JPH0745124A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
- Publication number
- JPH0745124A JPH0745124A JP5187875A JP18787593A JPH0745124A JP H0745124 A JPH0745124 A JP H0745124A JP 5187875 A JP5187875 A JP 5187875A JP 18787593 A JP18787593 A JP 18787593A JP H0745124 A JPH0745124 A JP H0745124A
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- Prior art keywords
- piezoelectric
- constant
- curie temperature
- composition
- strain constant
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、圧電磁器組成物に係わ
り、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，圧電アクチュエータおよび加速度センサ，ノッキン
グセンサ，ＡＥセンサ等の圧電センサ等に適する圧電磁
器組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition, for example, a ceramic filter, an ultrasonic transducer, a piezoelectric buzzer, a piezoelectric ignition unit, an ultrasonic motor, a piezoelectric fan, a piezoelectric actuator, an acceleration sensor, and a knocking sensor. , A piezoelectric ceramic composition suitable for a piezoelectric sensor such as an AE sensor.
【０００２】[0002]
【従来技術】従来から、圧電磁気組成物を利用した製品
としては、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，圧電センサ，圧電アクチュエータ等がある。2. Description of the Related Art Conventionally, products using a piezoelectric magnetic composition include, for example, ceramic filters, ultrasonic transducers, piezoelectric buzzers, piezoelectric ignition units, ultrasonic motors, piezoelectric fans, piezoelectric sensors, piezoelectric actuators and the like. .
【０００３】ここで、圧電アクチュエータは、圧電現象
を介して発生する変位や力を機械的駆動源として利用す
るものであり、特に最近、メカトロニクスの分野におい
て注目されているものの一つである。圧電アクチュエー
タは、圧電効果を利用した固体素子であるので、磁性体
にコイルを巻いた構成の従来の電磁式アクチュエータと
比較して、消費電力が少ない、応答速度が速い、変位量
が大きい、発熱が少ない、寸法及び重量が小さい等の優
れた特徴を有している。このため、メカトロニクスの高
度化に伴い多方面にわたる研究開発が進められている。Here, the piezoelectric actuator utilizes a displacement or force generated through a piezoelectric phenomenon as a mechanical drive source, and is one of the ones that have recently attracted attention in the field of mechatronics. Piezoelectric actuators are solid-state devices that utilize the piezoelectric effect, so they consume less power, have a faster response speed, have a larger displacement, and generate more heat than conventional electromagnetic actuators that have a coil wound around a magnetic body. It has excellent characteristics such as small amount and small size and weight. For this reason, research and development in various fields are being promoted with the advancement of mechatronics.
【０００４】ところで、上述したアクチュエータの用途
が拡大するに従い、より大きな機械的変位が必要とされ
るとともに、広い温度範囲（−３０〜１５０℃）での使
用に耐えうることが必要とされてきている。即ち、キュ
リー温度が高いことが望まれる。また、一般的にアクチ
ュエータ用素子としての機能上、圧電歪定数、特にｄ33
定数ができるだけ大きいことが望まれる。このように、
圧電アクチュエータの用途に適する圧電材料の特性は、
この種の材料において通常用いられる諸定数（電気機械
結合係数、誘電率、圧電歪定数等）及びキュリー温度に
よりその良否が判定できる。By the way, as the application of the above-mentioned actuator is expanded, a larger mechanical displacement is required, and it is required that it can withstand use in a wide temperature range (-30 to 150 ° C). There is. That is, it is desired that the Curie temperature is high. Further, in general, in terms of the function as an actuator element, the piezoelectric strain constant, especially d 33
It is desired that the constant be as large as possible. in this way,
The characteristics of piezoelectric materials suitable for piezoelectric actuator applications are:
The quality can be judged by various constants (electromechanical coupling coefficient, dielectric constant, piezoelectric strain constant, etc.) normally used in this kind of material and the Curie temperature.
【０００５】このような目的に合致する圧電磁器組成物
としてＰＺＴ系にＰｂ（Ｎｉ1/3 Ｎｂ2/3 ）Ｏ3 を第３
成分として置換させたものがある。例えば、Ｐｂ（Ｎｉ
1/3Ｎｂ2/3 ）0.50Ｚｒ0.15Ｔｉ0.35Ｏ3 があるが、こ
の例では、表２の試料Ｎo.３２に示すように、圧電歪定
数（ｄ33定数）が６３３×１０-12 ｍ／ｖと大きい特性
を有する。A PZT system containing Pb (Ni 1/3 Nb 2/3 ) O 3 as a third piezoelectric ceramic composition which meets such an object.
Some components have been replaced. For example, Pb (Ni
1/3 Nb 2/3 ) 0.50 Zr 0.15 Ti 0.35 O 3 , but in this example, as shown in sample No. 32 in Table 2, the piezoelectric strain constant (d 33 constant) is 633 × 10 −12 m 2. It has a large characteristic of / v.
【０００６】[0006]
【発明が解決しようとする問題点】しかしながら、上記
のようなＰＺＴ系にＰｂ（Ｎｉ1/3 Ｎｂ2/3 ）Ｏ3 を第
３成分として置換させたものを圧電アクチュエータ用と
して利用する場合、キュリー温度（Ｔｃ）が低く、１０
０〜１５０℃と高温にさらされるような環境下では使用
できないという問題があった。このように、この組成系
では、圧電歪定数が大きいものはキュリー温度が低く、
変位素子としての利用が極めて狭い範囲に限定されると
いう欠点があった。However, when the above PZT system in which Pb (Ni 1/3 Nb 2/3 ) O 3 is substituted as the third component is used for a piezoelectric actuator, Curie temperature (Tc) is low, 10
There is a problem that it cannot be used in an environment where it is exposed to a high temperature of 0 to 150 ° C. As described above, in this composition system, a material having a large piezoelectric strain constant has a low Curie temperature,
It has a drawback that its use as a displacement element is limited to an extremely narrow range.
【０００７】また、アクチュエータには常に圧縮応力が
加わっていることから、アクチュエータ用途の場合、通
常圧電歪定数の減衰、即ち、耐久性が問題となるが、上
記組成では圧電歪定数の減衰が大きく、耐久性が劣ると
いう問題があった。即ち、図１の試料Ｎo.３２の曲線か
ら判るように、１ｔ／ｃｍ2 の荷重を１０回繰り返し加
えるとｄ33定数が４０〜５０％減衰することから、大き
な応力が加わる用途には適さないことになる。Further, since the actuator is always subjected to compressive stress, in the case of actuator application, the attenuation of the piezoelectric strain constant, that is, the durability is usually a problem. However, in the above composition, the attenuation of the piezoelectric strain constant is large. However, there was a problem of poor durability. That is, as can be seen from the curve of the sample No. 32 in FIG. 1, when the load of 1 t / cm 2 is repeatedly applied 10 times, the d 33 constant is attenuated by 40 to 50%, so that it is not suitable for the application of large stress. It will be.
【０００８】本発明は、圧電歪特性、キュリー温度及び
耐久性の面で優れており、特に圧電アクチュエータや圧
電センサ等に適した圧電磁器組成物を提供することを目
的とする。An object of the present invention is to provide a piezoelectric ceramic composition which is excellent in piezoelectric strain characteristics, Curie temperature and durability and which is particularly suitable for piezoelectric actuators, piezoelectric sensors and the like.
【０００９】[0009]
【問題点を解決するための手段】本発明者等は、ＰｂＺ
ｒＯ3 −ＰｂＴｉＯ3 に固溶する最適な第３成分の探索
を行った結果、Ｐｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 となる組
成を第３成分とすることにより、圧電歪特性、キュリー
温度及び耐久性の面で優れた圧電磁器組成物を得ること
ができることを知見し、本発明に至った。[Means for Solving the Problems]
As a result of searching for an optimum third component that forms a solid solution in rO 3 -PbTiO 3 , the composition which becomes Pb (Zn 1/3 Sb 2/3 ) O 3 is used as the third component, so that the piezoelectric strain characteristic, The inventors have found that a piezoelectric ceramic composition excellent in terms of Curie temperature and durability can be obtained, and completed the present invention.
【００１０】即ち、本発明の圧電磁器組成物は、金属成
分として少なくともＰｂ、Ｚｒ、Ｔｉ、Ｓｒ、Ｂａ、Ｚ
ｎ、Ｓｂを含む複合ペロブスカイト型化合物であって、
これらの金属元素のモル比による組成式をＰｂ1-x-y Ｓ
ｒx Ｂａy （Ｚｎ1/3 Ｓｂ2/3 ）a Ｚｒb Ｔｉ1-a-b Ｏ
3 と表わした時、ｘ，ｙ，ａ，ｂが０≦ｘ≦０．１４、
０≦ｙ≦０．１４、０＜ｘ＋ｙ、０．０１≦ａ≦０．１
２、０．４３≦ｂ≦０．５８を満足するものである。That is, the piezoelectric ceramic composition of the present invention contains at least Pb, Zr, Ti, Sr, Ba and Z as metal components.
A compound perovskite compound containing n and Sb,
The composition formula based on the molar ratio of these metal elements is Pb 1-xy S
r x Ba y (Zn 1/3 Sb 2/3) a Zr b Ti 1-ab O
When expressed as 3 , x, y, a, and b are 0 ≦ x ≦ 0.14,
0 ≦ y ≦ 0.14, 0 <x + y, 0.01 ≦ a ≦ 0.1
2, 0.43 ≦ b ≦ 0.58 is satisfied.
【００１１】ここで、ｘ，ｙ，ａ，ｂを上記の範囲に設
定した理由について説明する。Ｓｒの置換は極めて大き
な圧電歪定数ｄ33を得るのに有効であるが、その置換量
ｘを０≦ｘ≦０．１４としたのは、ｘが０．１４より多
いとキュリー温度が急激に低下し、１５０℃を大きく下
回るからである。また、Ｂａの置換によりキュリー温度
が２００℃以上で圧電歪定数ｄ33を６００×１０-12 ｍ
／ｖ以上とすることもでき、極めて大きなキュリー温度
および圧電歪定数ｄ33を得るのに有効であるが、その置
換量ｙを０≦ｙ≦０．１４としたのは、ｙが０．１４よ
りも多いと、キュリー温度が大きく低下し、１５０℃以
下となるからである。Here, the reason why x, y, a, and b are set in the above range will be described. Substitution of Sr is effective for obtaining an extremely large piezoelectric strain constant d 33 , but the substitution amount x is set to 0 ≦ x ≦ 0.14, because the Curie temperature becomes abrupt when x is more than 0.14. This is because the temperature drops and falls significantly below 150 ° C. Further, by replacing Ba, the Curie temperature is 200 ° C. or higher and the piezoelectric strain constant d 33 is 600 × 10 −12 m.
/ V or more, which is effective in obtaining an extremely large Curie temperature and piezoelectric strain constant d 33. However, the substitution amount y is 0 ≦ y ≦ 0.14 because y is 0.14. If it is more than the above range, the Curie temperature is greatly lowered to 150 ° C. or less.
【００１２】また、Ｔｉの（Ｚｎ1/3 Ｓｂ2/3 ）による
置換量ａを０．０１≦ａ≦０．１２としたのは、ａが多
いと大きな圧電歪定数が得られ、圧電アクチュエータに
有用な特性となる。逆にａが少ないと、加速度センサー
等の圧電センサに有用な大きな圧電出力定数ｇ33が得ら
れる。しかし、ａが０．０１よりも少ないと圧電歪定数
ｄ33を４００×１０-12 ｍ／ｖ以上とすることができ
ず、また、圧電出力定数ｇ33の経時変化や温度変化が大
きくなるため、圧電センサーとしても有用性に欠けるか
らであり、ａが０．１２よりも多いと、キュリー温度の
低下が大きくなり、誘電損失も非常に大きくなるからで
ある。本発明の圧電磁器組成物を圧電アクチュエータと
して用いる場合には、０．０５≦ａ≦０．１２とするこ
とにより大きな圧電歪定数を得ることができ、圧電セン
サとして用いる場合には０．０１≦ａ≦０．０５とする
ことにより大きな圧電出力定数ｇ33を得ることができ
る。Further, the substitution amount a of Ti by (Zn 1/3 Sb 2/3 ) is set to 0.01 ≦ a ≦ 0.12, because a large piezoelectric strain constant is obtained when a is large, and the piezoelectric actuator is It will be a useful property. On the contrary, when a is small, a large piezoelectric output constant g 33 useful for a piezoelectric sensor such as an acceleration sensor can be obtained. However, if a is less than 0.01, the piezoelectric strain constant d 33 cannot be set to 400 × 10 −12 m / v or more, and the piezoelectric output constant g 33 changes with time and changes greatly with temperature. This is because the piezoelectric sensor lacks usefulness as well, and when a is more than 0.12, the Curie temperature is greatly lowered and the dielectric loss is also very large. When the piezoelectric ceramic composition of the present invention is used as a piezoelectric actuator, a large piezoelectric strain constant can be obtained by setting 0.05 ≦ a ≦ 0.12, and when it is used as a piezoelectric sensor, 0.01 ≦ By setting a ≦ 0.05, a large piezoelectric output constant g 33 can be obtained.
【００１３】ＰＺＴを主成分とした圧電磁器組成物は、
ＰｂＺｒＯ3 とＰｂＴｉＯ3 の固溶比率を変化させると
圧電歪定数の極大値を示すＭＰＢ（組成相境界）が存在
する。圧電アクチュエータ材料としては、このＭＰＢ及
びその近傍の組成値を用いることになる。このＭＰＢは
ｘ，ａの量により変化するため、ｂの値はｘ，ａの組成
範囲内でＭＰＢを捉えうる組成範囲とした。即ち、０．
４３≦ｂ≦０．５８としたのは、この範囲外となるとＭ
ＰＢを捉えることができないからである。A piezoelectric ceramic composition containing PZT as a main component is
When the solid solution ratio of PbZrO 3 and PbTiO 3 is changed, there is MPB (composition phase boundary) that shows the maximum value of the piezoelectric strain constant. As the piezoelectric actuator material, the composition value of MPB and its vicinity will be used. Since this MPB changes depending on the amounts of x and a, the value of b is set to a composition range in which MPB can be captured within the composition range of x and a. That is, 0.
43 ≦ b ≦ 0.58 is because M is out of this range.
This is because PB cannot be captured.
【００１４】そして、本発明の圧電磁器は、例えば、原
料としてＰｂＯ、ＺｒＯ2 、ＴｉＯ2 、ＳｒＣＯ3 、Ｂ
ａＣＯ3 、ＺｎＯ及びＳｂ2 Ｏ3 の各粉末を秤量混合
し、次いで、この混合物を脱水、乾燥した後、８５０〜
９００℃で１〜３時間仮焼し、当該仮焼物を再びボール
ミル等で粉砕する。In the piezoelectric ceramic of the present invention, for example, PbO, ZrO 2 , TiO 2 , SrCO 3 and B are used as raw materials.
Each powder of aCO 3 , ZnO and Sb 2 O 3 is weighed and mixed, and then the mixture is dehydrated and dried, and then 850-
It is calcined at 900 ° C. for 1 to 3 hours, and the calcined product is ground again with a ball mill or the like.
【００１５】その後、この粉砕物に有機バインダー（Ｐ
ＶＡ）を混合し、造粒した。得られた粉末を所定圧力で
成形して成形体を作製し、これらを１２４０〜１３００
℃で１〜３時間焼成することにより得られる。Then, an organic binder (P
VA) was mixed and granulated. The obtained powder is molded at a predetermined pressure to prepare a molded body, and these are molded in the range of 1240 to 1300.
It is obtained by firing at 1 ° C for 1 to 3 hours.
【００１６】[0016]
【作用】本発明の圧電磁器組成物では、Ｐｂの一部をＳ
ｒ，Ｂａで置換し、ＰｂＺｒＯ3 −ＰｂＴｉＯ3 に、Ｐ
ｂ（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 となる組成を第３成分とし
て固溶させることにより、高い圧電歪特性、高いキュリ
ー温度を得ることができるとともに、従来のように、第
３成分としてＰｂ（Ｎｉ1/3 Ｎｂ2/3 ）Ｏ3 を用いない
ため、一定荷重を繰り返し作用させた場合でも圧電歪定
数の減衰が抑制され、耐久性が向上する。In the piezoelectric ceramic composition of the present invention, a part of Pb is S
Substituting with r and Ba, PbZrO 3 —PbTiO 3 with P
By forming a solid solution containing b (Zn 1/3 Sb 2/3 ) O 3 as the third component, it is possible to obtain high piezoelectric strain characteristics and high Curie temperature. Since Pb (Ni 1/3 Nb 2/3 ) O 3 is not used as the material, attenuation of the piezoelectric strain constant is suppressed and durability is improved even when a constant load is repeatedly applied.
【００１７】[0017]
【実施例】以下、本発明を次の実施例で説明する。原料
粉末としてＰｂＯ、ＺｒＯ2 、ＴｉＯ2 、ＳｒＣＯ3 、
ＢａＣＯ3 、ＺｎＯ及びＳｂ2 Ｏ3 の各粉末を用いて、
これらを表１，２に示す割合に秤量し、ボールミルにて
２４時間湿式混合した。次いで、この混合物を脱水、乾
燥した後、８７０℃で３時間仮焼し、当該仮焼物を再び
ボールミルで２４時間湿式粉砕した。The present invention will be described in the following examples. As raw material powder, PbO, ZrO 2 , TiO 2 , SrCO 3 ,
Using BaCO 3 , ZnO and Sb 2 O 3 powders,
These were weighed in the ratios shown in Tables 1 and 2 and wet-mixed in a ball mill for 24 hours. Next, this mixture was dehydrated and dried, and then calcined at 870 ° C. for 3 hours, and the calcined material was wet-ground with a ball mill again for 24 hours.
【００１８】その後、この粉砕物に有機バインダー（Ｐ
ＶＡ）を混合し、造粒した。得られた粉末を１．５ｔ／
ｃｍ2 の圧力で直径２３ｍｍ、厚さ３ｍｍの寸法からな
る円板と直径８ｍｍ、厚さ１８ｍｍの円柱の２種の成形
体を作製した。更に、これらを１２７０℃で３時間の条
件で焼成した。Then, an organic binder (P
VA) was mixed and granulated. 1.5 t / of the obtained powder
With a pressure of cm 2 , two types of molded bodies were produced, a disk having a diameter of 23 mm and a thickness of 3 mm and a cylinder having a diameter of 8 mm and a thickness of 18 mm. Further, these were fired at 1270 ° C. for 3 hours.
【００１９】得られた焼結体を直径２０ｍｍ、厚さ１ｍ
ｍの円板と直径６ｍｍ、厚さ１５ｍｍの円柱状に研磨加
工し、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以上の直流電圧を印加
して分極処理を行った。The obtained sintered body has a diameter of 20 mm and a thickness of 1 m.
It is polished into a circular plate with a diameter of 6 m and a cylindrical shape with a diameter of 6 mm and a thickness of 15 mm, silver electrodes are baked on both sides, and a DC voltage of 1.5 kv / mm or more is applied in silicon oil at 80 ° C. for polarization treatment. went.
【００２０】分極処理された円板及び円柱を１００℃恒
温の中で１時間エイジングした後、２４時間放置した。
このようにして得られたそれぞれの磁器から、電子材料
工業会（ＥＭＡＳ）の規格化された測定法に基づき、圧
電諸定数（電気機械結合係数Ｋ33、比誘電率ε33 T ／ε
0 、コンプライアンス定数ｓ33 E 、圧電歪定数ｄ33、機
械的品質係数Ｑｍ、誘電損失ｔａｎδ E）を調べた。ま
たキュリー温度Ｔｃは高温側の常誘電性から低温側の強
誘電相へ相転移する時の比誘電率の極大値を示す温度と
した。また、耐久性を、一軸油圧プレス機を用いて円柱
状磁器に１ｔ／ｃｍ2 の圧力を１サイクル４秒の間隔で
繰り返し印加し、圧電歪定数ｄ33の保持率を測定するこ
とで求めた。ここで、繰り返し加圧を１０回加えた場合
における圧電歪定数ｄ33の減衰率が２０％以内のものを
○とし、２０％を越える場合を×とした。結果を表１，
２に示す。The polarized disks and cylinders were aged in a constant temperature of 100 ° C. for 1 hour and then left for 24 hours.
Piezoelectric constants (electromechanical coupling coefficient K 33 , relative permittivity ε 33 T / ε) were obtained from each of the porcelains obtained in this manner based on the standardized measurement method of the Electronic Material Industries Association (EMAS).
0 , compliance constant s 33 E , piezoelectric strain constant d 33 , mechanical quality factor Qm, dielectric loss tan δ E ) were investigated. Further, the Curie temperature Tc is set to a temperature at which the relative dielectric constant has a maximum value at the time of phase transition from the high temperature side paraelectric property to the low temperature side ferroelectric phase. Further, the durability was obtained by repeatedly applying a pressure of 1 t / cm 2 to a cylindrical porcelain using a uniaxial hydraulic press machine at intervals of 4 seconds per cycle, and measuring the retention rate of the piezoelectric strain constant d 33 . . Here, when the attenuation rate of the piezoelectric strain constant d 33 is 20% or less after the repeated pressurization is applied 10 times, the result is ◯, and when it exceeds 20%, the result is x. The results are shown in Table 1,
2 shows.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】これらの表１，２において、コンプライア
ンス定数ｓ33 E の単位は×１０-12ｍ2 ／Ｎ，圧電歪定
数ｄ33の単位は×１０-12 ｍ／Ｖ，圧電出力定数ｇ33の
単位は×１０-12 Ｖｍ／Ｎであり、圧電歪定数ｄ33およ
び圧電出力定数ｇ33は、それぞれｄ33＝Ｋ33（ε33 T ・
ｓ33 E ）1/2 、ｇ33＝ｄ33／ε33 T で得た。In these Tables 1 and 2, the unit of the compliance constant s 33 E is × 10 -12 m 2 / N, the unit of the piezoelectric strain constant d 33 is × 10 -12 m / V, and the piezoelectric output constant g 33 is The unit is × 10 -12 Vm / N, and the piezoelectric strain constant d 33 and the piezoelectric output constant g 33 are respectively d 33 = K 33 (ε 33 T
s 33 E ) 1/2 , g 33 = d 33 / ε 33 T.
【００２４】また表１における試料Ｎo.３，２０，３２
について、耐久性の評価を図１に示す。Further, the samples No. 3, 20, 32 in Table 1
The durability evaluation is shown in FIG.
【００２５】圧電アクチュエータを使用する温度環境が
１００℃あるいはそれ以下である場合、キュリー温度は
１５０℃あることが必要とされる。多くの場合、このよ
うな環境下で使用され、キュリー温度の下限は１５０℃
となるが、表１，２によれば、試料番号３はキュリー温
度が１５０℃と比較的高い温度に保ちながら、圧電歪定
数ｄ33が８０４×１０-12 ｍ／ｖと他に類のない極めて
大きなｄ定数を有している。更に０．５ｔ／ｃｍ2 の圧
力を５０回繰り返し加える耐久性の試験を行った結果、
ｄ33定数の減衰は５％であったことから耐久性において
も優れた特性を示した。また、更に圧電アクチュエータ
が１００乃至１５０℃と高温下にさらされる用途に使用
される場合、キュリー温度が２００℃を越えることが必
要される。アクチュエータ材料の場合、その機能上から
ｄ33定数ができるかぎり大きいことが望まれ、試料番号
１９，２０，２５はキュリー温度が２００℃を越え、か
つ圧電歪定数ｄ33が６００×１０-12 ｍ／ｖを上回る大
きな圧電歪定数を得ている。更に０．５ｔ／ｃｍ2 の荷
重を５０回繰り返し加える耐久性試験でもｄ33定数の減
衰は約３％と優れた特性を示したことから、圧電アクチ
ュエータ材料として非常に優れたものがある。If the temperature environment in which the piezoelectric actuator is used is 100 ° C. or lower, the Curie temperature is required to be 150 ° C. In most cases, it is used in such an environment and the lower limit of Curie temperature is 150 ° C.
However, according to Tables 1 and 2, Sample No. 3 has a unique piezoelectric strain constant d 33 of 804 × 10 −12 m / v while maintaining a relatively high Curie temperature of 150 ° C. It has an extremely large d constant. As a result of a durability test in which a pressure of 0.5 t / cm 2 was repeatedly applied 50 times,
Since the attenuation of the d 33 constant was 5%, the durability was excellent. Further, when the piezoelectric actuator is used for applications exposed to a high temperature of 100 to 150 ° C., the Curie temperature needs to exceed 200 ° C. In the case of an actuator material, it is desired that the d 33 constant is as large as possible in view of its function. Sample Nos. 19, 20, and 25 have Curie temperatures exceeding 200 ° C. and piezoelectric strain constants d 33 of 600 × 10 −12 m 2. A large piezoelectric strain constant exceeding / v is obtained. Further, even in a durability test in which a load of 0.5 t / cm 2 is repeatedly applied 50 times, the attenuation of the d 33 constant is about 3%, which is an excellent characteristic. Therefore, some piezoelectric actuator materials are very excellent.
【００２６】また、試料Ｎo.２６，２７のようにＰｂ
（Ｚｎ1/3 Ｓｂ2/3 ）Ｏ3 の固溶量ａが０．０５より小
さい場合、圧電歪定数ｄ33はそれ程大きくないが、大き
な圧電出力定数ｇ33が得られ、加速度センサー等の圧電
センサに最適である。Further, as in Sample Nos. 26 and 27, Pb
When the solid solution amount a of (Zn 1/3 Sb 2/3 ) O 3 is smaller than 0.05, the piezoelectric strain constant d 33 is not so large, but a large piezoelectric output constant g 33 can be obtained, and the piezoelectric strain constant d 33 Best suited for piezoelectric sensors.
【００２７】このように本発明品は大きな圧電歪定数ｄ
33および高いキュリー温度を得ることができるととも
に、繰り返し荷重を印加した場合でも圧電歪定数ｄ33の
減衰率が極めて小さい優れた特性を有することが判る。
また大きな圧電出力定数が得られることが判る。As described above, the product of the present invention has a large piezoelectric strain constant d.
It can be seen that 33 and a high Curie temperature can be obtained, and the piezoelectric strain constant d 33 has excellent characteristics such that the attenuation rate of the piezoelectric strain constant d 33 is extremely small even when a repeated load is applied.
Also, it can be seen that a large piezoelectric output constant can be obtained.
【００２８】[0028]
【発明の効果】以上詳述した通り、本発明によれば、Ｐ
ｂＯ、ＺｒＯ2 、ＴｉＯ2 、ＳｒＣＯ3 、ＢａＣＯ3 、
ＺｎＯ及びＳｂ2 Ｏ3 を所定の割合で配合することによ
り、圧電歪定数及びキュリー温度いずれの面でも大き
く、かつ繰り返し荷重を印加した場合でも圧電歪定数の
減衰率が小さく耐久性においても優れた特性を得ること
ができ、圧電アクチュエータ用素子として好適な特性を
有していることわかる。また、大きな圧電出力定数が得
られることから、加速度センサ，ノッキングセンサ，Ａ
Ｅセンサ等の圧電センサーにおいても優れた特性を得る
ことができる。As described in detail above, according to the present invention, P
bO, ZrO 2 , TiO 2 , SrCO 3 , BaCO 3 ,
By blending ZnO and Sb 2 O 3 in a predetermined ratio, both the piezoelectric strain constant and the Curie temperature are large, and the attenuation rate of the piezoelectric strain constant is small even when a repeated load is applied, and the durability is excellent. It can be seen that the characteristics can be obtained and that the characteristics are suitable as a piezoelectric actuator element. Further, since a large piezoelectric output constant can be obtained, the acceleration sensor, the knocking sensor, the A
Excellent characteristics can be obtained even in a piezoelectric sensor such as an E sensor.
【図１】繰り返し加圧回数と圧電歪定数の保持率との関
係を示すグラフである。FIG. 1 is a graph showing the relationship between the number of repeated pressurizations and the piezoelectric strain constant retention rate.
Claims (1)
ｉ、Ｓｒ、Ｂａ、Ｚｎ、Ｓｂを含む複合ペロブスカイト
型化合物であって、これらの金属元素のモル比による組
成式をＰｂ1-x-y Ｓｒx Ｂａy （Ｚｎ1/3 Ｓｂ2/3 ）a
Ｚｒb Ｔｉ1-a-b Ｏ3 と表わした時、ｘ，ｙ，ａ，ｂが ０ ≦ｘ≦０．１４ ０ ≦ｙ≦０．１４ ０ ＜ｘ＋ｙ ０．０１≦ａ≦０．１２ ０．４３≦ｂ≦０．５８ を満足することを特徴とする圧電磁器組成物。1. A metal component containing at least Pb, Zr, and T.
i, Sr, Ba, Zn, a composite perovskite compound including Sb, the composition formula by molar ratio of the metal elements Pb 1-xy Sr x Ba y (Zn 1/3 Sb 2/3) a
When expressed as Zr b Ti 1-ab O 3 , x, y, a, and b are 0 ≤ x ≤ 0.14 0 ≤ y ≤ 0.14 0 <x + y 0.01 ≤ a ≤ 0.12 0.43 A piezoelectric ceramic composition satisfying ≦ b ≦ 0.58.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18787593A JP3210782B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition for actuator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18787593A JP3210782B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition for actuator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0745124A true JPH0745124A (en) | 1995-02-14 |
| JP3210782B2 JP3210782B2 (en) | 2001-09-17 |
Family
ID=16213741
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18787593A Expired - Fee Related JP3210782B2 (en) | 1993-07-29 | 1993-07-29 | Piezoelectric ceramic composition for actuator |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645753A (en) * | 1994-05-19 | 1997-07-08 | Kyocera Corporation | Piezo-electric ceramic composition |
| JP2001278661A (en) * | 2000-03-31 | 2001-10-10 | Kyocera Corp | Dielectric ceramic composition and recording head for inkjet printer |
| JP2002220281A (en) * | 2001-01-23 | 2002-08-09 | Kyocera Corp | Piezoelectric ceramic composition and ink-jet recording head using it |
| US10177300B2 (en) | 2014-08-29 | 2019-01-08 | Kyocera Corporation | Piezoelectric ceramic, manufacturing method therefor, and electronic component |
-
1993
- 1993-07-29 JP JP18787593A patent/JP3210782B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645753A (en) * | 1994-05-19 | 1997-07-08 | Kyocera Corporation | Piezo-electric ceramic composition |
| JP2001278661A (en) * | 2000-03-31 | 2001-10-10 | Kyocera Corp | Dielectric ceramic composition and recording head for inkjet printer |
| JP2002220281A (en) * | 2001-01-23 | 2002-08-09 | Kyocera Corp | Piezoelectric ceramic composition and ink-jet recording head using it |
| JP4688301B2 (en) * | 2001-01-23 | 2011-05-25 | 京セラ株式会社 | Piezoelectric ceramic composition and ink jet recording head using the same |
| US10177300B2 (en) | 2014-08-29 | 2019-01-08 | Kyocera Corporation | Piezoelectric ceramic, manufacturing method therefor, and electronic component |
| US10297744B2 (en) | 2014-08-29 | 2019-05-21 | Kyocera Corporation | Piezoelectric ceramic plate, plate-shaped substrate and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3210782B2 (en) | 2001-09-17 |
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