JPH107460A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
- Publication number
- JPH107460A JPH107460A JP8160193A JP16019396A JPH107460A JP H107460 A JPH107460 A JP H107460A JP 8160193 A JP8160193 A JP 8160193A JP 16019396 A JP16019396 A JP 16019396A JP H107460 A JPH107460 A JP H107460A
- Authority
- JP
- Japan
- Prior art keywords
- displacement
- amount
- sample
- piezoelectric ceramic
- ceramic 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 229910052573 porcelain Inorganic materials 0.000 title abstract 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims abstract description 28
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 25
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 24
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 22
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 13
- 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 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 43
- 239000011651 chromium Substances 0.000 claims description 34
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910017895 Sb2 O3 Inorganic materials 0.000 abstract 1
- 229910004446 Ta2 O5 Inorganic materials 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 description 74
- 238000005259 measurement Methods 0.000 description 23
- 230000005684 electric field Effects 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 13
- 238000006467 substitution reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000008188 pellet Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 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、アクチュエータ等
の圧電素子に利用することができる、チタン酸ジルコン
酸鉛（ＰＺＴ）を主体とする圧電磁器組成物に関し、特
に自動車等に使用される圧電素子に利用可能な広温度範
囲での高変位性能と高耐久性とを有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 mainly composed of lead zirconate titanate (PZT) which can be used for a piezoelectric element such as an actuator. The present invention relates to a piezoelectric ceramic composition having high displacement performance and high durability in a wide temperature range, which can be used for a piezoelectric ceramic.
【０００２】[0002]
【従来の技術】従来、アクチュエータ等に利用される圧
電材料として、ＰＺＴを主体とする圧電磁器組成物が多
く提案されている。特にＰＺＴにドナー元素を置換し
た、いわゆるソフト圧電材料は、電界誘起変位量（以
下、変位量と略する）が大きく変位性能に優れ、アクチ
ュエータ等への応用に適した材料として注目されてお
り、こうしたソフト圧電材料に種々の元素を添加するな
どしてさらに種々の特性を付与する試みがなされてい
る。2. Description of the Related Art Hitherto, many piezoelectric ceramic compositions mainly composed of PZT have been proposed as piezoelectric materials used for actuators and the like. In particular, a so-called soft piezoelectric material obtained by substituting a donor element for PZT has a large electric field-induced displacement (hereinafter abbreviated as displacement), has excellent displacement performance, and is attracting attention as a material suitable for application to actuators and the like. Attempts have been made to further impart various characteristics by adding various elements to such soft piezoelectric materials.
【０００３】このような圧電磁器組成物として、例え
ば、特開平５−８４５号公報、特開平５−８４６号公報
では、ＰＺＴのＰｂサイト（Ａサイト）をＬａで置換
し、ＳｂもしくはＮｂを添加したものが開示されてい
る。これらの圧電磁器組成物では、ＳｂもしくはＮｂの
添加によりｄ定数が高くなり、主に線形変位（印加電界
に比例した変位）を利用するバイモルフ用の高変位量を
もつ圧電材料となることが知られている。As such a piezoelectric ceramic composition, for example, in JP-A-5-845 and JP-A-5-846, the Pb site (A site) of PZT is replaced with La, and Sb or Nb is added. Is disclosed. In these piezoelectric ceramic compositions, it is known that the addition of Sb or Nb increases the d constant, resulting in a piezoelectric material having a large displacement for a bimorph mainly using linear displacement (displacement proportional to an applied electric field). Have been.
【０００４】一方、さらなる高変位量、高出力を得るた
めには、抗電界を超える高い電界を印加し、９０°ドメ
イン反転に伴う非線形変位を利用することが必要とな
る。しかし、ドメイン反転が起きるほどの高電界下で長
時間にわたって駆動させると、変位量およびエネルギー
変換効率の低下が生じてしまう。しかし、従来のソフト
圧電材料は、抗電界が低く、またドメイン反転が起こり
やすいため、高電界下での駆動によって変位量やエネル
ギー変換効率の低下が生じていた。このため、高電界下
での長時間の駆動がなされるような用途においては、従
来のソフト圧電材料を圧電アクチュエータに利用するこ
とは難しかった。On the other hand, in order to obtain an even higher displacement and higher output, it is necessary to apply a high electric field exceeding the coercive electric field and use the non-linear displacement accompanying the 90 ° domain inversion. However, when driving is performed for a long time under a high electric field such that domain inversion occurs, the displacement amount and the energy conversion efficiency decrease. However, since the conventional soft piezoelectric material has a low coercive electric field and easily causes domain inversion, the driving amount under a high electric field causes a decrease in displacement and energy conversion efficiency. For this reason, it has been difficult to use a conventional soft piezoelectric material for a piezoelectric actuator in an application in which driving is performed for a long time under a high electric field.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記実情に鑑
みてなされたものであり、エネルギー変換効率および変
位量が大きく、また広温度範囲での温度変化に対する変
位量の変化が小さく温度安定性に優れ、かつ高電界下で
長時間駆動しても特性変化の小さな耐久性の高い圧電磁
器組成物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a large energy conversion efficiency and a large displacement, and a small change in the displacement with respect to a temperature change in a wide temperature range. It is an object of the present invention to provide a highly durable piezoelectric ceramic composition having excellent characteristics and having a small characteristic change even when driven for a long time under a high electric field.
【０００６】[0006]
【課題を解決するための手段】本発明者は、ＰＺＴのＡ
サイトにＬａを置換し、またＴｉおよびＺｒサイト（Ｂ
サイト）にＳｂ、Ｎｂ、Ｔａの少なくとも一種を置換
し、かつこのＰＺＴに酸化クロムを添加することによ
り、エネルギー変換効率および変位量が大きくなり、広
温度範囲での温度安定性に優れ、かつ耐久性の高い圧電
磁器組成物が得られることを見出し、本発明に至ったも
のである。Means for Solving the Problems The inventor of the present invention has proposed the AZ of PZT.
La at the site and Ti and Zr sites (B
By substituting at least one of Sb, Nb, and Ta for (Site) and adding chromium oxide to this PZT, the energy conversion efficiency and displacement are increased, and the temperature stability in a wide temperature range is excellent and the durability is high. It has been found that a piezoelectric ceramic composition having high properties can be obtained, and the present invention has been accomplished.
【０００７】即ち、本発明の圧電磁器組成物は、チタン
酸ジルコン酸鉛（ＰＺＴ）のＰｂサイトの一部にＬａを
置換し、Ｔｉ・ＺｒサイトにＮｂ、Ｔａ、Ｓｂのうちの
少なくとも一種を置換し、かつ酸化クロムを添加したこ
とを特徴とする。一方、ＰＺＴの一部をドナー元素で置
換し、Ｃｒを添加した圧電磁器組成物は、特開平５−１
４８０１６号公報でＰＺＴのＡサイトにＳｒ、Ｃａ、Ｂ
ａを置換し、Ｓｂ、Ｎｂ、ＴａおよびＣｒ等を添加した
ものが開示されているように従来からあった。しかし、
この公報の圧電磁器組成物は、主にセラミックフィルタ
等に利用される比較的ハードな圧電材料であり、変位量
が小さい。またＣｒはＰＺＴをハード化する目的で添加
されており、Ｃｒの添加による耐久性の向上については
示唆していない。That is, in the piezoelectric ceramic composition of the present invention, La is substituted for a part of the Pb site of lead zirconate titanate (PZT), and at least one of Nb, Ta, and Sb is substituted for the Ti.Zr site. It is characterized by substitution and addition of chromium oxide. On the other hand, a piezoelectric ceramic composition in which a part of PZT is replaced by a donor element and Cr is added is disclosed in
No. 48016, Sr, Ca, B
There has conventionally been one in which a is substituted and Sb, Nb, Ta, Cr and the like are added as disclosed. But,
The piezoelectric ceramic composition disclosed in this publication is a relatively hard piezoelectric material mainly used for ceramic filters and the like, and has a small displacement. Further, Cr is added for the purpose of hardening PZT, and does not suggest improvement in durability by the addition of Cr.
【０００８】本発明の圧電磁器組成物は、ＰＺＴの一部
をＬａおよびＳｂ、Ｎｂ、Ｔａの少なくとも一種により
置換してＰＺＴをソフト化してエネルギー変換効率およ
び変位量を大きくし、−３０℃〜１５０℃の広温度範囲
での温度安定性を向上させ、またＣｒの添加によって耐
久性を向上させたものである。この圧電磁器組成物によ
り、こうした広温度範囲で安定して動作し、高電界下で
長時間の駆動にも特性が劣化しない圧電素子の圧電材料
とすることができる。In the piezoelectric ceramic composition of the present invention, a part of PZT is replaced with at least one of La and Sb, Nb, and Ta to soften PZT to increase energy conversion efficiency and displacement, and to increase the temperature from -30 ° C. The temperature stability in a wide temperature range of 150 ° C. is improved, and the durability is improved by adding Cr. This piezoelectric ceramic composition can be used as a piezoelectric material for a piezoelectric element that operates stably in such a wide temperature range and does not deteriorate in characteristics even when driven for a long time under a high electric field.
【０００９】[0009]
【発明の実施の形態】本発明では、ＰＺＴのドナー元素
として、ＬａおよびＮｂ、Ｔａ、Ｓｂを用い、Ａサイト
の一部をＬａで置換し、Ｂサイトの一部をＮｂ、Ｔａ、
Ｓｂの少なくとも一種で置換する。これらの元素で置換
することにより、ＰＺＴの変位性能を向上させることが
できる。特に、Ｌａは変位量についての温度安定性に著
しい効果を示し、Ｎｂ、Ｔａ、Ｓｂは変位量の向上に著
しい効果を示す。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, La and Nb, Ta, and Sb are used as donor elements of PZT, a part of the A site is replaced with La, and a part of the B site is Nb, Ta, and Sb.
Substitute with at least one of Sb. By substituting these elements, the displacement performance of PZT can be improved. In particular, La has a remarkable effect on the temperature stability of the displacement, and Nb, Ta, and Sb have a remarkable effect on the improvement of the displacement.
【００１０】このとき、一般式：Ｐｂ1-(3/2)xＬａ
x （（Ｚｒy Ｔｉ1-y ）1-z Ｍz ）Ｏ3において、Ｌａ
の置換量（ｘ）とＮｂ、Ｔａ、Ｓｂの少なくとも一種の
置換量（ｚ）の組成で表される圧電磁器組成物とするこ
とにより、エネルギー変換効率および変位量が大きく、
変位量についての温度安定性に優れるものとすることが
できる。At this time, the general formula: Pb 1- (3/2) x La
x In ((Zr y Ti 1-y ) 1-z M z) O 3, La
By using the piezoelectric ceramic composition represented by the composition of the substitution amount (x) and at least one substitution amount (z) of Nb, Ta, and Sb, the energy conversion efficiency and the displacement amount are large,
The temperature stability of the displacement amount can be excellent.
【００１１】この一般式において、特にＬａの置換量と
Ｎｂ、Ｔａ、Ｓｂの少なくとも一種の置換量との合計置
換量（ｘ＋ｚ）を０．０３以上とすることにより、従来
から圧電素子として利用されている圧電磁器組成物の歪
量（１．５×１０-3（％）（±２ｋＶ／ｍｍ印加時））
を上回る歪量が得られ、変位量が向上するため望まし
い。In this general formula, the total substitution amount (x + z) of the substitution amount of La and the substitution amount of at least one of Nb, Ta, and Sb is set to 0.03 or more. Of the piezoelectric ceramic composition (1.5 × 10 −3 (%) (when ± 2 kV / mm is applied))
Is preferable because a strain amount exceeding the above is obtained and the displacement amount is improved.
【００１２】また、安定した特性を得るためには、キュ
リー温度（Ｔｃ）の１／２程度以下の温度範囲で圧電素
子を使用することが必要である。これはＴｃの１／２の
温度より高温で使用すると、圧電素子の脱分極が起こり
やすくなり、エネルギー変換効率および変位量の低下が
生じるなど素子性能が劣化してしまうためである。従っ
て、高温で安定した特性を得るためにはＴｃが大きいこ
とが条件となる。特に、自動車用の圧電アクチュエータ
として利用するためには、−３０℃〜１５０℃の広温度
範囲で安定に動作することが必要となるため、２５０℃
以上のＴｃが要求される。本発明の圧電磁器組成物にお
いては、（ｘ＋ｚ）が０．０６より小さいときに２５０
℃以上のＴｃを得ることができる。一方、（ｘ＋ｚ）が
０．０６以上となるとＴｃは２５０℃を下回り好ましく
ない。In order to obtain stable characteristics, it is necessary to use a piezoelectric element in a temperature range of about 1/2 or less of the Curie temperature (Tc). This is because when used at a temperature higher than half the temperature of Tc, depolarization of the piezoelectric element is likely to occur, and the element performance deteriorates, such as a decrease in energy conversion efficiency and displacement. Therefore, in order to obtain stable characteristics at a high temperature, Tc must be large. In particular, in order to use as a piezoelectric actuator for an automobile, it is necessary to operate stably in a wide temperature range of −30 ° C. to 150 ° C.
The above Tc is required. In the piezoelectric ceramic composition of the present invention, when (x + z) is smaller than 0.06, 250
It is possible to obtain Tc of not less than ° C. On the other hand, when (x + z) is 0.06 or more, Tc is lower than 250 ° C., which is not preferable.
【００１３】従って、変位量を大きくし、かつ広温度範
囲で安定した変位量を得るためには、ｘおよびｚが０．
０３≦ｘ＋ｚ≦０．０６を満たすことが望ましい。ま
た、０．０３≦ｘ＋ｚ≦０．０６の範囲内で、ｘとｚの
範囲をそれぞれ０．０１≦ｘ≦０．０５、０．０１≦ｚ
≦０．０３となる様にＬａとＮｂ、Ｔａ、Ｓｂの少なく
とも一種との双方をバランスよく置換すると、変位量の
温度変化をさらに小さくすることができる。Ｌａの置換
量が上記範囲外となると変位特性が不十分となり、ま
た、Ｎｂ、Ｔａ、Ｓｂの置換量が上記範囲外となると変
位量の温度安定性が失われ、好ましくない。Therefore, in order to increase the amount of displacement and obtain a stable amount of displacement over a wide temperature range, x and z must be equal to 0.
It is desirable to satisfy 03 ≦ x + z ≦ 0.06. Further, within the range of 0.03 ≦ x + z ≦ 0.06, the ranges of x and z are 0.01 ≦ x ≦ 0.05 and 0.01 ≦ z, respectively.
When both La and at least one of Nb, Ta, and Sb are replaced in a well-balanced manner so that ≦ 0.03, the temperature change of the displacement amount can be further reduced. If the replacement amount of La is out of the above range, the displacement characteristics become insufficient, and if the replacement amount of Nb, Ta, Sb is out of the above range, the temperature stability of the displacement is lost, which is not preferable.
【００１４】ＺｒとＴｉの比（ｙ）を適当にとり、モル
フォトロピック相境界（ＭＰＢ）近傍の組成とすること
により、変位量を大きくすることができる。しかし、組
成がＭＰＢの組成からずれると、変位量およびエネルギ
ー変換効率が急激に低下してしまう。本発明では、Ｌａ
の置換によりこのＭＰＢがシフトするため、Ｌａの置換
量に応じてｙを適当に変えて、ＭＰＢ近傍の組成となる
ようにする必要がある。本発明における上記Ｌａの置換
量では、ｙを０．５〜０．６の範囲内とすることによ
り、ＭＰＢ近傍組成とすることができるため好ましい。By appropriately setting the ratio (y) between Zr and Ti and setting the composition near the morphotropic phase boundary (MPB), the amount of displacement can be increased. However, if the composition deviates from the composition of MPB, the amount of displacement and the energy conversion efficiency sharply decrease. In the present invention, La
, The MPB shifts. Therefore, it is necessary to appropriately change y in accordance with the amount of La to obtain a composition near the MPB. In the La substitution amount in the present invention, it is preferable to set y in the range of 0.5 to 0.6 because the composition near the MPB can be obtained.
【００１５】さらに、ＬａおよびＮｂ、Ｔａ、Ｓｂを置
換したＰＺＴに酸化クロムを微量添加することにより、
高電界を印加した状態での繰り返し駆動による変位性能
の低下を少なくすることができ、耐久性を向上させるこ
とができる。この効果の発現機構の詳細は不明である
が、少なくともドナー元素とクロム元素が共存すること
により発現するものと考えられる。ＬａおよびＮｂ、Ｔ
ａ、Ｓｂの少なくとも一種のドナー元素によるＰＺＴの
置換の有無で酸化クロム添加効果を比較すると、ドナー
元素で置換してある場合は、機械的品質係数（Ｑｍ）の
低下、内部電界の低下が生じ、一方でドナー元素が少な
い、もしくは添加されていない場合には、Ｑｍの増加、
損失の低下が生じ（例えば、特開昭５８−９６７８７号
公報）、ドナー元素の有無で酸化クロム添加効果が著し
く異なる。このことから、ドナー元素で置換されていな
い場合や、ドナー元素で置換されていてもその置換量が
小さい場合には、酸化クロム添加による耐久性の改善効
果は得られない。Further, by adding a small amount of chromium oxide to PZT in which La and Nb, Ta, and Sb are substituted,
A decrease in displacement performance due to repeated driving in a state where a high electric field is applied can be reduced, and durability can be improved. Although the details of the mechanism of the development of this effect are unknown, it is considered that it is manifested at least when the donor element and the chromium element coexist. La and Nb, T
Comparing the effect of adding chromium oxide with the presence or absence of PZT by at least one donor element of a and Sb, when the PZT is replaced with a donor element, the mechanical quality factor (Qm) decreases and the internal electric field decreases. On the other hand, when the donor element is small or not added, Qm increases,
The loss is reduced (for example, JP-A-58-96787), and the effect of adding chromium oxide is significantly different depending on the presence or absence of a donor element. For this reason, in the case where the chromium oxide is not substituted with the donor element, or in the case where the chromium oxide is substituted with the donor element, the effect of improving the durability cannot be obtained.
【００１６】このとき、例えば、酸化クロムとしてＣｒ
2 Ｏ3 を添加する場合、Ｃｒ2 Ｏ3を添加した圧電磁器
組成物の全体の量を１００重量％とすると、Ｃｒ2 Ｏ3
の添加量は０．０１重量％以上０．３重量％以下である
ことが望ましい。これにより、エネルギー変換効率、変
位量、変位量の温度安定性、Ｔｃ等の特性にほとんど影
響を与えずに、耐久性を向上させることができる。Ｃｒ
2 Ｏ3 添加量が０．３重量％を超える場合、抗電界の低
下が生じ、高電界を印加した繰り返し駆動により脱分極
されやすくなるため、変位量等の特性の低下を招き好ま
しくない。At this time, for example, Cr is used as chromium oxide.
When adding 2 O 3 , if the total amount of the piezoelectric ceramic composition to which Cr 2 O 3 is added is 100% by weight, Cr 2 O 3
Is desirably 0.01% by weight or more and 0.3% by weight or less. Thereby, the durability can be improved without substantially affecting the characteristics such as the energy conversion efficiency, the displacement amount, the temperature stability of the displacement amount, and Tc. Cr
If the added amount of 2 O 3 exceeds 0.3% by weight, the coercive electric field is reduced, and it is easy to be depolarized by repeated driving with application of a high electric field.
【００１７】このとき、添加されたＣｒは、Ｎｂ、Ｔ
ａ、Ｓｂと同様にＰＺＴのＢサイトに置換していると考
えられる。その理由としては、ＣｒイオンのサイズがＢ
サイトイオンのサイズに近いこと、Ｘ線回折等の構造解
析によりＣｒの粒界析出が観察されていないことが挙げ
られる。（こうしたＣｒとは異なり、Ｖ、Ｍｏ等を少量
添加した場合には、Ｐｂ2 Ｖ3 Ｏ8 、Ｐｂ2 ＭｏＯ5 と
いった形態で粒界析出が観察される。） 本発明の圧電磁器組成物の製造方法としては特に限定さ
れないが、ＰｂＯ、ＺｒＯ2 、ＴｉＯ2 、Ｌａ2 Ｏ3 あ
るいはＬａ2 （ＣＯ3 ）3 、Ｎｂ2 Ｏ5 、Ｔａ 2 Ｏ5 、
Ｓｂ2 Ｏ3 、Ｃｒ2 Ｏ3 等の酸化物粉末あるいは炭酸塩
を用い、一般式：Ｐｂ1-(3/2)xＬａx （（Ｚｒy Ｔｉ
1-y ）1-z Ｍz ）Ｏ3 の組成となる様にこれらの原料粉
末を秤量、混合して圧電磁器組成物の原料粉末を調製
し、この原料粉末を一旦仮焼して仮焼粉末を得た後、ボ
ールミル、媒体攪拌ミル等の粉砕装置により粉砕し粉末
状の圧電磁器組成物を得ることができる。At this time, the added Cr is Nb, T
It is considered that it is substituted for the B site of PZT as in the case of a and Sb.
available. The reason is that the size of the Cr ion is B
Close to site ion size, structural solution such as X-ray diffraction
Precipitation of grain boundary of Cr was not observed by precipitation
Can be (Unlike such Cr, V, Mo, etc.
When added, PbTwoVThreeO8, PbTwoMoOFiveWhen
Grain boundary precipitation is observed in such a form. The method for producing the piezoelectric ceramic composition of the present invention is not particularly limited.
But not PbO, ZrOTwo, TiOTwo, LaTwoOThreeAh
Rui LaTwo(COThree)Three, NbTwoOFive, Ta TwoOFive,
SbTwoOThree, CrTwoOThreeOxide powder or carbonate such as
Using the general formula: Pb1- (3/2) xLax((ZryTi
1-y)1-zMz) OThreeThese raw material powders have a composition of
The powder is weighed and mixed to prepare the raw material powder of the piezoelectric ceramic composition
After calcining the raw material powder to obtain a calcined powder,
Pulverized with a pulverizing device such as
A piezoelectric ceramic composition in the form of a solid can be obtained.
【００１８】これをそのまま、あるいは造粒して、一軸
プレスあるいはＣＩＰ（冷間静水圧プレス）により成形
し、所望の試料形状の成形体を得た後、造粒したものに
関しては脱脂を施して、その後、密閉容器を用い、鉛の
揮散を防ぐために調整した雰囲気下で焼成することによ
り圧電体を製造することができる。あるいはまた、粉砕
後の仮焼粉末をバインダー、分散材、可塑剤と混合し、
スラリー状にした後、テープ形成あるいは押し出し成形
等により成形を行い、これを脱脂、焼成して圧電体を得
ることも可能である。This is directly or granulated and formed by a uniaxial press or a CIP (cold isostatic press) to obtain a formed body having a desired sample shape. The formed body is degreased. Thereafter, the piezoelectric body can be manufactured by baking in an atmosphere adjusted to prevent volatilization of lead by using a closed container. Alternatively, the calcined powder after grinding is mixed with a binder, a dispersant, and a plasticizer,
It is also possible to obtain a piezoelectric body by forming a slurry, forming by tape forming or extrusion forming, etc., and degreased and fired.
【００１９】[0019]
【作用】本発明の圧電磁器組成物により、エネルギー変
換効率および変位量が大きく、また広温度範囲で特性の
温度安定性に優れ、かつ、高電界下で長時間駆動しても
特性変化の小さな耐久性の高い圧電磁器組成物とするこ
とができる。特に、一般式：Ｐｂ1-(3/2)xＬａx （（Ｚ
ｒy Ｔｉ1-y ）1-z Ｍz ）Ｏ3 （但し、Ｍは、Ｎｂ、Ｔ
ａ、Ｓｂのうちの少なくとも一種である。）の組成で表
されるＰＺＴに、酸化クロムを添加した圧電磁器組成物
において、前記式中のｘ、ｙ、ｚが、０．０３≦ｘ＋ｚ
≦０．０６、および０．５≦ｘ＋ｚ≦０．６を満たし、
かつＣｒ2 Ｏ3 の添加量が、Ｃｒ2 Ｏ3 を添加した圧電
磁器組成物の全体の量を１００重量％とすると、０．０
１重量％以上０．３重量％以下である圧電磁器組成物
は、さらにエネルギー変換効率および変位量が大きく、
かつ−３０℃〜１５０℃の広温度範囲で特性の温度安定
性に優れ、耐久性の高い圧電磁器組成物とすることがで
きる。According to the piezoelectric ceramic composition of the present invention, the energy conversion efficiency and displacement amount are large, the temperature stability of characteristics is excellent in a wide temperature range, and the characteristics change is small even when driven for a long time under a high electric field. A highly durable piezoelectric ceramic composition can be obtained. In particular, the general formula: Pb 1- (3/2) x La x ((Z
r y Ti 1-y) 1 -z M z) O 3 ( where, M is, Nb, T
a and Sb. In the piezoelectric ceramic composition obtained by adding chromium oxide to PZT represented by the composition of the formula (1), x, y, and z in the above formula are 0.03 ≦ x + z
≦ 0.06 and 0.5 ≦ x + z ≦ 0.6,
And the addition amount of Cr 2 O 3 is, when the entire amount of the piezoelectric ceramic composition with the addition of Cr 2 O 3 and 100 wt%, 0.0
The piezoelectric ceramic composition of 1% by weight or more and 0.3% by weight or less has further higher energy conversion efficiency and displacement,
In addition, a piezoelectric ceramic composition having excellent temperature stability of characteristics in a wide temperature range of −30 ° C. to 150 ° C. and high durability can be obtained.
【００２０】さらに、前記ｘおよびｚは、０．０３≦ｘ
＋ｚ＜０．０６の範囲において、０．０１≦ｘ≦０．０
５かつ０．０１≦ｚ≦０．０３を満たす圧電磁器組成物
とすることにより、広温度範囲で変位量の温度安定性が
さらに優れる圧電磁器組成物とすることができる。Further, x and z are in the range of 0.03 ≦ x
In the range of + z <0.06, 0.01 ≦ x ≦ 0.0
By setting the piezoelectric ceramic composition to satisfy 5 and 0.01 ≦ z ≦ 0.03, it is possible to obtain a piezoelectric ceramic composition having more excellent temperature stability of displacement in a wide temperature range.
【００２１】[0021]
【実施例】ＰｂＯ、ＺｒＯ2 、ＴｉＯ2 、Ｌａ2 Ｏ3 、
Ｎｂ2 Ｏ5 、Ｔａ2 Ｏ5 、Ｓｂ2Ｏ3 、Ｃｒ2 Ｏ3 の各
原料粉末を用い、一般式：Ｐｂ1-(3/2)xＬａx （（Ｚｒ
yＴｉ1-y ）1-z Ｍz ）Ｏ3 （但し、Ｍは、Ｎｂ、Ｔ
ａ、Ｓｂのうちの少なくとも一種である。）において、
それぞれｘ、ｙ、ｚ、Ｍ、およびＣｒ2 Ｏ3 の添加量を
変えて原料粉末を秤量して乾式で混合し、組成およびＣ
ｒ2 Ｏ3 の添加量の異なる２１種類の原料粉末を得た。
これらの原料粉末を８００℃で５時間仮焼した後、得ら
れた仮焼粉末をボールミルにより２４時間湿式混合およ
び粉砕して粉末とし、これを乾燥して２１種類の圧電磁
器組成物（試料１〜試料２１）を得た。また、原料粉末
としてＬａ2 Ｏ3 の代わりにＳｒもしくはＢａを用いる
以外は、試料１〜試料２１と同様にして試料２２および
試料２３を作製した。EXAMPLES PbO, ZrO 2 , TiO 2 , La 2 O 3 ,
Using each raw material powder of Nb 2 O 5 , Ta 2 O 5 , Sb 2 O 3 , and Cr 2 O 3 , a general formula: Pb 1-(3/2) x La x ((Zr
y Ti 1-y ) 1-z M z ) O 3 (where M is Nb, T
a and Sb. )
The raw material powders were weighed while varying the amounts of x, y, z, M, and Cr 2 O 3 , and mixed in a dry system, and the composition and C
21 types of raw material powders having different amounts of added r 2 O 3 were obtained.
After calcining these raw material powders at 800 ° C. for 5 hours, the calcined powder obtained is wet-mixed and pulverized by a ball mill for 24 hours to obtain powders, which are dried to obtain 21 kinds of piezoelectric ceramic compositions (sample 1). ~ Sample 21) was obtained. Samples 22 and 23 were produced in the same manner as Samples 1 to 21, except that Sr or Ba was used instead of La 2 O 3 as the raw material powder.
【００２２】こうして表１に示される２３種類の組成を
もつ圧電磁器組成物（試料１〜試料２３）を得た。試料
２〜試料５、試料７〜試料１０、試料１２、試料１６は
実施例であり、試料１、試料６、試料１１、試料１３〜
１５、試料１７〜２３は比較例である。なお、表１では
比較例の試料番号に＊の記号を付した。また、表１中の
Ｃｒ2 Ｏ3 の欄の値はＣｒ2 Ｏ3 の添加量を表し、Ｃｒ
2 Ｏ3 を添加した圧電磁器組成物の全体の量を１００重
量％としたときのＣｒ2 Ｏ3 の添加量（重量％）を示
す。Thus, piezoelectric ceramic compositions (Samples 1 to 23) having 23 kinds of compositions shown in Table 1 were obtained. Sample 2 to Sample 5, Sample 7 to Sample 10, Sample 12, and Sample 16 are Examples, and are Sample 1, Sample 6, Sample 11, Sample 13 to
15. Samples 17 to 23 are comparative examples. In Table 1, the symbol * was added to the sample number of the comparative example. The values in the column of Cr 2 O 3 in Table 1 represent the amount of Cr 2 O 3 added,
The amount (% by weight) of Cr 2 O 3 is shown when the total amount of the piezoelectric ceramic composition to which 2 O 3 is added is 100% by weight.
【００２３】[0023]
【表１】 [Table 1]
【００２４】得られた圧電磁器組成物（試料１〜試料２
３）にそれぞれＰＶＡ（ポリビニルアルコール）を１重
量％加え、４０ＭＰａで、直径１８ｍｍ、厚さ２ｍｍの
円板に成形し、さらにＣＩＰ（冷間静水圧プレス）によ
り３００ＭＰａで成形し、脱脂を行った後、１２５０℃
で２時間、鉛の揮散を防ぐために調整した雰囲気下で焼
結した。The obtained piezoelectric ceramic composition (Sample 1 and Sample 2)
Each of 3) was added with 1% by weight of PVA (polyvinyl alcohol), molded at 40 MPa into a disc having a diameter of 18 mm and a thickness of 2 mm, and further molded at 300 MPa by CIP (cold isostatic press) to perform degreasing. After 1250 ° C
For 2 hours under an atmosphere adjusted to prevent the volatilization of lead.
【００２５】得られた焼結体を直径１１ｍｍ、厚さ０．
５ｍｍに加工した後、両平面に金電極を蒸着し、１００
℃のシリコンオイル中で２ｋＶ／ｍｍの直流電界を１０
分印加し分極処理を行って圧電体ペレットを形成した。
そして、この圧電体ペレットを測定試料とした。得られ
た圧電体ペレットの測定試料についてエネルギー変換効
率を評価するため、ベクトルインピーダンスアナライザ
（ＨＰ ４１９４Ａ）と恒温恒湿槽（タバイエスペック
ＰＬ−１Ｆ）とを組み合わせたシステムを用い、−３
０℃〜１５０℃におけるＫｐを測定した。The obtained sintered body was 11 mm in diameter and 0.1 mm in thickness.
After processing to 5 mm, gold electrodes were deposited on both planes,
DC electric field of 2 kV / mm in silicon oil
A minute application was performed to perform a polarization treatment to form a piezoelectric pellet.
Then, this piezoelectric pellet was used as a measurement sample. In order to evaluate the energy conversion efficiency of the obtained measurement sample of the piezoelectric pellet, a system combining a vector impedance analyzer (HP 4194A) and a thermo-hygrostat (Tabayespec PL-1F) was used.
Kp at 0 ° C. to 150 ° C. was measured.
【００２６】また、高圧縮応力下でペレット単体の変位
量（１μｍ以下）を精度良く測定できる微小変位測定装
置を用い、室温中で厚み方向の圧縮荷重２０ＭＰａの条
件下で、厚み方向に−０．４〜１．２ｋＶ／ｍｍ、０．
１Ｈｚの三角波電界を印加した時の試料の厚み方向（電
界方向）の変位量（μｍ）を測定した。変位量について
の温度安定性については、上記の変位量測定において温
度のみを−３０〜１５０℃の範囲で変えて変位量を測定
し、次の式に従って温度変化率（％）を求めた。Further, a small displacement measuring device capable of accurately measuring the amount of displacement (1 μm or less) of a single pellet under high compressive stress is used. 0.4-1.2 kV / mm, 0.
The amount of displacement (μm) in the thickness direction (electric field direction) of the sample when a 1 Hz triangular wave electric field was applied was measured. Regarding the temperature stability of the displacement, the displacement was measured by changing only the temperature in the range of −30 to 150 ° C. in the above-described displacement measurement, and the temperature change rate (%) was obtained according to the following equation.
【００２７】 Ｔｃは、比誘電率が極大となる温度とし、上記のベクト
ルインピーダンスアナライザと恒温恒湿槽とを組み合わ
せたシステムを用いて測定した。[0027] Tc was measured at a temperature at which the relative permittivity becomes a maximum, using a system in which the above-described vector impedance analyzer and a thermo-hygrostat were combined.
【００２８】得られた測定試料（試料１〜試料２３）の
Ｋｐ、室温での変位量の値、変位量の温度変化率（−３
０〜１５０℃の温度範囲での値、小さい方が望まし
い）、Ｔｃをそれぞれ表１に併せて示す。表１より、得
られた測定試料（試料１〜２３）はいずれもＫｐが０．
６とほぼ同じであるか、もしくは０．６を超え、その値
が大きいことがわかる。The Kp of the obtained measurement samples (Sample 1 to Sample 23), the value of the amount of displacement at room temperature, and the temperature change rate of the amount of displacement (−3)
Table 1 also shows the values in the temperature range of 0 to 150 ° C, and the smaller the value, the better. From Table 1, all of the obtained measurement samples (Samples 1 to 23) have a Kp of 0.
It can be seen that the value is almost the same as 6, or exceeds 0.6, and the value is large.
【００２９】また、ＰＺＴのＡサイトの一部をＬａで置
換した測定試料（試料１〜試料２０）は、変位量および
Ｔｃが大きく、また温度変化率は小さいことがわかる。
一方、Ｌａで置換していない測定試料（試料２１）は、
変位量およびＴｃが小さいことがわかる。また、Ｌａの
代わりにＳｒで置換した測定試料（試料２２）、および
Ｂａで置換した測定試料（試料２３）についても、変位
量およびＴｃが小さいことがわかる。この結果より、Ｌ
ａの置換は温度変化率を変えずに変位量を大きくするこ
とがわかる。Further, it can be seen that the measurement samples (samples 1 to 20) in which a part of the A site of PZT was replaced with La have a large displacement and a large Tc and a small temperature change rate.
On the other hand, the measurement sample not replaced by La (sample 21)
It can be seen that the displacement and Tc are small. In addition, it can be seen that the displacement amount and the Tc of the measurement sample (sample 22) replaced with Sr instead of La and the measurement sample (sample 23) replaced with Ba are also small. From this result, L
It can be seen that the substitution of a increases the displacement without changing the temperature change rate.
【００３０】また、Ｎｂ、Ｔａ、Ｓｂで置換された測定
試料（試料１〜試料１４、試料１５〜試料２３）は、い
ずれも置換量によって変位量が大きくなり、かつ、その
置換量の増加に対する変位量の増加量はそれぞれ同程度
であることがわかる。一方、Ｎｂ、Ｔａ、Ｓｂで置換さ
れていない測定試料（試料１５）は、変位量が小さいこ
とがわかる。この結果より、Ｎｂ、Ｔａ、Ｓｂの置換に
より変位量が大きくなることがわかる。The displacement of the measurement samples (Samples 1 to 14, and Samples 15 to 23) substituted with Nb, Ta, and Sb increases with the amount of substitution, and the amount of displacement increases. It can be seen that the amount of increase in the displacement is almost the same. On the other hand, it can be seen that the displacement of the measurement sample (sample 15) not replaced by Nb, Ta, and Sb is small. From this result, it can be seen that the displacement amount is increased by the replacement of Nb, Ta, and Sb.
【００３１】一方、試料１１の温度変化率が３５％であ
るように、その置換量（ｚ）が０．０３より大きい測定
試料では温度変化率が大きいことがわかる。この結果よ
り、ｚが０．０３より大きいＮｂ、Ｔａ、Ｓｂの置換は
温度変化率を大きくすることがわかる。また、ＬａとＮ
ｂ、Ｔａ、Ｓｂの少なくとも一種との合計置換量（ｘ＋
ｚ）が０．０３以上の範囲の測定試料（試料１４）で
は、０．３５〜０．３８μｍと変位量が大きいことがわ
かり、この置換量が０．０３より小さい測定試料（試料
１４）では０．２６μｍと変位量が小さいことがわか
る。この結果より、ｘ＋ｚが０．０３以上であるときは
変位量が大きく、０．０３より小さいとき変位量が小さ
いことがわかる。On the other hand, it can be seen that the measured sample whose replacement amount (z) is larger than 0.03 has a large temperature changed ratio, such that the temperature changed ratio of the sample 11 is 35%. From this result, it can be seen that the substitution of Nb, Ta, and Sb with z greater than 0.03 increases the rate of temperature change. Also, La and N
b, Ta, Sb and the total replacement amount (x +
In the measurement sample (sample 14) in which z) is 0.03 or more, the displacement amount is large at 0.35 to 0.38 μm, and in the measurement sample (sample 14) in which the replacement amount is smaller than 0.03, It can be seen that the displacement amount is as small as 0.26 μm. From this result, it can be seen that when x + z is 0.03 or more, the displacement is large, and when x + z is less than 0.03, the displacement is small.
【００３２】また、置換量（ｘ＋ｚ）が０．０６より大
きい測定試料（試料１１、試料１３）では、２５０℃以
下とＴｃが小さいことがわかる。この結果より、置換量
（ｘ＋ｚ）が０．０６より大きいとき、Ｔｃが著しく低
下することがわかる。また、０．３重量％以下のＣｒ2
Ｏ3 が添加された測定試料（試料２、試料３、試料７〜
試料１０、試料１２、試料１６）は、Ｃｒ2 Ｏ3 が添加
されていない測定試料（試料１、試料６、試料１１、試
料１３〜試料１５、試料１７〜試料２３）に比べても、
変位量、Ｔｃについてはほぼ同じ大きさである。しか
し、その添加量が０．３重量％を超える測定試料（試料
４、試料５）は、０．３重量％以下のＣｒ2 Ｏ3 が添加
された測定試料に比べると、変位量が小さいことがわか
る。Further, in the measurement samples (samples 11 and 13) in which the substitution amount (x + z) is larger than 0.06, it can be seen that Tc is as small as 250 ° C. or less. From this result, it can be seen that when the substitution amount (x + z) is larger than 0.06, Tc is significantly reduced. In addition, Cr 2 of 0.3% by weight or less
Measurement samples to which O 3 was added (sample 2, sample 3, sample 7 to
Sample 10, Sample 12, and Sample 16) were compared with the measurement samples to which Cr 2 O 3 was not added (Sample 1, Sample 6, Sample 11, Samples 13 to 15, and Samples 17 to 23).
The displacement and Tc are almost the same. However, the measurement samples (samples 4 and 5) in which the amount of addition exceeds 0.3% by weight have a smaller displacement compared to the measurement samples to which 0.3% by weight or less of Cr 2 O 3 is added. I understand.
【００３３】従って、実施例となる測定試料（試料２〜
５、試料７〜１０、試料１２、試料１６）は、Ｋｐおよ
び変位量が大きく、かつ温度変化率が小さいことがわか
る。中でも、ｘおよびｚが、０．０３≦ｘ＋ｚ＜０．０
６を満たし、かつＣｒ2 Ｏ3の添加量が、０．０１重量
％以上０．３重量％以下であり、また、ｘおよびｚが、
０．０１≦ｘ≦０．０５かつ０．０１≦ｚ≦０．０３を
満たしている測定試料（試料２、試料３、試料７〜１
０、試料１２、試料１６）は、特に温度変化率が小さい
ことがわかる。 （耐久試験による耐久性の評価）実施例である測定試料
（試料２〜５、試料７〜１０、試料１２、試料１６）の
うち、Ｃｒ2 Ｏ3 添加量が０．１５重量％、０．３重量
％、０．４重量％添加された３種類の粉末（試料２〜試
料４）を用い、温度１５０℃、荷重２０ＭＰａ、−０．
４〜１．２ｋＶ／ｍｍの駆動条件において耐久試験をそ
れぞれおこなった。また、Ｃｒ2 Ｏ3 が無添加の比較例
である測定試料（試料１）を用い、同じ駆動条件におい
て耐久試験をおこなった。Therefore, the measurement samples (Samples 2
5, samples 7 to 10, sample 12, and sample 16) have a large Kp and a large displacement and a small temperature change rate. Among them, x and z are 0.03 ≦ x + z <0.0
6 and the amount of Cr 2 O 3 added is 0.01% by weight or more and 0.3% by weight or less, and x and z are:
Measurement samples satisfying 0.01 ≦ x ≦ 0.05 and 0.01 ≦ z ≦ 0.03 (sample 2, sample 3, sample 7-1
0, Sample 12, and Sample 16) have a particularly small temperature change rate. (Evaluation of Durability by Durability Test) Of the measurement samples (Samples 2 to 5, Samples 7 to 10, Sample 12, and Sample 16) as examples, the amount of Cr 2 O 3 added was 0.15% by weight, and 0.1% by weight. Using three kinds of powders (Samples 2 to 4) added at 3% by weight and 0.4% by weight, the temperature was 150 ° C., the load was 20 MPa, and −0.05%.
Endurance tests were performed under driving conditions of 4 to 1.2 kV / mm. A durability test was performed under the same driving conditions using a measurement sample (sample 1) as a comparative example in which Cr 2 O 3 was not added.
【００３４】このとき、それぞれの測定試料について、
０．１Ｈｚ三角波で得られる変位を測定し、初回、１０
6 回、８×１０6 回、３．３×１０7 回の駆動回数にお
ける変位量を測定した。試料１〜試料４について、高電
界駆動による変位量の変化を図１に示す。なお、試料４
については、変位量が試料１〜試料３に比べ初期から小
さかったため、本耐久試験を行っていない。At this time, for each measurement sample,
Measure the displacement obtained with a 0.1 Hz triangular wave,
The amount of displacement was measured at the number of driving times of 6 times, 8 × 10 6 times, and 3.3 × 10 7 times. FIG. 1 shows a change in the amount of displacement of Samples 1 to 4 due to high electric field driving. Sample 4
As for, the endurance test was not performed because the amount of displacement was smaller than that of Samples 1 to 3 from the beginning.
【００３５】図１より、試料２および試料３の変位量の
低下量は、初期の変位量の５％以下であり、試料１の低
下量は初期の変位量の約１５％であることがわかる。こ
の結果から、Ｃｒ2 Ｏ3 の添加は、高電界駆動による変
位量低下の抑制に効果的であり、特に、Ｃｒ2 Ｏ3 添加
量が０．０１重量％以上０．３重量％以下の範囲内の圧
電磁器組成物では変位量の低下を５％以下とすることが
でき、Ｃｒ2 Ｏ3 の無添加の圧電磁器組成物に比べ変位
量の低下を１／３程度に小さくできることがわかる。From FIG. 1, it can be seen that the amount of decrease in the displacement of Samples 2 and 3 is 5% or less of the amount of initial displacement, and the amount of decrease in Sample 1 is about 15% of the amount of initial displacement. . From the results, the addition of Cr 2 O 3 is effective in suppressing the amount of displacement decreases due to high electric field driving, in particular, Cr 2 O 3 amount ranging less 0.3 wt% 0.01 wt% added It can be seen that in the piezoelectric ceramic composition in the figure, the decrease in displacement can be reduced to 5% or less, and the decrease in displacement can be reduced to about 1/3 as compared with the piezoelectric ceramic composition without Cr 2 O 3 added.
【００３６】以上の結果より、チタン酸ジルコン酸鉛
（ＰＺＴ）のＰｂサイトの一部にＬａを置換し、Ｔｉ・
ＺｒサイトにＮｂ、Ｔａ、Ｓｂのうちの少なくとも一種
を置換し、かつＣｒ2 Ｏ3 を添加した圧電磁器組成物
は、エネルギー変換効率および変位量が大きく、かつ広
温度範囲で特性の温度安定性に優れることがわかる。ま
た、高電界下で長時間駆動しても変位量の低下が小さ
く、耐久性が高いことがわかる。From the above results, La was substituted for a part of the Pb site of lead zirconate titanate (PZT), and Ti ·
A piezoelectric ceramic composition in which at least one of Nb, Ta, and Sb is substituted for the Zr site and Cr 2 O 3 is added has a large energy conversion efficiency and a large displacement, and has a temperature stability characteristic over a wide temperature range. It turns out that it is excellent. In addition, it can be seen that even when the device is driven for a long time under a high electric field, the decrease in displacement is small and the durability is high.
【００３７】[0037]
【効果】本発明の圧電磁器組成物は、エネルギー変換効
率および変位量が大きく、温度安定性に優れるため、ア
クチュエータ等の圧電素子に利用できる。特に、本発明
の圧電磁器組成物は、広温度範囲での温度安定性に優
れ、また耐久性が高いため自動車用の圧電アクチュエー
タとして利用することができる。The piezoelectric ceramic composition of the present invention has a large energy conversion efficiency and a large amount of displacement, and is excellent in temperature stability, so that it can be used for a piezoelectric element such as an actuator. In particular, the piezoelectric ceramic composition of the present invention has excellent temperature stability in a wide temperature range and has high durability, and can be used as a piezoelectric actuator for an automobile.
【図１】この図は、本実施例において作製した試料１〜
試料４についての高電界駆動による変位量の変化を示す
図である。FIG. 1 shows Samples 1 to 3 produced in this example.
FIG. 9 is a diagram illustrating a change in a displacement amount of a sample 4 due to high electric field driving.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 牧野 浩明 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 神谷 信雄 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroaki Makino 41-Cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Laboratory Co., Ltd. 41, Yokomichi, Toyota Central Research Institute, Inc.
Claims (3)
イトの一部にＬａを置換し、Ｔｉ・ＺｒサイトにＮｂ、
Ｔａ、Ｓｂのうちの少なくとも一種を置換し、かつ酸化
クロムを添加したことを特徴とする圧電磁器組成物。1. A method according to claim 1, wherein part of the Pb site of lead zirconate titanate (PZT) is substituted with La, and Nb,
A piezoelectric ceramic composition wherein at least one of Ta and Sb is substituted and chromium oxide is added.
ｉ1-y ）1-z Ｍz ）Ｏ3 （但し、Ｍは、Ｎｂ、Ｔａ、Ｓ
ｂのうちの少なくとも一種である。）の組成で表される
ＰＺＴに、酸化クロムとしてＣｒ2 Ｏ3 を添加したもの
であり、式中のｘ、ｙ、ｚは、０．０３≦ｘ＋ｚ≦０．
０６、および０．５≦ｙ≦０．６を満たし、かつ該Ｃｒ
2 Ｏ3 の添加量は、該Ｃｒ2 Ｏ3 を添加した圧電磁器組
成物の全体の量を１００重量％とすると、０．０１重量
％以上０．３重量％以下である請求項１に記載の圧電磁
器組成物。Wherein the general formula: Pb 1- (3/2) x La x ((Zr y T
i 1-y ) 1-z M z ) O 3 (where M is Nb, Ta, S
b. ) Is obtained by adding Cr 2 O 3 as chromium oxide to PZT represented by the composition of formula (1), where x, y, and z are 0.03 ≦ x + z ≦ 0.
06 and 0.5 ≦ y ≦ 0.6, and the Cr
Amount of 2 O 3, when the entire amount of the piezoelectric ceramic composition with the addition of the Cr 2 O 3 and 100% by weight, according to claim 1 or less 0.3 wt% 0.01 wt% Piezoelectric ceramic composition.
５、および０．０１≦ｚ≦０．０３を満たす請求項２に
記載の圧電磁器組成物。3. The method according to claim 1, wherein x and z are 0.01 ≦ x ≦ 0.0.
3. The piezoelectric ceramic composition according to claim 2, wherein the piezoelectric ceramic composition satisfies 5 and 0.01 ≦ z ≦ 0.03.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8160193A JPH107460A (en) | 1996-06-20 | 1996-06-20 | Piezoelectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8160193A JPH107460A (en) | 1996-06-20 | 1996-06-20 | Piezoelectric porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH107460A true JPH107460A (en) | 1998-01-13 |
Family
ID=15709834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8160193A Pending JPH107460A (en) | 1996-06-20 | 1996-06-20 | Piezoelectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH107460A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2791974A1 (en) * | 1999-04-08 | 2000-10-13 | Murata Manufacturing Co | Piezoelectric ceramic, useful for piezoelectric vibrators and actuators, comprises lead zirconate-titanate with partial lead substitution by lanthanum and partial titanium and zirconium substitution by antimony, chromium and tin |
| US6279878B1 (en) * | 2000-04-28 | 2001-08-28 | Rockwell Technologies, Llc | High temperature, high strain piezoelectric compositions |
| JP2006504277A (en) * | 2002-10-25 | 2006-02-02 | エプコス アクチエンゲゼルシャフト | Piezoelectric element |
| JP2007273853A (en) * | 2006-03-31 | 2007-10-18 | Kyocera Corp | Piezoelectric actuator unit |
| JP2016199432A (en) * | 2015-04-10 | 2016-12-01 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric element |
| CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
-
1996
- 1996-06-20 JP JP8160193A patent/JPH107460A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2791974A1 (en) * | 1999-04-08 | 2000-10-13 | Murata Manufacturing Co | Piezoelectric ceramic, useful for piezoelectric vibrators and actuators, comprises lead zirconate-titanate with partial lead substitution by lanthanum and partial titanium and zirconium substitution by antimony, chromium and tin |
| CN1104395C (en) * | 1999-04-08 | 2003-04-02 | 株式会社村田制作所 | Piazoelectric ceramic composition, buzzer thereof and controller |
| US6279878B1 (en) * | 2000-04-28 | 2001-08-28 | Rockwell Technologies, Llc | High temperature, high strain piezoelectric compositions |
| JP2006504277A (en) * | 2002-10-25 | 2006-02-02 | エプコス アクチエンゲゼルシャフト | Piezoelectric element |
| JP2007273853A (en) * | 2006-03-31 | 2007-10-18 | Kyocera Corp | Piezoelectric actuator unit |
| JP2016199432A (en) * | 2015-04-10 | 2016-12-01 | Tdk株式会社 | Piezoelectric ceramic and piezoelectric element |
| CN114075073A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院上海硅酸盐研究所 | PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof |
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