JP2001097774A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
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- JP2001097774A JP2001097774A JP27959899A JP27959899A JP2001097774A JP 2001097774 A JP2001097774 A JP 2001097774A JP 27959899 A JP27959899 A JP 27959899A JP 27959899 A JP27959899 A JP 27959899A JP 2001097774 A JP2001097774 A JP 2001097774A
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- Prior art keywords
- piezoelectric
- temperature
- mol
- piezoelectric ceramic
- curie temperature
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えばセラミック
フィルタ、超音波応用振動子、圧電ブザー、圧電点火ユ
ニット、超音波モータ、圧電ファン、および、加速度セ
ンサ、ノッキングセンサ、ＡＥセンサなどで、特に圧電
アクチュエータに適する圧電磁器を作製するための組成
物に関する。The present invention relates to, for example, ceramic filters, ultrasonic transducers, piezoelectric buzzers, piezoelectric ignition units, ultrasonic motors, piezoelectric fans, acceleration sensors, knocking sensors, AE sensors, and the like. The present invention relates to a composition for producing a piezoelectric ceramic suitable for an actuator.
【０００２】[0002]
【従来技術】近年、インクジェクター用プリンターヘッ
ドや車載用の燃料噴射弁等の高速連続駆動が要求される
用途に対して圧電アクチュエータの応用が広がりつつあ
る。この圧電アクチュエータは、圧電体に電圧を印可し
て圧電体が歪む逆圧電効果を利用するものであり、圧電
歪定数の大きな圧電磁器が要求されている。2. Description of the Related Art In recent years, piezoelectric actuators have been increasingly used for applications requiring high-speed continuous driving, such as a printer head for an ink jet or a fuel injection valve for a vehicle. This piezoelectric actuator utilizes an inverse piezoelectric effect in which a voltage is applied to the piezoelectric body to distort the piezoelectric body, and a piezoelectric ceramic having a large piezoelectric distortion constant is required.
【０００３】圧電アクチュエータの誘電率はキュリー温
度付近で爆発的に増大し、その結果、駆動時の応答速度
が極度に低下する。特に、燃料噴射弁に圧電アクチュエ
ータを使用する場合、高い雰囲気温度に加えて、連続駆
動による自己発熱が加わり、アクチュエータが２００℃
程度の高温に曝される危険性があり、キュリー温度付近
の急激な誘電率上昇を避ける為に、圧電磁器はこれまで
以上に高いキュリー温度が求められている。[0003] The dielectric constant of a piezoelectric actuator explosively increases near the Curie temperature, and as a result, the response speed during driving is extremely reduced. In particular, when a piezoelectric actuator is used for a fuel injection valve, self-heating is caused by continuous driving in addition to a high ambient temperature, and the actuator is operated at 200 °
There is a danger of exposure to such a high temperature, and piezoelectric ceramics are required to have a higher Curie temperature than ever before in order to avoid a rapid rise in dielectric constant near the Curie temperature.
【０００４】さらに、圧電アクチュエータの小型化、低
電圧駆動を可能ならしめるためには、薄層磁器と内部電
極との同時焼成をすることが容易に考えられるが、焼成
温度を１０００℃以下に低下させることによって、鉛の
飛散を抑えることによる特性の安定化を図ることができ
る。また、１０００℃以下の焼成温度にすると鉛の大気
中への飛散が大幅に削減でき、環境汚染の観点でも好ま
しい。しかし、１０００℃以下で焼成すると、磁器の緻
密化が十分進まず、圧電特性が低下するという問題があ
った。Further, in order to make the piezoelectric actuator smaller and to be driven at a lower voltage, simultaneous firing of the thin-layer ceramic and the internal electrode is easily considered. However, the firing temperature is reduced to 1000 ° C. or less. By doing so, the characteristics can be stabilized by suppressing the scattering of lead. When the firing temperature is 1000 ° C. or lower, the scattering of lead into the air can be greatly reduced, which is preferable from the viewpoint of environmental pollution. However, when firing at 1000 ° C. or lower, there has been a problem that the densification of the porcelain does not proceed sufficiently and the piezoelectric characteristics are reduced.
【０００５】そこで、キュリー温度を高く維持するとと
もに、圧電歪定数を大きくするために、従来からＰｂ(
Ｚｒ，Ｔｉ）Ｏ3 （ＰＺＴ、ジルコン酸チタン酸鉛）に
キュリー温度が１４０℃と比較的高い複合ペロブスカイ
ト化合物Ｐｂ（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 を固溶させるこ
とによって優れた圧電特性と高いキュリー温度とを有す
る圧電材料が開示されている。In order to keep the Curie temperature high and to increase the piezoelectric distortion constant, Pb (
An excellent piezoelectric material is obtained by dissolving a complex perovskite compound Pb (Zn 1/3 Nb 2/3 ) O 3 having a relatively high Curie temperature of 140 ° C. in Zr, Ti) O 3 (PZT, lead zirconate titanate). Piezoelectric materials having properties and high Curie temperatures are disclosed.
【０００６】例えば、ＰｂＺｒＯ3 −ＰｂＴｉＯ3 （ジ
ルコン酸チタン酸鉛）に複合ペロブスカイト化合物Ｐｂ
（Ｚｎ1/3 Ｎｂ2/3 ）を固溶させ、Ｐｂサイトの一部を
Ｌａ等の希土類元素やアルカリ土類元素で置換すること
によって２００℃程度の比較的高いキュリー温度と大き
な圧電歪定数を合わせ持つ組成物が開示されている（特
開平６−２４８４１号公報）。For example, PbZrO 3 —PbTiO 3 (lead zirconate titanate) is combined with a composite perovskite compound Pb
(Zn 1/3 Nb 2/3 ) is dissolved, and a part of the Pb site is replaced by a rare earth element such as La or an alkaline earth element, so that a relatively high Curie temperature of about 200 ° C. and a large piezoelectric strain constant are obtained. (JP-A-6-24841).
【０００７】一方、焼結温度を低下させた材料として、
Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3 −Ｐｂ（Ｍｎ1/3 Ｓｂ2/3 ）Ｏ
3 −Ｐｂ（Ｚｎ1/3 Ｎｂ2/3 ) Ｏ3 系圧電磁器材料が、
特開平９−１９４２５８号公報に開示されている。On the other hand, as a material whose sintering temperature is lowered,
Pb (Zr, Ti) O 3 -Pb (Mn 1/3 Sb 2/3 ) O
3- Pb (Zn 1/3 Nb 2/3 ) O 3 piezoelectric ceramic material is
It is disclosed in JP-A-9-194258.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、特開平
６−２４８４１号公報で開示されているＰｂ（Ｚｎ1/3
Ｎｂ2/3 ) Ｏ3 を固溶させたジルコン酸チタン酸鉛で
は、大きな圧電歪定数を有しているがキュリー温度は、
最大２１０℃と燃料噴射弁用の圧電アクチュエータとし
ては不十分あった。さらに、この組成では１０００℃以
下の焼成で密度が低くなり特性がさらに悪化するという
問題があった。However, Pb (Zn 1/3 ) disclosed in Japanese Patent Application Laid-Open No.
Nb 2/3 ) O 3 in a solid solution of lead zirconate titanate has a large piezoelectric strain constant, but the Curie temperature is
The maximum temperature of 210 ° C. was insufficient for a piezoelectric actuator for a fuel injection valve. Further, with this composition, there was a problem that the density was lowered by firing at 1000 ° C. or lower, and the characteristics were further deteriorated.
【０００９】また、特開平９−１９４２５８号公報の圧
電磁器材料は、１０００℃以下での低温焼成を可能とし
た上でキュリー温度も最大３００℃程度と非常に優れた
特性を有しているものの、キュリー温度が２５０℃以上
になると圧電歪定数が４００ｐｐｍ／Ｖ以下となり大き
な歪みを確保することができなかった。Further, the piezoelectric ceramic material disclosed in Japanese Patent Application Laid-Open No. 9-194258 has a very excellent property of being capable of firing at a low temperature of 1000 ° C. or less and having a Curie temperature of about 300 ° C. at the maximum. When the Curie temperature was 250 ° C. or higher, the piezoelectric strain constant was 400 ppm / V or lower, and large strain could not be secured.
【００１０】このように、圧電歪定数の大きな材料は、
キュリー温度が低下してしまう傾向があり、そのため応
答性が極端に悪化して実用上問題となり、低温焼成の可
能な組成で、かつ高い圧電歪み定数とキュリー温度を実
現した圧電磁器を実現することは困難であった。Thus, a material having a large piezoelectric strain constant is
The Curie temperature tends to decrease, resulting in extremely poor responsiveness, which poses a practical problem.A piezoelectric ceramic with a composition that can be fired at low temperatures, and that has a high piezoelectric strain constant and Curie temperature has been realized. Was difficult.
【００１１】したがって、本発明では、キュリー温度お
よび圧電歪定数が優れていることに加え、１０００℃以
下の焼結温度が可能な圧電磁器組成物を提供することを
目的としている。Accordingly, it is an object of the present invention to provide a piezoelectric ceramic composition which has excellent Curie temperature and piezoelectric strain constant and can be sintered at a temperature of 1000 ° C. or lower.
【００１２】[0012]
【課題を解決するための手段】本発明の圧電磁器組成物
は、Ｐｂ( Ｚｒ，Ｔｉ）Ｏ3 からなる主成分に対して、
副成分としてＰｂ（Ｙｂ1/2 Ｎｂ1/2 ）Ｏ3 と、Ｐｂ(
Ｃｏ1/3 Ｎｂ2/3 ) Ｏ 3 と、Ｐｂ（Ｚｎ1/3 Ｎｂ2/3 ）
Ｏ3 、Ｐｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 の少なくとも１種
とが固溶してなるＡＢＯ3 型ペロブスカイト型複合酸化
物からなることを特徴とする。Means for Solving the Problems The piezoelectric ceramic composition of the present invention
Is Pb (Zr, Ti) OThreeFor the main component consisting of
Pb (Yb1/2Nb1/2) OThreeAnd Pb (
Co1/3Nb2/3) O ThreeAnd Pb (Zn1/3Nb2/3)
OThree, Pb (Zn1/3Sb2/3) OThreeAt least one of
ABO with solid solutionThree-Type perovskite-type composite oxidation
It is characterized by consisting of things.
【００１３】このように、主成分のＰｂ( Ｚｒ，Ｔｉ）
Ｏ3 に、少なくとも３種類のＡＢＯ3 型ペロブスカイト
型複合酸化物を固溶させることにより、キュリー温度を
高く維持しつつ圧電歪定数を大きくできるとともに、焼
成温度を１０００℃以下にできるため、電極との同時焼
成を可能にし、環境の鉛汚染を低減することができる。
その結果、応答速度の温度変化を小さくでき、安定して
特性が得られる。Thus, the main component Pb (Zr, Ti)
By forming at least three kinds of ABO 3 type perovskite-type composite oxides into solid solution in O 3 , the piezoelectric strain constant can be increased while the Curie temperature is kept high, and the firing temperature can be reduced to 1000 ° C. or less. At the same time, and lead pollution in the environment can be reduced.
As a result, the temperature change of the response speed can be reduced, and characteristics can be obtained stably.
【００１４】また、副成分の含有量を全量中１０〜２０
モル％とすることが、さらに圧電歪み定数とキュリー温
度を向上させるので好ましい。Further, the content of the auxiliary component is set to 10 to 20 in the total amount.
Molar% is preferable because the piezoelectric strain constant and the Curie temperature are further improved.
【００１５】さらに、Ａサイト中にアルカリ土類元素お
よび／または希土類元素を８モル％以下の割合で含有さ
せることが、圧電歪み定数を向上させるうえで好まし
い。Further, it is preferable that the site A contains an alkaline earth element and / or a rare earth element at a ratio of 8 mol% or less from the viewpoint of improving the piezoelectric strain constant.
【００１６】また、Ｂサイト中にＮｂを１モル％以下の
割合で含有させることが、圧電歪み定数を向上させるう
えで好ましい。Further, it is preferable that Nb be contained in the B site at a ratio of 1 mol% or less in order to improve the piezoelectric strain constant.
【００１７】さらに、副成分であるＰｂ（Ｚｎ1/3 Ｎｂ
2/3 ）Ｏ3 および／またはＰｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ
3 の少なくとも一部をＰｂ（Ｆｅ2/3 Ｗ1/3 ）Ｏ3 で置
換することが、圧電磁器の圧電歪定数を維持したまま、
さらに焼成温度を低下させることができるので、好まし
い。Furthermore, Pb (Zn 1/3 Nb)
2/3 ) O 3 and / or Pb (Zn 1/3 Sb 2/3 ) O
Replacing at least a part of 3 with Pb (Fe 2/3 W 1/3 ) O 3 can maintain the piezoelectric strain constant of the piezoelectric ceramic,
This is preferable because the firing temperature can be further reduced.
【００１８】[0018]
【発明の実施の形態】本発明の圧電磁器組成物は、ＡＢ
Ｏ3 型ペロブスカイト型複合酸化物で広く用いられてい
るＰｂ( Ｚｒ，Ｔｉ）Ｏ3 （以下、ＰＺＴと記する場合
もある。）を主成分とすることによって、キュリー温度
を高く維持することができる。しかし、ＰＺＴは、１０
００℃以下の温度では焼成できず、また、圧電歪み定数
が小さい。BEST MODE FOR CARRYING OUT THE INVENTION The piezoelectric ceramic composition of the present invention comprises AB
By using Pb (Zr, Ti) O 3 (hereinafter sometimes referred to as PZT) as a main component, which is widely used in O 3 -type perovskite-type composite oxides, the Curie temperature can be kept high. it can. However, PZT is 10
At temperatures below 00 ° C., sintering is not possible, and the piezoelectric strain constant is small.
【００１９】これに対し、本発明に従い、Ｐｂ( Ｚｒ，
Ｔｉ）Ｏ3 にＰｂ（Ｙｂ1/2 Ｎｂ1/2 ）Ｏ3 およびＰｂ
( Ｃｏ1/3 Ｎｂ2/3 ) Ｏ3 を固溶させることにより、焼
成温度温度の低温化が可能となる。また、合わせてＰｂ
（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 、Ｐｂ（Ｚｎ1/3 Ｓｂ2/3 ）
Ｏ3 の少なくとも１種を添加することにより、１０００
℃以下の温度で焼成が可能となり、圧電歪み定数を高め
ることができる。On the other hand, according to the present invention, Pb (Zr,
Ti) O 3 with Pb (Yb 1/2 Nb 1/2 ) O 3 and Pb
By making (Co 1/3 Nb 2/3 ) O 3 a solid solution, the firing temperature can be lowered. Also, Pb
(Zn 1/3 Nb 2/3 ) O 3 , Pb (Zn 1/3 Sb 2/3 )
By adding at least one of O 3 , 1000
Baking can be performed at a temperature of not more than ° C., and the piezoelectric distortion constant can be increased.
【００２０】副成分を個々に添加しても、キュリー温
度、圧電歪み定数および焼成温度を十分に改善できない
が、上記のように少なくとも特定の３種のＡＢＯ3 型ペ
ロブスカイト型複合酸化物を固溶させることにより、こ
れらの特性を同時に改善することができる。なお、Ｐｂ
( Ｚｒ，Ｔｉ）Ｏ3 は、ＰｂＺｒＯ3 とＰｂＴｉＯ3 と
の固溶体であり、ＰｂＺｒＯ3 は４５乃至５０モル％、
ＰｂＴｉＯ3 は５０乃至５５モル％であることが望まし
い。Although the Curie temperature, the piezoelectric strain constant and the firing temperature cannot be sufficiently improved by adding individual subcomponents, at least three specific ABO 3 -type perovskite-type composite oxides are dissolved as described above. By doing so, these characteristics can be simultaneously improved. Note that Pb
(Zr, Ti) O 3 is a solid solution of PbZrO 3 and PbTiO 3 , wherein PbZrO 3 is 45 to 50 mol%,
PbTiO 3 is desirably 50 to 55 mol%.
【００２１】したがって、ＰＺＴをベースとし、Ｂサイ
トの一部を（Ｙｂ1/2 Ｎｂ1/2 ）と、( Ｃｏ1/3 Ｎｂ
2/3 ) と、（Ｚｎ1/3 Ｎｂ2/3 ）、（Ｚｎ1/3 Ｓ
ｂ2/3 ）のうち少なくとも１種で置換することで、高い
キュリー温度で、大きな圧電定数を有し、低い焼成温度
が実現できる。Therefore, based on PZT, a part of the B site is (Yb 1/2 Nb 1/2 ) and (Co 1/3 Nb
2/3 ), (Zn 1/3 Nb 2/3 ), (Zn 1/3 S
By substituting at least one of b 2/3 ), a high Curie temperature, a large piezoelectric constant, and a low firing temperature can be realized.
【００２２】特に、上記副成分の含有量が、全量中１０
モル％未満では圧電歪定数向上の効果が顕著ではなく、
２０モル％以上より多いとＰＺＴの割合が少なくなり、
ＰＺＴ自体の有する高いキュリー温度が低下してしまう
恐れがある。したがって、副成分の含有量を、全量中１
０〜２０モル％とすることにより、高いキュリー温度と
大きな圧電歪定数を同時に達成することができる。Particularly, when the content of the above-mentioned subcomponent is 10% of the total amount,
If it is less than mol%, the effect of improving the piezoelectric strain constant is not remarkable,
If it is more than 20 mol%, the proportion of PZT decreases,
The high Curie temperature of PZT itself may be lowered. Therefore, the content of the sub-component should be 1% of the total amount.
By setting the content to 0 to 20 mol%, a high Curie temperature and a large piezoelectric strain constant can be simultaneously achieved.
【００２３】なお、Ｐｂ（Ｙｂ1/2 Ｎｂ1/2 ）Ｏ3 は３
〜８モル％、Ｐｂ( Ｃｏ1/3 Ｎｂ2/3 ) Ｏ3 は３〜６モ
ル％、Ｐｂ（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 またはＰｂ（Ｚｎ
1/3Ｓｂ2/3 ）Ｏ3 は３〜９モル％が好適である。Note that Pb (Yb 1/2 Nb 1/2 ) O 3 is 3
８8 mol%, Pb (Co 1/3 Nb 2/3 ) O 3 is 3-6 mol%, and Pb (Zn 1/3 Nb 2/3 ) O 3 or Pb (Zn
1/3 Sb 2/3 ) O 3 is preferably 3 to 9 mol%.
【００２４】さらに、Ａサイト中にＣａ、Ｓｒ、Ｂａな
どのアルカリ土類元素および／またはＹ、Ｌａ、Ｃｅ、
Ｎｄ、Ｓｍ、Ｅｒ、Ｙｂ、Ｌｕなどの希土類元素を８モ
ル％以下の割合で含有させると、さらに圧電歪定数を高
めることができる。すなわち、ｄ33を３３方向の圧電歪
定数、Ｋ33を３３方向の電気機械結合係数、ε33 T を３
３方向の誘電率、Ｓ33 E をコンプライアンスとした時
に、圧電歪定数は、ｄ33＝Ｋ33（ε33 T ・Ｓ33 E ）1/2
で表されるため、Ａサイト中にアルカリ土類元素および
／または希土類元素を８モル％以下の割合で含有させる
と、ε33を高める効果が大きいため、その結果ｄ33を大
きくすることができる。しかし、Ａサイト中にアルカリ
土類元素および／または希土類元素を、８モル％を越え
る割合で含有させると、高いキュリー温度が得られなく
なってしまう。Further, in the A site, alkaline earth elements such as Ca, Sr and Ba and / or Y, La, Ce,
When a rare earth element such as Nd, Sm, Er, Yb, or Lu is contained at a ratio of 8 mol% or less, the piezoelectric strain constant can be further increased. That is, d 33 is the piezoelectric strain constant in the 33 direction, K 33 is the electromechanical coupling coefficient in the 33 direction, and ε 33 T is 3
When the dielectric constant in three directions, S 33 E , is defined as compliance, the piezoelectric strain constant is d 33 = K 33 (ε 33 T · S 33 E ) 1/2.
When an alkaline earth element and / or a rare earth element is contained in the A site at a ratio of 8 mol% or less, the effect of increasing ε 33 is large, and as a result, d 33 can be increased. . However, if an alkaline earth element and / or a rare earth element is contained in the A site at a ratio exceeding 8 mol%, a high Curie temperature cannot be obtained.
【００２５】さらにまた、Ｂサイト中にＮｂを１モル％
以下の割合で含有させると、Ｋ33を大きくし、その結果
ｄ33を大きくすることができる。しかし、Ｂサイト中に
Ｎｂを１モル％を越える割合で含有させるとその効果が
低下し、大きなＫ33が得られない。Further, 1 mol% of Nb is contained in the B site.
The inclusion in the following proportions by increasing the K 33, it is possible to increase the resulting d 33. However, the inclusion in a proportion exceeding 1 mole% of Nb in the B site decreases its effect, a large K 33 can not be obtained.
【００２６】また、副成分であるＰｂ（Ｚｎ1/3 Ｎｂ
2/3 ）Ｏ3 および／またはＰｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ
3 の少なくとも一部をＰｂ（Ｚｎ1/2 Ｗ1/2 ）Ｏ3 で置
換すると、ε33を高めるとともに、焼成温度を低下させ
る効果が著しくなる。Pb (Zn 1/3 Nb)
2/3 ) O 3 and / or Pb (Zn 1/3 Sb 2/3 ) O
When at least a part of 3 is substituted with Pb (Zn 1/2 W 1/2 ) O 3 , the effect of increasing ε 33 and lowering the firing temperature becomes remarkable.
【００２７】なお、副成分についてはＰｂ（Ｙｂ1/2 Ｎ
ｂ1/2 ）Ｏ3 、Ｐｂ( Ｃｏ1/3 Ｎｂ2/3 ) Ｏ3 、Ｐｂ
（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 、Ｐｂ（Ｚｎ1/3 Ｓｂ2/3 ）
Ｏ3 またはＰｂ（Ｆｅ1/3 Ｗ1/2 ）Ｏ3 以外のＰｂ系Ａ
ＢＯ3 型ペロブスカイト型複合酸化物を固溶しても良い
が、６モル％以下であれば特に問題はない。The sub-component is Pb (Yb 1/2 N
b 1/2 ) O 3 , Pb (Co 1/3 Nb 2/3 ) O 3 , Pb
(Zn 1/3 Nb 2/3 ) O 3 , Pb (Zn 1/3 Sb 2/3 )
Pb-based A other than O 3 or Pb (Fe 1/3 W 1/2 ) O 3
The BO 3 -type perovskite-type composite oxide may be dissolved in solid solution, but there is no particular problem as long as it is 6 mol% or less.
【００２８】特に、本発明の圧電磁器組成物によれば、
全体組成として、Ｐｂa-x Ｂａx （Ｙｂ1/2 Ｎｂ1/2 ）
b ( Ｚｎ1/3 Ｎｂ2/3 ) c ( Ｃｏ1/3 Ｎｂ2/3 ) d Ｎｂ
y （Ｚｒe Ｔｉ1-e )1-b-c-d-yＯ3 で表わした時、前記
ａ、ｂ、ｃ、ｄ、ｅ、ｘおよびｙが、０．９９５≦ａ≦
１．００５、０．０３≦ｂ≦０．０８、０．０３≦ｃ≦
０．０９、０．０８≦ｂ＋ｃ≦０．１５、０．０３≦ｄ
≦０．０６、０．１０≦ｂ＋ｃ＋ｄ≦０．２、０．４５
≦ｅ≦０．５、ｘ≦０．０８、ｙ≦０．０１を満たすこ
とで、１０００℃以下の低い焼成温度が可能となり、か
つキュリー温度と圧電歪定数を顕著に高めることができ
る。In particular, according to the piezoelectric ceramic composition of the present invention,
Overall composition, Pb ax Ba x (Yb 1/2 Nb 1/2)
b (Zn 1/3 Nb 2/3 ) c (Co 1/3 Nb 2/3 ) d Nb
When expressed in y (Zr e Ti 1-e ) 1-bcdy O 3, wherein a, b, c, d, e, x and y are, 0.995 ≦ a ≦
1.005, 0.03 ≦ b ≦ 0.08, 0.03 ≦ c ≦
0.09, 0.08 ≦ b + c ≦ 0.15, 0.03 ≦ d
≦ 0.06, 0.10 ≦ b + c + d ≦ 0.2, 0.45
By satisfying .ltoreq.e.ltoreq.0.5, x.ltoreq.0.08, and y.ltoreq.0.01, a low firing temperature of 1000.degree.
【００２９】本発明の圧電磁器組成物は以下のように製
造することができる。原料粉末として、例えばＰｂ3 Ｏ
4 、ＺｒＯ2 、ＴｉＯ2 、ＢａＣＯ3 、ＺｎＯ、Ｎｂ2
Ｏ5、Ｙｂ2 Ｏ3 、Ｓｂ2 Ｏ3 およびＣｏ3 Ｏ4 の各原
料粉末を所定量秤量し、ボールミル等で１０〜２４時間
湿式混合し、次いで、この混合物を脱水、乾燥した後、
７００〜９００℃で２〜３時間仮焼して得られた仮焼物
を再びボールミル等で湿式粉砕した後、この粉砕物に有
機バインダーを混合し、造粒して得られる。得られた粉
末を所定の圧力でプレス成形を行い脱バイ、焼成するこ
とにより得られる。The piezoelectric ceramic composition of the present invention can be manufactured as follows. As a raw material powder, for example, Pb 3 O
4 , ZrO 2 , TiO 2 , BaCO 3 , ZnO, Nb 2
A predetermined amount of each raw material powder of O 5 , Yb 2 O 3 , Sb 2 O 3 and Co 3 O 4 is weighed and wet-mixed with a ball mill or the like for 10 to 24 hours, and then the mixture is dehydrated and dried.
The calcined material obtained by calcining at 700 to 900 ° C. for 2 to 3 hours is wet-pulverized again by a ball mill or the like, and then the pulverized material is mixed with an organic binder and granulated. It is obtained by subjecting the obtained powder to press molding at a predetermined pressure, removing the binder, and firing.
【００３０】本発明の圧電磁器組成物は径方向の電気機
械結合係数Ｋr も大きくすることができるため、フィル
ターや圧電ブザーなどにも使用することができる。Since the piezoelectric ceramic composition of the present invention can increase the electromechanical coupling coefficient K r in the radial direction, it can be used for a filter, a piezoelectric buzzer, and the like.
【００３１】なお、本発明における圧電組成物はＡＢＯ
3 で表わされるペロブスカイト型結晶を主結晶相とする
ものであるが、他の結晶相としてパイロクロア相等が少
々存在していてもよい。また、Ａｌ、Ｓ、Ｃｌ、Ｅｕ、
Ｙ、Ｋ、Ｐ、Ｃｕ、Ｍｇ、Ｓｉ等が不可避不純物として
混入する場合もあるが、特性上は何ら問題はない。In the present invention, the piezoelectric composition is ABO
Although the perovskite-type crystal represented by 3 has a main crystal phase, a pyrochlore phase or the like may be slightly present as another crystal phase. Al, S, Cl, Eu,
Y, K, P, Cu, Mg, Si and the like may be mixed as unavoidable impurities, but there is no problem in characteristics.
【００３２】[0032]
【実施例】実施例１ 原料粉末として高純度のＰｂ3 Ｏ4 、ＺｒＯ2 、ＴｉＯ
2 、ＢａＣＯ3 、ＺｎＯ、Ｎｂ2 Ｏ5 、Ｙｂ2 Ｏ3 およ
びＣｏ3 Ｏ4 の各原料粉末を所定量秤量し、ボールミル
等で１８時間湿式で混合し、次いで、この混合物を脱
水、乾燥した後で、７００〜９００℃で２時間仮焼し、
当該仮焼物を再びボールミル等で湿式粉砕する。Example 1 High-purity Pb 3 O 4 , ZrO 2 , and TiO 2 were used as raw material powders.
2 , a predetermined amount of each raw material powder of BaCO 3 , ZnO, Nb 2 O 5 , Yb 2 O 3 and Co 3 O 4 was weighed and mixed by a ball mill or the like for 18 hours in a wet manner, and then the mixture was dehydrated and dried. Later, calcined at 700-900 ° C for 2 hours,
The calcined product is wet-pulverized again by a ball mill or the like.
【００３３】その後、この粉砕物に有機バインダーを混
合し、造粒した。得られた粉末を１．５ｔｏｎ／ｃｍ2
の圧力で円柱形状となるようにプレス成形を行い、１０
００℃で焼成を３時間行った。純粋なＰＺＴは、１００
０℃では通常焼結せず、相対密度が７５％と低く使用で
きるものは得られなかった。しかし、本発明の圧電磁器
組成物の焼結体は１０００℃の焼成温度にもかかわら
ず、すべて９９％以上の相対密度を有しており、緻密で
あることがわかった。Thereafter, an organic binder was mixed with the pulverized product and granulated. 1.5 ton / cm 2 of the obtained powder
Press forming into a columnar shape with pressure of 10
Baking was performed at 00 ° C. for 3 hours. Pure PZT is 100
At 0 ° C., sintering was not usually performed, and a material having a relative density as low as 75% could not be obtained. However, the sintered bodies of the piezoelectric ceramic composition of the present invention all had a relative density of 99% or more despite the firing temperature of 1000 ° C., and were found to be dense.
【００３４】圧電歪定数の評価試料は直径３ｍｍ、長さ
５ｍｍの円柱状となるよう焼結体を研磨加工を行い、両
面にそれぞれ銀電極を焼き付け、８０℃のシリコンオイ
ル中で１．５ｋＶ／ｍｍの直流電界を印加することで分
極処理を行い、分極処理された円柱状試料を２４時間放
置した。このようにして得られた磁器について電子材料
工業会の規格に基づきｄ33の評価を行った。The sample for evaluation of the piezoelectric strain constant was polished on a sintered body so as to have a cylindrical shape with a diameter of 3 mm and a length of 5 mm, and silver electrodes were baked on both sides, respectively, and 1.5 kV / The polarization treatment was performed by applying a DC electric field of 2 mm, and the polarized cylindrical sample was left for 24 hours. For porcelain obtained in this way were evaluated in the d 33 on the basis of the electronic materials Industry Association standards.
【００３５】また、キュリー温度（Ｔc ）の算出は、静
電容量の温度依存性をマルチメーターで測定し、最大値
を示す温度をキュリー温度とした。In calculating the Curie temperature (T c ), the temperature dependence of the capacitance was measured with a multimeter, and the temperature showing the maximum value was defined as the Curie temperature.
【００３６】これらの結果を表１に示した。なお、表１
中のｘ，ｙ，ａ，ｂ，ｃ，ｄおよびｅは、Ｐｂa-x Ｂａ
x （Ｙｂ1/2 Ｎｂ1/2 ）b ( Ｚｎ1/3 Ｎｂ2/3 ) c ( Ｃ
ｏ1/3 Ｎｂ2/3 ) d Ｎｂy （Ｚｒe Ｔｉ1-e )1-b-c-d-y
Ｏ3 で表わした組成式で与えられる原子比を百分率換算
したものである。The results are shown in Table 1. Table 1
X, y, a, b, c, d and e in the above are Pba x Ba
x (Yb 1/2 Nb 1/2 ) b (Zn 1/3 Nb 2/3 ) c (C
o 1/3 Nb 2/3) d Nb y (Zr e Ti 1-e) 1-bcdy
The atomic ratio given by the composition formula represented by O 3 is converted into a percentage.
【００３７】[0037]
【表１】 [Table 1]
【００３８】本発明の試料Ｎｏ．１〜２１、２６および
２７は、いずれも焼成温度１０００℃で緻密な焼結体が
得られ、ｄ33が４００ｐｍ／Ｖ以上、Ｔc が２５０℃以
上と大きな値が得られた。Sample No. of the present invention 1～21,26 and 27 are both dense sintered body is obtained at a firing temperature 1000 ° C., d 33 is 400 pm / V or more, T c was obtained high as 250 ° C. or higher.
【００３９】一方、Ｐｂ（Ｙｂ1/2 Ｎｂ1/2 ）Ｏ3 の添
加していない試料Ｎｏ．２２はｄ33が５３０ｐｍ／Ｖと
高いものの、Ｔc が２００℃と低かった。また、Ｐｂ
（Ｃｏ1/3 Ｎｂ2/3 ）Ｏ3 とＰｂ（Ｚｎ1/3 Ｎｂ2/3 ）
Ｏ3 との添加してない試料Ｎｏ．２３，Ｐｂ( Ｃｏ1/3
Ｎｂ2/3 ) Ｏ3 の添加していない試料Ｎｏ．２４、およ
びＰｂ（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 の添加していない試料
Ｎｏ．２５はいずれも、ｄ33が４００ｐｍ／Ｖ未満と小
さな値となった。On the other hand, Sample No. to which Pb (Yb 1/2 Nb 1/2 ) O 3 was not added. 22 Although d 33 is 530pm / V and high, T c was as low as 200 ° C.. Also, Pb
(Co 1/3 Nb 2/3 ) O 3 and Pb (Zn 1/3 Nb 2/3 )
O 3 was not added to the sample No. 23, Pb (Co 1/3
Sample No. Nb 2/3 ) O 3 was not added. Sample No. 24 to which no Pb (Zn 1/3 Nb 2/3 ) O 3 was added. 25 Both, d 33 becomes small as less than 400 pm / V.
【００４０】実施例２ Ｐｂa-x Ｓｒx （Ｙｂ1/2 Ｎｂ1/2 ）b ( Ｚｎ1/3 Ｓｂ
2/3 ) c ( Ｃｏ1/3 Ｎｂ2/3 ) d Ｎｂy （Ｚｒe Ｔｉ
1-e )1-b-c-d-yＯ3 で表わした組成式になるように、実
施例１と同様に試料を作製した。ただし、ＢａＣＯ3 の
代わりにＳｒＣＯ3 を用い、またＳｂ2 Ｏ3 を新規に加
えて原料を作製し、ＳｒをＡサイトに置換した試料を作
製した。測定法も実施例１と同様に行った。これらの結
果を表２に示した。なお、表２中のｘ，ｙ，ａ，ｂ，
ｃ，ｄおよびｅは、Ｐｂa-x Ｓｒx （Ｙｂ1/2 Ｎ
ｂ1/2 ）b ( Ｚｎ1/3 Ｎｂ2/3 ) c ( Ｃｏ1/3 Ｎ
ｂ2/3 ) d Ｎｂy （Ｚｒe Ｔｉ1-e )1-b-c-d-yＯ3 で表
わした組成式で与えられる原子比を百分率換算したもの
である。Example 2 Pb ax Sr x (Yb 1/2 Nb 1/2 ) b (Zn 1/3 Sb
2/3) c (Co 1/3 Nb 2/3 ) d Nb y (Zr e Ti
1-e ) A sample was prepared in the same manner as in Example 1 so as to obtain a composition formula represented by 1-bcdy O 3 . However, SrCO 3 was used in place of BaCO 3 , and Sb 2 O 3 was newly added to prepare a raw material, and a sample in which Sr was replaced with an A site was prepared. The measurement was performed in the same manner as in Example 1. Table 2 shows the results. In Table 2, x, y, a, b,
c, d and e are Pb ax Sr x (Yb 1/2 N
b 1/2 ) b (Zn 1/3 Nb 2/3 ) c (Co 1/3 N
b 2/3) is d Nb y (which Zr e Ti 1-e) was percentage terms atomic ratios given by the composition formula expressed by 1-bcdy O 3.
【００４１】[0041]
【表２】 [Table 2]
【００４２】ＳｒをＡサイトに置換した本発明の試料Ｎ
ｏ．２８〜３３は、いずれもｄ33が４００ｐｍ／Ｖ以
上、Ｔc が２５０℃以上と大きな値が得られた。Sample N of the present invention in which Sr was replaced with A site
o. 28 to 33 , d33 was 400 pm / V or more and Tc was 250 ° C. or more.
【００４３】実施例３ Ｐｂa-x Ｌａx （Ｙｂ1/2 Ｎｂ1/2 ）b ( Ｚｎ1/3 Ｎｂ
2/3 ) c ( Ｃｏ1/3 Ｎｂ2/3 ) d ( Ｆｅ2/3 Ｗ1/3 ) f
Ｎｂy （Ｚｒe Ｔｉ1-e )1-b-c-d-f-yＯ3 で表わした組
成式になるように、実施例１と同様に試料を作製した。
ただし、ＢａＣＯ3 の代わりにＬａ2 Ｏ3 を用い、新た
にＦｅ2 Ｏ3 とＷＯ3 を加えてて原料を作成し、Ｓｒを
Ａサイトに置換した試料を作製した。測定法も実施例１
と同様に行った。これらの結果を表３に示した。表３中
のｘ，ｙ，ａ，ｂ，ｃ，ｄ，ｅおよびｆは、Ｐｂa-x Ｌ
ａx （Ｙｂ1/2 Ｎｂ1/2 ）b ( Ｚｎ1/3 Ｎｂ2/3 ) c (
Ｃｏ1/3 Ｎｂ2/3 ) d ( Ｆｅ2/3 Ｗ1/3 ) f Ｎｂy （Ｚ
ｒe Ｔｉ1-e )1-b-c-d-f-yＯ3 で表わした組成式で与え
られる原子比を百分率換算したものである。Example 3 Pb ax La x (Yb 1/2 Nb 1/2 ) b (Zn 1/3 Nb
2/3 ) c (Co 1/3 Nb 2/3 ) d (Fe 2/3 W 1/3 ) f
Nb y (Zr e Ti 1- e) so that the composition formula expressed by 1-bcdfy O 3, a sample was prepared in the same manner as in Example 1.
However, La 2 O 3 was used instead of BaCO 3 , Fe 2 O 3 and WO 3 were newly added to prepare a raw material, and a sample was prepared in which Sr was replaced with the A site. Example 1
The same was done. Table 3 shows the results. X, y, a, b, c, d, e and f in Table 3 are Pb ax L
a x (Yb 1/2 Nb 1/2 ) b (Zn 1/3 Nb 2/3 ) c (
Co 1/3 Nb 2/3) d (Fe 2/3 W 1/3) f Nb y (Z
The r e Ti 1-e) 1 -bcdfy O 3 atomic ratio given by the composition formula expressed by is obtained by percentage terms.
【００４４】[0044]
【表３】 [Table 3]
【００４５】ＬａをＡサイト置換した本発明の試料Ｎ
ｏ．３４とおよび( Ｆｅ2/3 Ｗ1/3 )f Ｎｂを３モル％
添加した本発明の試料Ｎｏ．３５とは、いずれもいずれ
もｄ33が４００ｐｍ／Ｖ以上、Ｔc が２５０℃以上と大
きな値が得られた。Sample N of the present invention in which La was replaced with A site
o. 34 and (Fe 2/3 W 1/3 ) f Nb in 3 mol%
The sample No. of the present invention added. 35 and are both either d 33 is 400 pm / V or more, T c was obtained high as 250 ° C. or higher.
【００４６】[0046]
【発明の効果】ＰＺＴをベースに種々のペロブスカイト
型複合酸化物を加えることによって１０００℃以下の低
温の焼成できとともに、かつ高いキュリー温度と大きな
圧電歪定数を併せ持つ圧電磁器組成物を提供することが
できる。According to the present invention, it is possible to provide a piezoelectric ceramic composition which can be fired at a low temperature of 1000 ° C. or less by adding various perovskite-type composite oxides based on PZT, and has both a high Curie temperature and a large piezoelectric strain constant. it can.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ０２Ｍ 51/00 Ｆ０２Ｍ 51/00 Ｅ Ｈ０１Ｌ 41/187 Ｈ０１Ｌ 41/18 １０１Ｄ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) F02M 51/00 F02M 51/00 E H01L 41/187 H01L 41/18 101D
Claims (5)
対して、副成分としてＰｂ（Ｙｂ1/2 Ｎｂ1/2 ）Ｏ
3 と、Ｐｂ( Ｃｏ1/3 Ｎｂ2/3 ) Ｏ3 と、Ｐｂ（Ｚｎ
1/3 Ｎｂ2/3 ）Ｏ3 、Ｐｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 の
少なくとも１種とが固溶してなるＡＢＯ3 型ペロブスカ
イト型複合酸化物からなることを特徴とする圧電磁器組
成物。1. A Pb (Zr, Ti) with respect to the main component consisting of O 3, as a sub-component Pb (Yb 1/2 Nb 1/2) O
3 , Pb (Co 1/3 Nb 2/3 ) O 3 and Pb (Zn
1/3 Nb 2/3 ) O 3 and at least one of Pb (Zn 1/3 Sb 2/3 ) O 3 in the form of an ABO 3 perovskite-type composite oxide formed as a solid solution. Piezoelectric ceramic composition.
％とすることを特徴とする請求項１記載の圧電磁器組成
物。2. The piezoelectric ceramic composition according to claim 1, wherein the content of the auxiliary component is 10 to 20 mol% based on the total amount.
たは希土類元素を、８モル％以下の割合で含有してなる
ことを特徴とする請求項１または２記載の圧電磁器組成
物。3. The piezoelectric ceramic composition according to claim 1, wherein the A site contains an alkaline earth element and / or a rare earth element in a proportion of 8 mol% or less.
で含有してなることを特徴とする請求項１乃至３のいず
れかに記載の圧電磁器組成物。4. The piezoelectric ceramic composition according to claim 1, wherein Nb is contained in the B site at a ratio of 1 mol% or less.
3 および／またはＰｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 の少な
くとも一部をＰｂ（Ｆｅ2/3 Ｗ1/3 ）Ｏ3 で置換したこ
とを特徴とする請求項１乃至４のいずれかに記載の圧電
磁器組成物。5. An auxiliary component Pb (Zn 1/3 Nb 2/3 ) O
3 and / or Pb (Zn 1/3 Sb 2/3) at least part of Pb (Fe 2/3 W 1/3) of O 3 any of claims 1 to 4, characterized in that substituted with O 3 A piezoelectric ceramic composition according to any one of the above.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001284668A (en) * | 2000-03-29 | 2001-10-12 | Kyocera Corp | Laminated piezoelectric element, piezoelectric actuator, and injection equipment |
| WO2002081404A1 (en) * | 2001-03-30 | 2002-10-17 | Tdk Corporation | Piezoelectric porcelain and method for preparation thereof, and piezoelectric element |
| EP1354861A1 (en) * | 2000-12-28 | 2003-10-22 | Bosch Automotive Systems Corporation | Ceramic material and piezoelectric element using the same |
| JP2007217238A (en) * | 2006-02-17 | 2007-08-30 | Kyocera Corp | Piezoelectric ceramic composition, piezoelectric ceramic, piezoelectric actuator element, and circuit module |
| US20120080636A1 (en) * | 2010-09-30 | 2012-04-05 | Tdk Corporation | Piezoelectric ceramic, piezoelectric element comprising it, and piezoelectric device comprising piezoelectric element |
| JP2014208562A (en) * | 2013-03-27 | 2014-11-06 | 太平洋セメント株式会社 | Piezoelectric ceramic, and piezoelectric element using the same |
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1999
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001284668A (en) * | 2000-03-29 | 2001-10-12 | Kyocera Corp | Laminated piezoelectric element, piezoelectric actuator, and injection equipment |
| EP1354861A1 (en) * | 2000-12-28 | 2003-10-22 | Bosch Automotive Systems Corporation | Ceramic material and piezoelectric element using the same |
| EP1354861A4 (en) * | 2000-12-28 | 2007-02-28 | Bosch Automotive Systems Corp | Ceramic material and piezoelectric element using the same |
| WO2002081404A1 (en) * | 2001-03-30 | 2002-10-17 | Tdk Corporation | Piezoelectric porcelain and method for preparation thereof, and piezoelectric element |
| US6979410B2 (en) | 2001-03-30 | 2005-12-27 | Tdk Corporation | Piezoelectric ceramic, method of manufacturing the same and piezoelectric device |
| JP2007217238A (en) * | 2006-02-17 | 2007-08-30 | Kyocera Corp | Piezoelectric ceramic composition, piezoelectric ceramic, piezoelectric actuator element, and circuit module |
| US20120080636A1 (en) * | 2010-09-30 | 2012-04-05 | Tdk Corporation | Piezoelectric ceramic, piezoelectric element comprising it, and piezoelectric device comprising piezoelectric element |
| US8562852B2 (en) * | 2010-09-30 | 2013-10-22 | Tdk Corporation | Piezoelectric ceramic, piezoelectric element comprising it, and piezoelectric device comprising piezoelectric element |
| JP2014208562A (en) * | 2013-03-27 | 2014-11-06 | 太平洋セメント株式会社 | Piezoelectric ceramic, and piezoelectric element using the same |
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