JPH09295864A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
- Publication number
- JPH09295864A JPH09295864A JP8107141A JP10714196A JPH09295864A JP H09295864 A JPH09295864 A JP H09295864A JP 8107141 A JP8107141 A JP 8107141A JP 10714196 A JP10714196 A JP 10714196A JP H09295864 A JPH09295864 A JP H09295864A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- heat resistance
- composition
- electromechanical coupling
- porcelain composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Oxide Ceramics (AREA)
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，セラミックレゾネータ，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に用いられ
る圧電磁器組成物に係わり、特に、アナログセルラーフ
ォン、デジタルセルラーフォン等の移動体通信機の第二
中間周波数フィルタ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 used in, for example, a ceramic filter, a ceramic resonator, an ultrasonic transducer, a piezoelectric buzzer, a piezoelectric ignition unit, an ultrasonic motor, a piezoelectric fan, a piezoelectric sensor, and a piezoelectric actuator. The present invention relates to a piezoelectric ceramic composition suitable for a second intermediate frequency filter of a mobile communication device such as an analog cellular phone or a digital cellular phone.
【０００２】[0002]
【従来技術】従来から、圧電磁器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，セラミックレゾ
ネータ，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 utilizing piezoelectric ceramic compositions include, for example, ceramic filters, ceramic resonators, ultrasonic transducers, piezoelectric buzzers, piezoelectric ignition units, ultrasonic motors, piezoelectric fans, piezoelectric sensors, and piezoelectric actuators. Etc.
【０００３】ここで、セラミックフィルタ，セラミック
レゾネータ等の素子としては、ＰｂＺｒＯ3 −ＰｂＴｉ
Ｏ3 を主成分とした磁器組成物が利用されており、これ
にＮｂ2 Ｏ5 やＭｎＯ2 等の金属酸化物、Ｐｂ（Ｎｂ
2/3 Ｍｇ1/3 ）Ｏ3 やＰｂ（Ｎｂ2/3 Ｃｏ1/3 ）Ｏ3 等
の複合ペロブスカイト型酸化物を添加したり置換するこ
とにより圧電特性の向上が図られている。Here, elements such as a ceramic filter and a ceramic resonator include PbZrO 3 -PbTi
A porcelain composition containing O 3 as a main component is used, and a metal oxide such as Nb 2 O 5 or MnO 2 or Pb (Nb
Piezoelectric properties have been improved by adding or substituting complex perovskite type oxides such as 2/3 Mg 1/3 ) O 3 and Pb (Nb 2/3 Co 1/3 ) O 3 .
【０００４】従来、電気機械結合係数Ｋｐが大きく圧電
性に優れた圧電磁器組成物として、Ｐｂ（Ｎｂ2/3 Ｃｏ
1/3 ）Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 系の組成物が
知られている。Conventionally, Pb (Nb 2/3 Co) has been used as a piezoelectric ceramic composition having a large electromechanical coupling coefficient Kp and excellent piezoelectricity.
1/3) O 3 -PbZrO 3 -PbTiO 3 system composition is known.
【０００５】一方、近年では、セラミックフィルタ，セ
ラミックレゾネータのような圧電部品においても、基板
等の表面に実装可能なように種々の条件に対応できるこ
とが要求されており、このような圧電部品においては、
部品を基板にリフロー半田付けする際、基板に実装され
た部品が２３０℃から３００℃程度の高温に曝されるた
めに部品に組み込まれる圧電素子にも耐熱性が要求され
ている。On the other hand, in recent years, piezoelectric components such as ceramic filters and ceramic resonators have been required to be able to cope with various conditions so that they can be mounted on a surface of a substrate or the like. ,
When a component is reflow-soldered to a substrate, the component mounted on the substrate is exposed to a high temperature of about 230 ° C. to 300 ° C., so that a piezoelectric element incorporated in the component also requires heat resistance.
【０００６】また、例えば、圧電セラミックスの拡がり
振動を利用した数百キロヘルツ帯のフィルターにおいて
は、電気機械結合係数Ｋｐが大きく、機械的品質係数Ｑ
ｍが小さく、かつ保証減衰量を大きくするために、比誘
電率εｒが小さく、耐熱性に優れた材料が必要になる。
特にデジタルセルラーフォンでは、隣接チャンネルの雑
音防止のために保証帯域内でのフィルターの群遅延特性
を安定化することが要求されている。Further, for example, in a filter of several hundreds of kilohertz band which utilizes the spreading vibration of piezoelectric ceramics, the electromechanical coupling coefficient Kp is large and the mechanical quality coefficient Q is large.
In order to reduce m and increase the guaranteed attenuation amount, a material having a small relative permittivity εr and excellent heat resistance is required.
Particularly in digital cellular phones, it is required to stabilize the group delay characteristics of the filter within the guaranteed band in order to prevent noise from adjacent channels.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、従来の
上記したＰｂ（Ｎｂ2/3 Ｃｏ1/3 ）Ｏ3 −ＰｂＺｒＯ3
−ＰｂＴｉＯ3 系の磁器組成物は、耐熱性が低くリフロ
ー半田付け前後の圧電特性や共振周波数の変化が大き
く、実用上の問題となっていた。また、熱衝撃試験後の
圧電特性や共振周波数の変化も大きいため、環境変化の
激しい車両搭載用通信装置などのフィルター等に用いた
場合、素子の特性変化によって安定した送受信ができな
くなるという問題があった。However, the above-mentioned conventional Pb (Nb 2/3 Co 1/3 ) O 3 -PbZrO 3 is used.
-PbTiO 3 -based porcelain compositions have low heat resistance and large changes in piezoelectric characteristics and resonance frequency before and after reflow soldering, which has been a practical problem. In addition, since the piezoelectric characteristics and the resonance frequency change greatly after the thermal shock test, when used in filters such as in-vehicle communication devices where the environment changes drastically, there is a problem that stable transmission and reception cannot be performed due to changes in element characteristics. there were.
【０００８】さらに、比誘電率εｒが１８００程度と高
いために、部分電極を形成して素子を形成する必要があ
り、また、機械的品質係数Ｑｍが大きいために群遅延特
性が悪いという問題点があった。Further, since the relative permittivity εr is as high as about 1800, it is necessary to form a partial electrode to form an element, and the mechanical delay coefficient Qm is large, so that the group delay characteristic is poor. was there.
【０００９】本発明の圧電磁器組成物は、電気機械結合
係数Ｋｐが大きく、更に機械的品質係数Ｑｍが小さく、
比誘電率εｒが小さく、耐熱性に優れた圧電磁器組成物
を提供することを目的とする。The piezoelectric ceramic composition of the present invention has a large electromechanical coupling coefficient Kp and a small mechanical quality coefficient Qm,
An object of the present invention is to provide a piezoelectric ceramic composition having a small relative permittivity εr and excellent heat resistance.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、Ｐｂ、Ｚ
ｒ、Ｔｉ、Ｎｂ、Ｃｒ、Ｙｂ、Ａｌ、およびＬａ，Ｃ
ｅ，Ｇｄ，Ｎｄ，Ｓｍ，Ｐｒ，Ｅｕのうち少なくとも一
種、並びにＳｒ，Ｂａのうち少なくとも一種を含む複合
ペロブスカイト型化合物であって、一定の組成を有する
ものは、電気機械結合係数Ｋｐが大きく、機械的品質係
数Ｑｍが小さく、比誘電率εｒが小さく、耐熱性および
耐熱衝撃性に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 The present inventors have proposed Pb, Z
r, Ti, Nb, Cr, Yb, Al, and La, C
A complex perovskite type compound containing at least one of e, Gd, Nd, Sm, Pr and Eu, and at least one of Sr and Ba and having a constant composition has a large electromechanical coupling coefficient Kp, The inventors have found that it is possible to obtain a piezoelectric ceramic composition having a small mechanical quality factor Qm, a small relative permittivity εr, and excellent heat resistance and thermal shock resistance, and arrived at the present invention.
【００１１】即ち、本発明の圧電磁器組成物は、金属成
分としてＰｂ、Ｚｒ、Ｔｉ、Ｎｂ、Ｃｒ、Ｙｂ、Ａｌを
含むペロブスカイト型化合物であって、その組成式を
（Ｐｂ1-x-y Ｌx Ｍy ) a (Ｎｂb Ｃｒc Ｙｂd Ａ
ｌe ) f Ｔｉg Ｚr1-f-g Ｏ3 （ここで、ＬはＳｒ，Ｂ
ａのうち少なくとも一種、ＭはＬａ，Ｃｅ，Ｇｄ，Ｎ
ｄ，Ｓｍ，Ｐｒ，Ｅｕのうち少なくとも一種）と表わし
た時、ｘ，ｙ，ａ，ｂ，ｃ，ｄ，ｅ，ｆ，ｇが０．０１
≦ｘ≦０．０８、０．００２≦ｙ≦０．０５、０．９５
≦ａ≦１．０５、０．４６≦ｂ≦０．６０、０．１１≦
ｃ≦０．４２、０．０２≦ｄ≦０．３１、０．０２≦ｅ
≦０．１８、０．０２≦ｆ≦０．１５、０．４６≦ｇ≦
０．５２、ｂ＋ｃ＋ｄ＋ｅ＝１．００を満足するもので
ある。That is, the piezoelectric ceramic composition of the present invention is a perovskite type compound containing Pb, Zr, Ti, Nb, Cr, Yb and Al as metal components, and its composition formula is (Pb 1-xy L x M y ) a (Nb b Cr c Yb d A
l e ) f Ti g Zr 1-fg O 3 (where L is Sr, B
at least one of a, M is La, Ce, Gd, N
d, Sm, Pr, and Eu), x, y, a, b, c, d, e, f, g are 0.01
≦ x ≦ 0.08, 0.002 ≦ y ≦ 0.05, 0.95
≦ a ≦ 1.05, 0.46 ≦ b ≦ 0.60, 0.11 ≦
c ≦ 0.42, 0.02 ≦ d ≦ 0.31, 0.02 ≦ e
≦ 0.18, 0.02 ≦ f ≦ 0.15, 0.46 ≦ g ≦
0.52 and b + c + d + e = 1.00 are satisfied.
【００１２】[0012]
【作用】本発明の圧電磁器組成物では、ＰｂＺｒＯ3 −
ＰｂＴｉＯ3 系の磁器組成物のＺｒおよびＴｉの一部を
Ｎｂ，Ｃｒ、Ｙｂ，Ａｌで置換し、Ｐｂの一部をＳｒお
よび／またはＢａやＬａ，Ｃｅ，Ｇｄ，Ｎｄ，Ｓｍ，Ｐ
ｒ，Ｅｕのうち少なくとも一種で置換することにより、
高い電気機械結合係数Ｋｐ、低い機械的品質係数Ｑｍ、
低い比誘電率εｒを示すとともに、耐熱性を向上でき
る。In the piezoelectric ceramic composition of the present invention, PbZrO 3 −
Part of Zr and Ti of the PbTiO 3 -based porcelain composition is replaced with Nb, Cr, Yb, and Al, and part of Pb is Sr and / or Ba, La, Ce, Gd, Nd, Sm, P.
By substituting at least one of r and Eu,
High electromechanical coupling factor Kp, low mechanical quality factor Qm,
It exhibits a low relative permittivity εr and can improve heat resistance.
【００１３】[0013]
【発明の実施の形態】本発明の圧電磁器組成物は、組成
式を（Ｐｂ1-x-y Ｌx Ｍy ) a (Ｎｂb Ｃｒc Ｙｂd Ａ
ｌe ) f Ｔｉg Ｚr1-f-g Ｏ3 と表わした時、ｘ，ｙ，
ａ，ｂ，ｃ，ｄ，ｅ，ｆ，ｇが０．０１≦ｘ≦０．０
８、０．００２≦ｙ≦０．０５、０．９５≦ａ≦１．０
５、０．４６≦ｂ≦０．６０、０．１１≦ｃ≦０．４
２、０．０２≦ｄ≦０．３１、０．０２≦ｅ≦０．１
８、０．０２≦ｆ≦０．１５、０．４６≦ｇ≦０．５
２、ｂ＋ｃ＋ｄ＋ｅ＝１．００を満足するものである。The piezoelectric ceramic composition of the present invention DETAILED DESCRIPTION OF THE INVENTION, the composition formula (Pb 1-xy L x M y) a (Nb b Cr c Yb d A
l e ) f Ti g Zr 1-fg O 3 , x, y,
a, b, c, d, e, f, g are 0.01 ≦ x ≦ 0.0
8, 0.002 ≦ y ≦ 0.05, 0.95 ≦ a ≦ 1.0
5, 0.46 ≦ b ≦ 0.60, 0.11 ≦ c ≦ 0.4
2, 0.02 ≦ d ≦ 0.31, 0.02 ≦ e ≦ 0.1
8, 0.02 ≦ f ≦ 0.15, 0.46 ≦ g ≦ 0.5
2, b + c + d + e = 1.00 is satisfied.
【００１４】ここで、ａ，ｂ，ｃ，ｄ，ｅ，ｆ，ｇを上
記の範囲に設定した理由について説明する。Ａサイトの
ａを０．９５≦ａ≦１．０５としたのは、ａが０．９５
未満の場合や１．０５よりも大きい場合には電気機械結
合係数Ｋｐが低下したり、耐熱性が低下するからであ
る。Ａサイトのａは０．９９≦ａ≦１．０１であること
が特に望ましい。Here, the reason why a, b, c, d, e, f, g are set in the above range will be described. The reason for setting a of the A site to 0.95 ≦ a ≦ 1.05 is that a is 0.95.
This is because the electromechanical coupling coefficient Kp decreases and the heat resistance decreases when the ratio is less than 1.0 or more than 1.05. It is particularly desirable that a of the A site is 0.99 ≦ a ≦ 1.01.
【００１５】また、Ｎｂ量のｂを０．４６≦ｂ≦０．６
０としたのは、ｂが０．４６未満では機械的品質係数Ｑ
ｍが大きくなり、ｂが０．６０よりも大きい場合には比
誘電率εｒが大きくなり耐熱性が低下するからである。
Ｎｂ量のｂは０．５２≦ｂ≦０．５８とすることが望ま
しい。Further, b of the Nb amount is 0.46≤b≤0.6
The reason for setting 0 is that when b is less than 0.46, the mechanical quality factor Q
This is because when m is large and b is larger than 0.60, the relative dielectric constant εr is large and the heat resistance is lowered.
It is desirable that the Nb amount b be 0.52 ≦ b ≦ 0.58.
【００１６】さらに、Ｃｒ量のｃを０．１１≦ｃ≦０．
４２としたのは、ｃが０．１１未満の場合には耐熱性が
低下し、０．４２よりも大きい場合には機械的品質係数
Ｑｍが大きくなり群遅延時間特性が低下するからであ
る。Ｃｒ量のｃは０．２２≦ｃ≦０．２６であることが
望ましい。Further, when the c of the Cr amount is 0.11≤c≤0.
The reason for setting 42 is that when c is less than 0.11, heat resistance decreases, and when it is greater than 0.42, the mechanical quality factor Qm increases and the group delay time characteristic decreases. It is desirable that the Cr content c be 0.22 ≦ c ≦ 0.26.
【００１７】Ｙｂ量のｄを０．０２≦ｄ≦０．３１とし
たのは、ｄが０．０２未満では機械的品質係数Ｑｍが大
きく増加し、０．３１よりも大きいと比誘電率εｒが高
くなり耐熱性が劣化するからである。Ｙｂ量のｄは０．
０２≦ｄ≦０．１７とすることが望ましい。The d of Yb amount is set to 0.02 ≦ d ≦ 0.31 because the mechanical quality factor Qm is greatly increased when d is less than 0.02 and the relative dielectric constant εr is greater than 0.31. Is high and heat resistance is deteriorated. The Yb amount d is 0.
It is desirable to set 02 ≦ d ≦ 0.17.
【００１８】Ａｌ量のｅを０．０２≦ｅ≦０．１８とし
たのは、ｅが０．０２未満では比誘電率εｒが大きくな
り、０．１８よりも大きいと機械的品質係数Ｑｍが大き
くなり過ぎるからである。Ａｌ量のｅは０．０２≦ｅ≦
０．１２とすることが望ましい。The amount e of Al is set to 0.02≤e≤0.18, because the relative permittivity εr becomes large when e is less than 0.02, and the mechanical quality factor Qm becomes larger when e is larger than 0.18. Because it becomes too big. The Al amount e is 0.02 ≦ e ≦
It is desirable to set it to 0.12.
【００１９】（Ｎｂb Ｃｒc Ｙｂd Ａｌe ) のＢサイト
への置換量ｆを０．０２≦ｆ≦０．１５としたのは、ｆ
が０．０２未満では電気機械結合係数Ｋｐが低下し、ま
た０．１５よりも大きいと比誘電率εｒが大きくなり、
また耐熱性が急激に低下するからである。（Ｎｂb Ｃｒ
c Ｙｂd Ａｌe ) のＢサイトへの置換量ｆは０．０５≦
ｆ≦０．０７とすることが望ましい。The substitution amount f of (Nb b Cr c Yb d Al e ) to the B site is 0.02 ≦ f ≦ 0.15 because
Is less than 0.02, the electromechanical coupling coefficient Kp decreases, and when it is more than 0.15, the relative dielectric constant εr increases.
In addition, the heat resistance sharply decreases. (Nb b Cr
The substitution amount f of C Yb d Al e ) to the B site is 0.05 ≦
It is desirable that f ≦ 0.07.
【００２０】ＴｉのＺｒへの置換量ｇを０．４６≦ｇ≦
０．５２としたのは、ｇが０．４６未満の場合は比誘電
率εｒが大きく、耐熱性が低下し、０．５２よりも大き
い場合には電気機械結合係数Ｋｐが低くなり過ぎるため
である。ＴｉのＺｒへの置換量ｇは０．４８≦ｇ≦０．
５１であることが望ましい。The substitution amount g of Ti with Zr is 0.46 ≦ g ≦
The reason for setting 0.52 is that when g is less than 0.46, the relative permittivity εr is large and the heat resistance is lowered, and when it is larger than 0.52, the electromechanical coupling coefficient Kp is too low. is there. The substitution amount g of Ti by Zr is 0.48 ≦ g ≦ 0.
It is preferably 51.
【００２１】Ｌ（Ｓｒおよび/ またはＢａ）の置換量ｘ
を０．０１≦ｘ≦０．０８としたのは、ｘが０．０１未
満の場合は電気機械結合係数Ｋｐが小さく、０．０８よ
りも大きい場合には比誘電率εｒが大きくなるためであ
る。Ｓｒおよび/ またはＢａの置換量ｘは０．０１≦ｘ
≦０．０１５であることが望ましい。本発明では特にＳ
ｒで置換することが望ましい。Substitution amount x of L (Sr and / or Ba) x
Is set to 0.01 ≦ x ≦ 0.08 because the electromechanical coupling coefficient Kp is small when x is less than 0.01 and the relative dielectric constant εr is large when x is greater than 0.08. is there. Substitution amount x of Sr and / or Ba is 0.01 ≦ x
It is desirable that ≦ 0.015. In the present invention, especially S
Substitution with r is desirable.
【００２２】Ｍ（Ｌａ，Ｃｅ，Ｇｄ，Ｎｄ，Ｓｍ，Ｐ
ｒ，Ｅｕのうち少なくとも一種）の置換量ｙを０．００
２≦ｙ≦０．０５としたのは、ｙが０．００２未満の場
合は電気機械結合係数Ｋｐが小さくなり、０．０５より
も大きい場合には比誘電率εｒが高く、耐熱性が低下す
るためである。Ｍの置換量ｙは０．００３≦ｙ≦０．０
０５であることが望ましい。M (La, Ce, Gd, Nd, Sm, P
The substitution amount y of at least one of r and Eu) is 0.00
2 ≦ y ≦ 0.05 is set so that when y is less than 0.002, the electromechanical coupling coefficient Kp becomes small, and when y is larger than 0.05, the relative dielectric constant εr is high and the heat resistance is deteriorated. This is because The substitution amount y of M is 0.003 ≦ y ≦ 0.0
A value of 05 is desirable.
【００２３】本発明の圧電磁器組成物としては、組成式
を（Ｐｂ1-x-y Ｌx Ｍy ) a (Ｎｂb Ｃｒc Ｙｂd Ａｌ
e ) f Ｔｉg Ｚr1-f-g Ｏ3 （ここで、ＬはＳｒ，Ｂａ
のうち少なくとも一種、ＭはＬａ，Ｇｄ，Ｎｄ，Ｓｍ，
Ｐｒ，Ｅｕのうち少なくとも一種）と表わした時、ｘ，
ｙ，ａ，ｂ，ｃ，ｄ，ｅ，ｆ，ｇが０．０１≦ｘ≦０．
０１５、０．００３≦ｙ≦０．００５、０．９９≦ａ≦
１．０１、０．５２≦ｂ≦０．５８、０．２２≦ｃ≦
０．２６、０．０２≦ｄ≦０．１７、０．０２≦ｅ≦
０．１２、０．０５≦ｆ≦０．０７、０．４８≦ｇ≦
０．５１を満足することが望ましい。[0023] As the piezoelectric ceramic composition of the present invention, the composition formula (Pb 1-xy L x M y) a (Nb b Cr c Yb d Al
e ) f Ti g Zr 1-fg O 3 (where L is Sr, Ba
At least one of them, M is La, Gd, Nd, Sm,
At least one of Pr and Eu), x,
y, a, b, c, d, e, f, g are 0.01 ≦ x ≦ 0.
015, 0.003 ≦ y ≦ 0.005, 0.99 ≦ a ≦
1.01, 0.52 ≦ b ≦ 0.58, 0.22 ≦ c ≦
0.26, 0.02 ≦ d ≦ 0.17, 0.02 ≦ e ≦
0.12, 0.05 ≦ f ≦ 0.07, 0.48 ≦ g ≦
It is desirable to satisfy 0.51.
【００２４】そして、本発明の圧電磁器は、例えば、原
料としてＰｂＯ、ＺｒＯ2 、ＴｉＯ2 、Ｎｂ2 Ｏ5 、Ｃ
ｒ2 Ｏ3 、Ｙｂ2 Ｏ3 、Ａｌ2 Ｏ3 およびＬａ，Ｃｅ，
Ｇｄ，Ｎｄ，Ｓｍ，Ｐｒ，Ｅｕのうち少なくとも一種の
酸化物、並びにＳｒＣＯ3 および／またはＢａＣＯ3 の
各原料粉末を所定量秤量し、ＺｒＯ2 ボールをボールミ
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、８００〜１０００℃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。The piezoelectric ceramic of the present invention can be manufactured, for example, by using PbO, ZrO 2 , TiO 2 , Nb 2 O 5 and C as raw materials.
r 2 O 3 , Yb 2 O 3 , Al 2 O 3 and La, Ce,
At least one oxide of Gd, Nd, Sm, Pr, Eu, and each raw material powder of SrCO 3 and / or BaCO 3 are weighed in a predetermined amount, and ZrO 2 balls are wet-mixed with a ball mill for 10 to 24 hours, Next, after dehydrating and drying this mixture, it is calcined at 800 to 1000 ° C. for 1 to 3 hours, and the calcined product is pulverized again by a ball mill or the like.
【００２５】その後、この粉砕物に有機バインダーを混
合し、造粒後、所定圧力で成形して成形体を作製し、こ
れらを大気中において１２００〜１３５０℃で０．５〜
４時間焼成することにより得られる。Then, an organic binder is mixed with the crushed product, and after granulation, the product is molded under a predetermined pressure to prepare a molded product, which is 0.5 to 0.5 at 1200 to 1350 ° C. in the atmosphere.
It is obtained by firing for 4 hours.
【００２６】本発明の圧電磁器組成物では、原料粉末か
ら希土類元素等の不可避不純物が混入する場合がある。
また、製造過程で、容器や粉砕ボール等からその成分が
混入する場合もある。In the piezoelectric ceramic composition of the present invention, inevitable impurities such as rare earth elements may be mixed from the raw material powder.
In addition, in the manufacturing process, the component may be mixed from a container, a crushed ball, or the like.
【００２７】[0027]
【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 、Ｎｂ2 Ｏ5 、
Ｃｒ2 Ｏ3 、Ｙｂ2 Ｏ3 、Ａｌ2 Ｏ3 、ＳｒＣＯ3 およ
び／またはＢａＣＯ3 、Ｌａ，Ｃｅ，Ｇｄ，Ｎｄ，Ｓ
ｍ，Ｐｒ，Ｅｕのうち少なくとも一種の酸化物の各原料
粉末を、表１および表２に示すような組成となるように
所定量秤量し、ボールミルで１２時間以上湿式混合し、
次いで、この混合物を脱水、乾燥した後、９５０℃で３
時間仮焼し、当該仮焼物を再びボールミルで粉砕した。The present invention will be described in the following examples. As raw material powder, PbO, ZrO 2 , TiO 2 , Nb 2 O 5 ,
Cr 2 O 3 , Yb 2 O 3 , Al 2 O 3 , SrCO 3 and / or BaCO 3 , La, Ce, Gd, Nd, S
A predetermined amount of each raw material powder of at least one oxide of m, Pr, and Eu was weighed so as to have a composition shown in Table 1 and Table 2, and wet-mixed for 12 hours or more in a ball mill,
Then, after dehydrating and drying the mixture, the mixture was dried at 950 ° C. for 3 hours.
It was calcined for a period of time, and the calcined product was pulverized again with a ball mill.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】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１．５乃至
２ｔ／ｃｍ2 の圧力で直径２３ｍｍ、厚さ２ｍｍの寸法
からなる円板形状にプレス成形した。さらに、これらの
成形体をＭｇＯ等からなる容器内に密閉し、大気中１３
００乃至１３５０℃で２時間の条件で焼成した。Then, an organic binder (P
VA) was mixed and granulated. The obtained powder was press-molded at a pressure of 1.5 to 2 t / cm 2 into a disk shape having a diameter of 23 mm and a thickness of 2 mm. Further, these molded bodies were sealed in a container made of MgO or the like and placed in the atmosphere.
Baking was performed at 00 to 1350 ° C. for 2 hours.
【００３１】得られた焼結体を研磨して厚み０．５ｍｍ
の円板を形成した。この円板の両主面にＡｇペーストを
６００℃で焼付けることにより電極を形成し、８０℃の
シリコンオイル中で３ｋｖ／ｍｍの直流電圧を３０分間
印加して分極処理した後、電気機械結合係数Ｋｐ、機械
的品質係数Ｑｍ、耐熱性を評価した。また、比誘電率ε
ｒをインピーダンスメータで求められた容量から計算し
て求めた。The obtained sintered body is polished to have a thickness of 0.5 mm.
Disk was formed. Electrodes were formed by baking Ag paste on both principal surfaces of this disc at 600 ° C., and a DC voltage of 3 kv / mm was applied for 30 minutes in silicon oil at 80 ° C. for polarization treatment, followed by electromechanical coupling. The coefficient Kp, mechanical quality coefficient Qm, and heat resistance were evaluated. Also, the relative permittivity ε
r was calculated and calculated from the capacity obtained by the impedance meter.
【００３２】電気機械結合係数Ｋｐ、機械的品質係数Ｑ
ｍはインピーダンスメータで測定した共振周波数と***
振周波数の値から計算により求めた。耐熱性は、２５０
℃をピークとする半田リフロー炉を３回連続して通過さ
せる試験を行った際の、試験前の共振周波数ｆｒ1 と試
験後の共振周波数ｆｒ2 の値から、 ｆｒa ＝｜（ｆｒ2 −ｆｒ1 ）｜／ｆｒ1 ×１００ の式を用いて算出した変化率ｆｒa で評価した。これら
の結果を表３および表４に示す。Electromechanical coupling coefficient Kp, mechanical quality coefficient Q
m was calculated from the values of the resonance frequency and the anti-resonance frequency measured with an impedance meter. Heat resistance is 250
From the values of the resonance frequency fr 1 before the test and the resonance frequency fr 2 after the test at the time of performing the test in which the solder reflow furnace having a peak temperature of 3 ° C. is passed three times continuously, fra = | (fr 2 −fr 1 ) | / fr 1 × 100 The rate of change fra calculated using the equation was evaluated. The results are shown in Tables 3 and 4.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】尚、表３および表４における試料Ｎo.５５
はＭとしてＧｄを用い、試料Ｎo.５６はＭとしてＳｍを
用い、試料Ｎo.５７はＭとしてＰｒを用い、試料Ｎo.５
８はＭとしてＮｄを用い、試料Ｎo.３４はＭとしてＬａ
を０．００３と、Ｃｅを０．００２とを用い、試料Ｎo.
３５はＭとしてＥｕを用いた。その他の試料ではＭとし
てＬａを用いた。Sample No. 55 in Tables 3 and 4
Gd as M, Sample No. 56 uses Sm as M, Sample No. 57 uses Pr as M, and Sample No. 5
8 uses Nd as M, and sample No. 34 has La as M
Is 0.003 and Ce is 0.002, and the sample No.
35 used Eu as M. In other samples, La was used as M.
【００３６】また、試料Ｎo.７０はＬとしてＢａを用
い、試料Ｎo.３３はＬとしてＢａを０．００７、Ｓｒを
０．００８用い、他はＬとしてＳｒを用いた。In Sample No. 70, Ba was used as L. In Sample No. 33, Ba was 0.007 and Sr was 0.008 as L, and Sr was used as L for others.
【００３７】これらの表３および表４から、本発明の圧
電磁器組成物は電気機械結合係数Ｋｐが４０％以上と大
きく、機械的品質係数Ｑｍが２００以下と低く、比誘電
率は１５００以下と低く、また、耐熱試験によるｆｒa
の変化が±０．１％以下と小さいことが判る。From these Tables 3 and 4, the piezoelectric ceramic composition of the present invention has a large electromechanical coupling coefficient Kp of 40% or more, a low mechanical quality coefficient Qm of 200 or less, and a relative dielectric constant of 1500 or less. Low and fra by heat resistance test
It can be seen that the change in is as small as ± 0.1% or less.
【００３８】[0038]
【発明の効果】以上詳述した通り、本発明によれば、Ｐ
ｂＺｒＯ3 −ＰｂＴｉＯ3 系の磁器組成物のＺｒおよび
Ｔｉの一部をＮｂ，Ｃｒ、Ｙｂ，Ａｌで置換し、Ｐｂの
一部をＳｒおよび／またはＢａやＬａ，Ｃｅ，Ｇｄ，Ｎ
ｄ，Ｓｍ，Ｐｒ，Ｅｕのうち少なくとも一種で置換する
ことにより、高い電気機械結合係数Ｋｐ、低い機械的品
質係数Ｑｍ、低い比誘電率εｒを示すとともに、耐熱性
を向上することができ、表面実装用圧電部品などの素子
として有効に用いられる圧電磁器組成物を得ることがで
きる。As described in detail above, according to the present invention, P
Part of Zr and Ti of the bZrO 3 —PbTiO 3 -based porcelain composition is replaced with Nb, Cr, Yb, and Al, and part of Pb is Sr and / or Ba, La, Ce, Gd, N.
By substituting at least one of d, Sm, Pr, and Eu, a high electromechanical coupling coefficient Kp, a low mechanical quality coefficient Qm, a low relative dielectric constant εr, and heat resistance can be improved. It is possible to obtain a piezoelectric ceramic composition that is effectively used as an element such as a mounting piezoelectric component.
Claims (1)
Ｃｒ、Ｙｂ、Ａｌを含むペロブスカイト型化合物であっ
て、その組成式を （Ｐｂ1-x-y Ｌx Ｍy ) a (Ｎｂb Ｃｒc Ｙｂd Ａ
ｌe ) f Ｔｉg Ｚr1-f-gＯ3 （ここで、ＬはＳｒ，Ｂａのうち少なくとも一種、Ｍは
Ｌａ，Ｃｅ，Ｇｄ，Ｎｄ，Ｓｍ，Ｐｒ，Ｅｕのうち少な
くとも一種）と表わした時、ｘ，ｙ，ａ，ｂ，ｃ，ｄ，
ｅ，ｆ，ｇが ０．０１ ≦ｘ≦０．０８ ０．００２≦ｙ≦０．０５ ０．９５ ≦ａ≦１．０５ ０．４６ ≦ｂ≦０．６０ ０．１１ ≦ｃ≦０．４２ ０．０２ ≦ｄ≦０．３１ ０．０２ ≦ｅ≦０．１８ ０．０２ ≦ｆ≦０．１５ ０．４６ ≦ｇ≦０．５２ ｂ＋ｃ＋ｄ＋ｅ＝１．００ を満足することを特徴とする圧電磁器組成物。1. A metal component of Pb, Zr, Ti, Nb,
Cr, Yb, a perovskite compound containing Al, the composition formula (Pb 1-xy L x M y) a (Nb b Cr c Yb d A
l e ) f Ti g Zr 1-fg O 3 (where L is at least one of Sr and Ba and M is at least one of La, Ce, Gd, Nd, Sm, Pr and Eu) , X, y, a, b, c, d,
e, f and g are 0.01 ≤ x ≤ 0.08 0.002 ≤ y ≤ 0.05 0.95 ≤ a ≤ 1.05 0.46 ≤ b ≤ 0.60 0.11 ≤ c ≤ 0. 42 0.02 ≤ d ≤ 0.31 0.02 ≤ e ≤ 0.18 0.02 ≤ f ≤ 0.15 0.46 ≤ g ≤ 0.52 b + c + d + e = 1.00 Piezoelectric composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10714196A JP3761970B2 (en) | 1996-04-26 | 1996-04-26 | Piezoelectric ceramic composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10714196A JP3761970B2 (en) | 1996-04-26 | 1996-04-26 | Piezoelectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09295864A true JPH09295864A (en) | 1997-11-18 |
| JP3761970B2 JP3761970B2 (en) | 2006-03-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005150694A (en) * | 2003-10-23 | 2005-06-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005150694A (en) * | 2003-10-23 | 2005-06-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
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|---|---|
| JP3761970B2 (en) | 2006-03-29 |
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