sample and the temperature change rate of εr at −40 ° C. to 170 ° C. Sample No. marked with * in Table 2
Indicates outside the scope of the present invention. The following can be read from Table 2 below. By decreasing the amount of Pb together with the addition of the additive, a larger amount of the additive can be added as compared with the case where the additive is simply added, and the deterioration of Δεr is small. Further, the sample No. having a balance of about 0.99 mol by adding the Pb reduction amount and the addition amount. 42, 47, 54, etc. show good d33 (500 kV) even if the added amount is relatively small.
【0032】[0032]
【表1】 [Table 1]
【0033】[0033]
【表2】 [Table 2]
【0034】(第4の実施の形態)酸化鉛(PbO),
酸化チタン(TiO2),酸化ジルコニウム(Zr
O2),酸化ニッケル(NiO),酸化ニオブ(Nb2
O5)の母成分原料と添加物元素として酸化ランタン
(La2O3),酸化ネオジウム(Nd2O3),炭酸
ストロンチウム(SrCO3),炭酸マンガン(MnC
O3)を目的組成となるように秤量し,第1の実施の形
態と同様に試料を作成し,−40℃,170℃それぞれ
での比抵抗を測定した。その結果の一例を図3に示す。
図3から,恒温領域では比抵抗が低下するものの,Mn
OとしてMnCO3を極微量添加するだけで,比抵抗が
顕著に向上し,本発明の目標値を満足することがわか
る。また,MnOの添加量は,0.05wt%を超える
と,それ以上の比抵抗向上効果は望め無いことがわかっ
た。MnOの過剰な添加は,圧電定数などの圧電特性を
劣化させる傾向もあるため,0.05wt%以下が,本
発明の目標に対して適当な値であると判断できる。(Fourth Embodiment) Lead oxide (PbO),
Titanium oxide (TiO 2 ), zirconium oxide (Zr
O 2 ), nickel oxide (NiO), niobium oxide (Nb 2
O 5) mother ingredient material and additive element as a lanthanum oxide (La 2 O 3) of neodymium oxide (Nd 2 O 3), strontium carbonate (SrCO 3), manganese carbonate (MnC
O 3 ) was weighed so as to have a target composition, a sample was prepared in the same manner as in the first embodiment, and the specific resistance was measured at −40 ° C. and 170 ° C., respectively. FIG. 3 shows an example of the result.
From FIG. 3, although the specific resistance decreases in the constant temperature region, Mn
It can be seen that the specific resistance is remarkably improved only by adding a very small amount of MnCO 3 as O, and the target value of the present invention is satisfied. Further, it was found that when the amount of MnO added exceeds 0.05 wt%, no further improvement in the specific resistance can be expected. Excessive addition of MnO also tends to degrade the piezoelectric properties such as the piezoelectric constant, so it can be determined that 0.05 wt% or less is an appropriate value for the target of the present invention.
【0035】[0035]
【発明の効果】以上説明したように,本発明において
は,高電圧印加時の圧電歪定数が大きく,かつ,比誘電
率の温度変化が小さく,高温度範囲での電気抵抗率も大
きいことから,広い温度範囲で安定な特性を有するとと
もに絶縁性に優れた圧電磁器組成物を提供でき、アクチ
ュエータ用材料として極めて有用である。As described above, according to the present invention, the piezoelectric strain constant at the time of applying a high voltage is large, the change in the relative dielectric constant with temperature is small, and the electric resistivity in the high temperature range is large. It can provide a piezoelectric ceramic composition having stable characteristics over a wide temperature range and excellent insulation properties, and is extremely useful as a material for an actuator.
【図1】本発明の圧電磁器組成物の母成分の組成を三角
座標で示す図である。FIG. 1 is a diagram showing the composition of a mother component of a piezoelectric ceramic composition of the present invention in triangular coordinates.
【図2】本発明の第1の実施の形態で示した,d33
(500kV)測定方法の概念を示す図であり,印加電
圧と圧電変位の関係を示す図である。FIG. 2 shows d33 shown in the first embodiment of the present invention.
FIG. 4 is a diagram illustrating a concept of a (500 kV) measuring method, and is a diagram illustrating a relationship between an applied voltage and a piezoelectric displacement.
【図3】本発明の第4の実施の形態によるMnO添加量
と,比抵抗の関係を示す図である。FIG. 3 is a diagram showing a relationship between an added amount of MnO and a specific resistance according to a fourth embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 間宮 洋一 宮城県仙台市太白区郡山六丁目7番1号 株式会社トーキン内 (72)発明者 川上 祥広 兵庫県宍粟郡山崎町須賀沢231番地 トー キンセラミクス株式会社内 Fターム(参考) 4G031 AA02 AA05 AA07 AA09 AA11 AA12 AA14 AA19 AA23 AA32 BA09 BA10 GA02 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoichi Mamiya 6-7-1, Koriyama, Taishiro-ku, Sendai, Miyagi Prefecture Tokin Co., Ltd. (72) Inventor Yoshihiro Kawakami 231 Sugazawa, Yamazaki-cho, Shiso-gun, Hyogo Tokin F-term (reference) in Ceramics Co., Ltd. 4G031 AA02 AA05 AA07 AA09 AA11 AA12 AA14 AA19 AA23 AA32 BA09 BA10 GA02
Claims (4)
+cPb(Ni1/ 3Nb2/3)O3(a+b+c=
100)で表され,その組成範囲が,図1のI点(a=
35mol%,b=30mol%,c=35mol
%)、J点(a=44mol%,b=16mol%,c
=40mol%)、K点(a=50mol%,b=40
mol%,c=10mol%)、およびL点(a=40
mol%,b=50mol%,c=10mol%)の各
組成点を結ぶ線上およびこの4点に囲まれた領域とする
範囲を母成分とし,Pb量を0〜3mol%(0を除
く)の範囲で減少させた,分極軸と同一方向に,500
kV/mの直流電界を印加したときの圧電変位が,50
0pm/V以上を示し,かつ,−40℃〜170℃の範
囲で,比誘電率の温度変化が300%以下であることを
特徴とする圧電磁器組成物。1. Composition formula aPbTiO 3 + bPbZrO 3
+ CPb (Ni 1/3 Nb 2/3) O 3 (a + b + c =
100), and the composition range of the point I (a =
35 mol%, b = 30 mol%, c = 35 mol
%), J point (a = 44 mol%, b = 16 mol%, c
= 40 mol%), point K (a = 50 mol%, b = 40)
mol%, c = 10 mol%) and L point (a = 40
mol%, b = 50 mol%, and c = 10 mol%) on the line connecting the respective composition points and the range defined by the area surrounded by these four points is defined as the mother component, and the Pb content is 0 to 3 mol% (excluding 0). Reduced in range, in the same direction as the polarization axis, 500
The piezoelectric displacement when applying a DC electric field of kV / m is 50
A piezoelectric ceramic composition exhibiting 0 pm / V or more, and having a temperature change of relative permittivity of 300% or less in a range of -40 ° C to 170 ° C.
て、母成分に対してLa,Nd等のランタノイド元素お
よびSr等のアルカリ土類元素のうち少なくとも1種を
0〜7mol%(0を除く)の範囲で添加し,かつPb
量を0〜5mol%(0を除く)の範囲で滅少させた,
分極軸と同一方向に,500kV/mの直流電界を印加
したときの圧電変位が,500pm/V以上を示し,か
つ,40℃〜170℃の範囲で,比誘電率の温度変化が
300%以下であることを特徴とする圧電磁器組成物。2. The piezoelectric ceramic composition according to claim 1, wherein at least one of a lanthanoid element such as La and Nd and an alkaline earth element such as Sr is 0 to 7 mol% (excluding 0) based on the mother component. ) And Pb
The amount was reduced in the range of 0 to 5 mol% (excluding 0),
When a DC electric field of 500 kV / m is applied in the same direction as the polarization axis, the piezoelectric displacement shows 500 pm / V or more, and the temperature change of the relative dielectric constant is 300% or less in the range of 40 ° C. to 170 ° C. A piezoelectric ceramic composition characterized by the following.
+cPb(Ni1/ 3Nb2/3)O3(a+b+c=
100)で表され,その組成範囲が,図1のI点(a=
35mol%,b=30mol%,c=35mol
%)、J点(a=44mol%,b=16mol%,c
=40mol%)、K点(a=50mol%,b=40
mol%,c=10mol%)、およびL点(a=40
mol%,b=50mol%,c=10mol%)の各
組成点を結ぶ線上およびこの4点に囲まれた領域とする
範囲を母成分とし,La,Nd等のランタノイド元素お
よびSr等のアルカリ土類元素のうち1種類以上を0〜
5mol%(0を除く)の範囲で添加した,分極軸と同
一方向に,500kV/mの直流電界を印加したときの
圧電変位が,500pm/V以上を示し,かつ,−40
℃〜170℃の範囲で,比誘電率の温度変化が300%
以下であることを特徴とする圧電磁器組成物。3. Composition formula aPbTiO 3 + bPbZrO 3
+ CPb (Ni 1/3 Nb 2/3) O 3 (a + b + c =
100), and the composition range of the point I (a =
35 mol%, b = 30 mol%, c = 35 mol
%), J point (a = 44 mol%, b = 16 mol%, c
= 40 mol%), point K (a = 50 mol%, b = 40)
mol%, c = 10 mol%) and L point (a = 40
mol%, b = 50 mol%, c = 10 mol%) on the line connecting the respective composition points and the range defined by the area surrounded by these four points as mother components, and lanthanoid elements such as La and Nd and alkaline earths such as Sr. One or more of the class elements
When a DC electric field of 500 kV / m is applied in the same direction as the polarization axis in a range of 5 mol% (excluding 0), the piezoelectric displacement is 500 pm / V or more, and -40.
Temperature change of relative permittivity is 300% in the range of ℃ ~ 170 ℃
A piezoelectric ceramic composition characterized by the following.
圧電磁器組成物において、総量に対して,MnをMnO
で表される酸化物に換算して,0〜0.05wt%(0
は含まない)の割合で含有し,−40℃〜170℃にお
ける比抵抗が1.0×1011Ω・cm以上であること
を特徴とする圧電磁器組成物。4. The piezoelectric ceramic composition according to claim 1, wherein Mn is MnO based on the total amount.
0 to 0.05 wt% (0
Wherein the specific resistance at −40 ° C. to 170 ° C. is 1.0 × 10 11 Ω · cm or more.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1400498A2 (en) * | 2002-07-29 | 2004-03-24 | Brother Kogyo Kabushiki Kaisha | Piezoelectric ceramic composition and piezolelectric actuator for ink-jet head |
WO2006038389A1 (en) * | 2004-10-01 | 2006-04-13 | Murata Manufacturing Co., Ltd | Piezoelectric porcelain composition and piezoelectric ceramic electronic component |
WO2006103143A1 (en) * | 2005-03-31 | 2006-10-05 | Siemens Aktiengesellschaft | Piezoceramic, piezoelectric component containing same and method for producing the piezoceramic |
US7362039B2 (en) | 2005-03-22 | 2008-04-22 | Seiko Epson Corporation | Piezoelectric element, method of manufacturing the same, liquid-jet head, method of manufacturing the same, and liquid-jet apparatus |
US7431785B2 (en) | 2002-07-25 | 2008-10-07 | Murata Manufacturing Co., Ltd. | Manufacturing method for monolithic piezoelectric part, and monolithic piezoelectric part |
US7498724B2 (en) | 2005-03-22 | 2009-03-03 | Seiko Epson Corporation | Piezoelectric element, liquid-jet head and liquid-jet apparatus |
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JPS60103079A (en) * | 1983-11-05 | 1985-06-07 | 住友特殊金属株式会社 | Piezoelectric ceramic composition |
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JPS60103079A (en) * | 1983-11-05 | 1985-06-07 | 住友特殊金属株式会社 | Piezoelectric ceramic composition |
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---|---|---|---|---|
US7431785B2 (en) | 2002-07-25 | 2008-10-07 | Murata Manufacturing Co., Ltd. | Manufacturing method for monolithic piezoelectric part, and monolithic piezoelectric part |
EP1400498A2 (en) * | 2002-07-29 | 2004-03-24 | Brother Kogyo Kabushiki Kaisha | Piezoelectric ceramic composition and piezolelectric actuator for ink-jet head |
EP1400498A3 (en) * | 2002-07-29 | 2004-06-09 | Brother Kogyo Kabushiki Kaisha | Piezoelectric ceramic composition and piezolelectric actuator for ink-jet head |
US6844661B2 (en) | 2002-07-29 | 2005-01-18 | Brother Kogyo Kabushiki Kaisha | Piezoelectric ceramic composition and piezoelectric actuator for ink-jet head based on use of the same |
JPWO2006038389A1 (en) * | 2004-10-01 | 2008-05-15 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric ceramic electronic component |
WO2006038389A1 (en) * | 2004-10-01 | 2006-04-13 | Murata Manufacturing Co., Ltd | Piezoelectric porcelain composition and piezoelectric ceramic electronic component |
US7504042B2 (en) | 2004-10-01 | 2009-03-17 | Murata Manufacturing Co., Ltd. | Piezoelectric ceramic composition and piezoelectric ceramic electronic component |
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JP4650695B2 (en) * | 2004-10-01 | 2011-03-16 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric ceramic electronic component |
US7362039B2 (en) | 2005-03-22 | 2008-04-22 | Seiko Epson Corporation | Piezoelectric element, method of manufacturing the same, liquid-jet head, method of manufacturing the same, and liquid-jet apparatus |
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WO2006103143A1 (en) * | 2005-03-31 | 2006-10-05 | Siemens Aktiengesellschaft | Piezoceramic, piezoelectric component containing same and method for producing the piezoceramic |
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