JP4804709B2 - PZT composition capable of low-temperature sintering and piezoelectric ceramic device using the same - Google Patents

PZT composition capable of low-temperature sintering and piezoelectric ceramic device using the same Download PDF

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JP4804709B2
JP4804709B2 JP2003193772A JP2003193772A JP4804709B2 JP 4804709 B2 JP4804709 B2 JP 4804709B2 JP 2003193772 A JP2003193772 A JP 2003193772A JP 2003193772 A JP2003193772 A JP 2003193772A JP 4804709 B2 JP4804709 B2 JP 4804709B2
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piezoelectric ceramic
piezoelectric
sintering
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ceramic composition
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JP2004051476A (en
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キム ヨン，ミン
ポノマレブ ヨウリ
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ドンギル テクノロジー カンパニー リミティッド
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Description

【０００１】
【発明の属する技術分野】
本発明は、低温焼結可能なＰＺＴセラミック組成物とそれを用いた圧電セラミック装置に係り、より詳しくは、１０５０℃以下の低温で焼結でき、ひいては９４０℃の低温でもＡｇ電極と共に同時に焼結できる低損失圧電セラミック物質とそれを用いた圧電セラミック装置に関する。
【０００２】
【従来の技術】
圧電トランスや圧電アクチュエータのような多層圧電サラミック装置の出願が最近増加している。しかし、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ３（ｌｅａｄ ｚｉｒｏｃｏｎａｔｅ ｔｉｔａｎａｔｅ，以下、「ＰＺＴ」と称す）物質からなる既存の多層圧電セラミック装置では、ＰＺＴ物質の高い焼結温度のため白金（Ｐｔ）、パラジウム（Ｐｄ）又は銀（Ａｇ）−パラジウム（Ｐｄ）ペーストを共に同時に焼結する必要があった。このような内部電極の高コストのため、多層圧電気装置の幅広い使用が制限された。従って、低温で特にＡｇの融点である９６２℃以下で焼結可能なＰＺＴ物質を開発しようとする多様な努力がなさてれきた。
【０００３】
圧電セラミックトランスのように連続的に駆動される応用において、高効率を達成するために、高い圧電定数（ｄｉｊ，ｐｉｅｚｏ ｍｏｄｕｌｕｓ）、高い電気械結合係数ｋｐ（ｅｌｅｃｔｒｏ−ｍｅｃｈａｎｉｃａｌ ｃｏｕｐｌｉｎｇ ｃｏｅｆｆｉｃｉｅｎｔ）、高い誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）を有する低損失硬質圧電セラミック物質が求められた。しかし、硬質圧電セラミックの圧電特性を悪化させずに焼結温度を低下させるのにはいろいろと困難なことがあった。
【０００４】
液相焼結によって低温で緻密化（ｄｅｎｓｉｆｉｃａｔｉｏｎ）を加速させるために、低融点を有するガラス・フリット（ｇｌａｓｓ ｆｒｉｔ）を単に添加することでＰＺＴ物質の焼結温度を低下させることができる。しかし、この方法は圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）を低下させるという問題点がある。
【０００５】
米国特許出願Ｎｏ．５７９２３７９は、９００℃以下の焼結温度を有し、内部電極物質として、Ａｇと同時に焼結できるＰＺＴセラミック組成物に関するものである。Ｂ２Ｏ３、Ｂｉ２Ｏ３、ＭｅＯ及びＣｕＯからなる焼結助剤（ここでＭｅとはＣａ，Ｓｒ，Ｂａ及びＺｎからなる群の中から選ばれた一つの金属である）を用いることによって焼結温度を低下させる。しかし、焼結温度が低下すると、０．６０以上のＫｐ（電気機械結合係数）を有する硬質圧電セラミックに比べて、Ｋｐが最高０．５５以下に減少する。
【０００６】
米国特許出願Ｎｏ．５４３３９１７は、ＣｕＯの共融混合物とアルカリ土金属の酸化物とを用いて、約１，０００℃の低い焼結温度を有するＰＺＴ組成物に関するものである。しかし、誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）及び誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ）を除いた他の詳細な圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）に関する報告はない。またＧｕｉ ｅｔ、ａｌにも、Ｂ２Ｏ３、Ｂｉ２Ｏ３、ＣｄＯを少量使用してＰＺＴの焼結温度を低下させる方法が説明されている。しかし、両先行技術における焼結温度はＡｇ電極と同時に焼結するのには依然として高いという問題点がある。
【０００７】
このような先行技術では低融点を有するガラス・フリット（ｇｌａｓｓ ｆｒｉｔ）が焼結助剤として使用されるが、ガラス・フリットにおいて全ての元素、例えばホウ素は焼結中にＰＺＴマトリックス（ｍａｔｒｉｘ）のペロブスカイト結晶格子構造で置換されない。しかし、焼結の後、これらが結晶粒界（ｇｒａｉｎ ｂｏｕｄａｒｙ）を沿ってガラス相に残り、これは圧電気的特性を悪化させる問題点になる。
【０００８】
【特許文献】
米国特許出願Ｎｏ．５７９２３７９
【特許文献】
米国特許出願Ｎｏ．５４３３９１７
【０００９】
【発明が解決しようとする課題】
本発明は、かかる問題点を解消するためになされたもので、その目的は、低い誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ）と高い圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）とを有し、低温焼結可能な圧電セラミック組成物を提供することにある。
【００１０】
本発明の他の目的は、Ａｇの融点である９６２℃以下で純Ａｇと同時に焼結できる低温焼結圧電セラミック組成物を提供することにある。
【００１１】
本発明のまた他の目的は、本発明に係る圧電セラミック組成物を用いて多層圧電セラミックトランス、多層圧電セラミックアクチュエータなどのように連続駆動を行うのに適した圧電セラミック装置を提供することにある。
【００１２】
【課題を解決するための手段】
上記目的を達成するために、本発明は、[（Ｐｂ１−ｍ−ｎーｐＳｒｍＢａｎＣｄｐ）（ＺｒｘＴｉ１−ｘ）１−ｋ（ＢｉａＭｎｂ）ｋ]Ｏ３（式中、モル比ｍ，ｎ，ｐ，ｘ，ａ，ｂ及びｋは、０．００≦ｍ＜０．１５、０．００≦ｎ＜０．１５、０．００＜ｍ＋ｎ＜０．２１、０．００＜ｐ＜０．０４、０．５０≦ｘ＜０．５６、０．００＜ａ≦１．００、０．００＜ｂ≦１．００、０．００＜ｋ＜０．０４である）セラミックを含む圧電セラミック組成物を提供する。
【００１３】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
本発明に係る圧電セラミック組成物は、必須成分として[（Ｐｂ１−ｍ−ｎーｐＳｒｍＢａｎＣｄｐ）（ＺｒｘＴｉ１−ｘ）１−ｋ（ＢｉａＭｎｂ）ｋ]Ｏ３（モル比ｍ，ｎ，ｐ，ｘ，ａ，ｂ及びｋは、０．００≦ｍ＜０．１５、０．００≦ｎ＜０．１５、０．００＜ｍ＋ｎ＜０．２１、０．００＜ｐ＜０．０４、０．５０≦ｘ＜０．５６、０．００＜ａ≦１．００、０．００＜ｂ≦１．００、０．００＜ｋ＜０．０４である。）セラミックを含む。前記セラミックは、ＰＺＴ（ｌｅａｄ ｚｉｒｃｏｎａｔｅ ｔｉｔａｎａｔｅ）の固溶体（ｓｏｌｉｄ ｓｏｌｕｔｉｏｎ）をストロンチウム、バリウム、カドミウム、ビスマスおよびマンガンイオンと共に合金したものである。圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）を悪化させずに焼結温度を低下させるために、反応性の高いＣｄとＢｉを添加する。Ｚｒ４＋または、Ｔｉ４＋をＢｉ３＋に置換する。異原子価のイオン（ａｌｉｏｖａｌｅｎｔ ｉｏｎ）の置換による電荷の均衡（ｃｈａｒｇｅｎｅｕｔｒａｌｉｔｙ）は、焼結する間に拡散過程（ｄｉｆｆｕｓｉｏｎ ｐｒｏｃｅｓｓ）を増加させる酸素原子空孔（ｏｘｙｇｅｎ ｖａｃａｎｃｙ）の生成によって維持され、従って焼結温度を効果的に低下させるようになる。このような物質システムにおいてＰｂ２＋をＣｄ２＋に置換し、Ｃｄ２＋の高い活性度は焼結過程で拡散過程を加速化しながら、焼結温度を効果的に低下させる。Ｃｄ量のｐは０＜ｐ＜０．０４であることが好ましい。Ｃｄ量がこの範囲から外れると、電気機械結合係数Ｋｐ（ｅｌｅｃｔｒｏｍｅｃｈａｎｉｃａｌ ｃｏｕｐｌｉｎｇ ｃｏｅｆｆｉｃｉｅｎｔ）と圧電定数ｄ３３（ｐｉｅｚｏ ｍｏｄｕｌｕｓ）とが非実用レベル（ｎｏｎｐｒａｃｔｉｃａｌ ｌｅｖｅｌ）に至るまで減少し、好ましくない。
【００１４】
Ｂｉは、ＢｉａＭｎｂに表現されるＭｎと共に添加される。Ｍｎは、機械的品質係数Ｑｍ（ｍｅｃｈａｎｉｃａｌ ｑｕａｌｉｔｙ ｆａｃｔｏｒ）を増加させるとともに、焼結体（ｓｉｎｔｅｒｅｄ ｅｌｅｍｅｎｔ）の結晶粒子の大きさを制御するために添加される。ＢｉとＭｎの相対的の量であるａ又はｂは０＜ａ又はｂ≦１の範囲であることが好ましく、３ａ＋４ｂ＝４を満足することがさらに好ましい。
【００１５】
例えば、それぞれａ＝１、２／３、１／２又は１／３であり、ｂ＝１／４、１／２、５／８又は３／４である。前記条件で万一Ｚｒ４＋とＴｉ４＋をＢｉ３＋またＭｎ４＋に置換した場合、マトリックス（ｍａｔｒｉｘ）１モル当たりｋ（ａ／４）モル量のＢｉ３＋またＭｎ４＋イオンが過剰になる。よって、ＰＺＴマトリックス（ｍａｔｒｉｘ）に置換されていない過量のＢｉ３＋またＭｎ４＋イオンは、焼結する間に液相を形成し、緻密化に役に立つ。ＢｉａＭｎｂの最大量（ｋ）は０＜ｋ＜０．０４であることが好ましい。このような範囲から外れると、Ｋｐ及びｄ３３は急激に減少し、好ましくない。また、ｋはｋ＝ｐを満足することが好ましい。
【００１６】
誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）を増加し、同時に圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）に対して明らかに逆効果なしに緻密化を向上させるために、ＳｒまたはＢａを添加する。Ｐｂを置換できるＳｒまたはＢａの最大量は、単独添加時、ＰＺＴにおいて約１５モル％である。しかし、一緒に添加するときは、Ｓｒ＋Ｂａその最大量は１８〜２０モル％まで拡張することができる。これによりさらに高い誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）を得ることができる。しかも、混合置換の場合、同一の原子比で添加すると、単独置換に比べてより良い焼結特性を示す。Ｓｒ又はＢａの量（ｍ又はｎ）は、０．０＜ｍ又はｎ ＜０．１５そして０＜ｍ＋ｎ＜０．２１であることが好ましい。このような範囲から外れると、焼結温度は非常に高くなり、好ましくない。
【００１７】
本発明に係る圧電セラミック組成物は、 焼結性又は機械的品質係数（ｍｅｃｈａａｎｉｃａｌ ｑｕａｌｉｔｙ ｆａｃｔｏｒ）を向上させるために、０．００１〜１重量％のＢｉ２Ｏ３をさらに含むことが好ましい。
【００１８】
本発明に係る圧電セラミック組成物は、ＬｉＦ又はＭｇＦ２をさらに含む。フッ素（Ｆ）は、高電場で圧電特性を向上させかつ誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）を増加させることから、このようなフッ素化合物が含まれると、高い機械適応力または高電場での高い圧電特性が改善され、好ましい。フッ素化合物であるＬｉＦ又はＭｇＦ２の量は０．００１〜１重量％である。
【００１９】
本発明に係る圧電セラミック組成物は、焼結性又は機械的品質係数（ｍｅｃｈａｎｉｃａｌ ｑｕａｌｉｔｙ ｆａｃｔｏｒ）を向上させるために、０．００１〜０．５０重量％のＭｎＯ２をさらに含むことが好ましい。
【００２０】
本発明は、また前記圧電セラミック組成物を１０７５℃以下で焼結して得た圧電セラミックを含んで構成される圧電セラミック装置を提供する。
【００２１】
本発明は、また前記圧電セラミック組成物をＡｇ内部電極と共に９６０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成される多層圧電セラミック装置を提供する。
【００２２】
本発明は、また前記圧電セラミック組成物をＡｇ−Ｐｄ内部電極と共に同時焼結を行って得た圧電セラミック層を含んで構成される多層圧電セラミック装置を提供する。前記Ｐｄの量は前記Ａｇ及びＰｄの１００重量％に対して０．００１〜２０重量％であることが好ましい。
【００２３】
本発明は、また前記圧電セラミック組成物をＡｇ内部電極と共に９６０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成され、多層部分と単層部分とを含む圧電セラミック装置を提供する。
【００２４】
本発明は、また前記圧電セラミック組成物をＡｇ−Ｐｄ内部電極と共に１０５０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成され、多層部分と単層部分とを含む圧電セラミック装置を提供する。前記Ｐｄの量は、前記Ａｇ及びＰｄの１００重量％に対して０．００１〜２０重量％であることが好ましい。
【００２５】
本発明は、圧電セラミック組成物とそれを用いた圧電セラミックトランスに関する次の実施例により容易に理解されるであろう。ただし、これら実施例はもっぱら本発明を説明するためのものであって、本発明の範囲を限定するものではない。
【００２６】
【実施例１】
圧電セラミック組成物
ＰｂＯ、ＺｒＯ２、ＴｉＯ２、ＳｒＣＯ３、ＢａＣＯ３、ＣｄＯ、Ｂｉ２Ｏ３、ＭｎＯ２とＬｉＦまたＭｇＦ２を出発原料として使用する。出発原料を表１に記載の量比で秤量した後、脱イオン水を添加してアトリションミル（ａｔｔｒｉｔｉｏｎ ｍｉｌｌ）を用いて２時間湿式混合を行い、そのスラリーを真空濾過する。濾過したものを１２０℃のオーブンで乾燥し、７００〜８７５℃で２時間か焼（ｃａｌｃｉｎｅ）する。得られたか焼物を再びアトリションミルを用いて平均粒径が約０．８μｍとなるまで微粉砕を行う。微粉砕によって得られたスラリーを乾燥し、乾燥粉末に１０％のＰＶＡ（Ｐｏｌｙ Ｖｉｎｙｌ Ａｌｃｏｈｏｌ）を少量（約２重量％）加えて造粒する。得られた造粒粉末である直径２５ｍｍ、厚さ約２．５ｍｍのグーリンディスク（未焼成のディスクを意味する。以下同様）（ｇｒｅｅｎ ｄｉｓｋ）を、１０００ｋｇ／ｃｍ２の圧力をかけて成形して成型物を得る。前記グーリンディスク（ｇｒｅｅｎ ｄｉｓｋ）を９２０〜１０００℃で２時間焼結する。焼結したディスクの両表面にＡｇペーストを印刷し、７００〜７７０℃で１５分間焼き付ける。電極を形成したディスクを１２０〜１４０℃のシリコンオイル槽で１５分間３〜４ｋＶ／ｍｍ電圧を印加して分極処理を行う。誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）と誘電損失係数（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ ｔａｎｇｅｎｔ）とは、１Ｖｒｍｓの入力レベル、１ｋＨｚでＬＣＲ ｍｅｔｅｒを用いて測定する。圧電定数ｄ３３はＢｅｒｌｉｎｃｏｕｒ ｄ３３ ｍｅｔｅｒを用いて測定する。平面結合係数（ｐｌａｎａｒ ｃｏｕｐｌｉｎｇ ｃｏｅｆｆｉｃｉｅｎｔ）と機械品質係数Ｑｍ（ｍｅｃｈａｎｉｃａｌ ｑｕａｌｉｔｙｆａｃｔｏｒ）とは、共振周波数ｆｒ（ｒｅｓｏｎａｎｔ ｆｒｅｑｕｅｎｃｙ）、反共振周波数ｆａ（ａｎｔｉｒｅｓｏｎａｎｔ ｆｒｅｑｕｅｎｃｙ）、ＬＣＲ ｍｅｔｅｒで測定した電気容量Ｃ０及びインピーダンスアナライザー（Ｉｍｐｅｄａｎｃｅ／Ｇａｉｎ−Ｐｈａｓｅ ａｎａｌｙｓｅｒ）で測定した共振インピーダンスＺｒ（ｒｅｓｏｎａｎｔ ｉｍｐｅｄａｎｃｅ）から次の式によって計算される。
【００２７】
１／ｋｐ＝０．３９５ｆｒ／（ｆａ-ｆｒ）＋０．５７４
Ｑｍ＝１／２πｆｒＺｒＣｏ（１-（ｆｒ／ｆａ）２）
【００２８】
表１に記載された＊付きの組成物、並びにサンプル♯６、♯８および♯１３〜１５の組成物は比較用サンプルであり、本発明の範囲を外れている。１０５０℃、９６５℃及び９５０℃で焼結されたサンプルの特性を表２に示す。同表に示すように、有用な圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）を１０５０℃、ひいては９５０℃で焼結した時にも得ることができる。Ｃｄ量のｐが０．０４（サンプル♯４）になると、ｋｐが急激に低下した。Ｂａ＋Ｓｒの総量が２２モル％（サンプル＃１とサンプル＃２）である時、Ｐｂに比べてＢａやＳｒの拡散速度が遅いため、ｋｐもこのような焼結温度で急激に減少する。サンプル＃１０およびサンプル＃１１によれば、Ｆがｋｐにあまり影響を与えずに１重量％以下の範囲で添加できることがわかる。なお、表１および以下の表３において、ｙはさらに含まれるＢｉ２Ｏ３の配合量（重量％）、ｚはＬｉＦ又はＭｇＦ２の配合量（重量％）を表す。ＭｇＦ２を使用することは可能であるが、ＭｇＦ２からなるサンプルのパラメーターはＬｉＦからなるサンプルに比べて好ましくない。
【００２９】
Ｚｒ／Ｔｉ組成比を変化させることでより多様な特性を得ることができる。本発明によってＺｒ／Ｔｉ組成比を変化させた低温焼結可能な圧電セラミック組成物を表３に示すように準備した。表３に記載された♯６１および♯６５の組成物は比較用サンプルであり、本発明の範囲を外れている。９４０℃で焼結し、準備された圧電ディスク（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｄｉｓｋ）の特性は表４に示す。全ての組成物は、９４０℃で容易に焼結され、良好な圧電気的特性である、０．２〜０．４％の低い誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ）、１４７０〜１８５０の高い誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）、３１０〜３９６のｄ３３、６１０〜７３０の機械的品質係数（ｍｅｃｈａｎｉｃａｌ ｑｕｌｉｔｙ ｆａｃｔｏｒ）を示した。Ｚｒ／Ｔｉ組成比を変化させることにより、サンプル＃６１〜＃６４に示すように、共振周波数の温度係数（ｔｅｍｐｅｒａｔｕｒｅ ｃｏｅｆｆｉｃｉｅｎｔ）と誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）とを調整することができる。さらにＬｉＦを添加することにより、サンプル＃６３とサンプル＃６５に示すように、共振周波数（ｒｅｓｏｎａｎｔ ｆｒｅｑｕｅｎｃｙ）の温度係数（ｔｅｍｐｅｒａｔｕｒｅ ｃｏｅｆｆｉｃｉｅｎｔ）のそれほど悪化せずに誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）を増加させることができる。このような低い焼結温度は、圧電セラミックトランスや圧電アクチュエーターのような多層圧電セラミック部品において、内部電極として純Ａｇペーストを使用することを可能にする。高い誘電定数（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ）と共振周波数の低い温度係数（ｔｅｍｐｅｒａｔｕｒｅ ｃｏｅｆｆｉｃｉｅｎｔ）は、圧電セラミックトランスのように共振モ-ドで動作する応用に有用に適用することができる。
【００３０】
【表１】

Figure 0004804709
【００３１】
【表２】
Figure 0004804709
Figure 0004804709
【００３２】
【表３】
Figure 0004804709
【００３３】
【表４】
Figure 0004804709
【００３４】
【実施例２】
純Ａｇ内部電極を有する圧電セラミックトランス
純Ａｇ内部電極を有する圧電セラミックトランスを本発明に係る組成物を用いて作製した。組成物のサンプル＃６３をその例として挙げる。作製したローゼン型圧電セラミックトランス（Ｒｏｓｅｎ−ｔｙｐｅ ｐｉｅｚｏｃｅｒａｍｉｃ ｔｒａｎｓｆｏｒｍｅｒ）を図１に示す。図１に示すように、入力部分Ｉは多層構造であり、多層構造の各層は、厚さ方向に上下交互に分極される。出力部分Ｏは単層になっており、トランスの長さ方向に分極Ｐされている。圧電セラミックトランスの作製は、まずＰＺＴ物質のグリーンシート（ｇｒｅｅｎ ｓｈｅｅｔ）を準備するところから始まる。か焼物をポリビニルブチラール（ＰＶＢ、Ｐｏｌｙｖｉｎｙｌ Ｂｕｔｙｒａｌ）、フタル酸ジブチル（ＤＢＰ、Ｄｉｂｕｔｙｌ Ｐｈｔｈａｌａｔｅ）、魚油（ｆｉｓｈ ｏｉｌ）、メチルエチルケトン（ＭＥＫ、Ｍｅｔｈｙｌ Ｅｔｈｙｌ Ｋｅｔｏｎｅ）及びトルエン（ｔｏｌｕｅｎｅ）からなる結合剤と共にボールミルを用いて３６時間混合する。粉砕されたスラリーを真空脱泡した後、ドクターブレード・キャスティングマシン（ｄｏｃｔｏｒ ｂｌａｄｅ ｃａｓｔｉｎｇ ｍａｃｈｉｎｅ）を用いてＰＥＴフィルム上に厚さ９５μｍのテープを成形する。グリーンテープ（ｇｒｅｅｎ ｔａｐｅ）を整列用穴を有する１５０ｍｍ×１５０ｍｍのシート（ｓｈｅｅｔ）に裁断する。交互になっている内部圧電は、Ａｇペーストをグリーンシート（ｇｒｅｅｎ ｓｈｅｅｔ）に印刷し、連続式オーブンで乾燥する。印刷されたグリーンシート（ｇｒｅｅｎ ｓｈｅｅｔ）を整列用穴を用いて積層するが、内部圧電が一定に配列されるようにし、８５℃、真空加熱圧着する。加熱圧着された（ｈｏｔ−ｌａｍｉｎａｔｅｄ）グリーンバー（ｇｒｅｅｎ ｂａｒ）をそれぞれのグリーンエレメント（ｇｒｅｅｎ ｅｌｅｍｅｎｔ）に切る。グリーンエレメント（ｇｒｅｅｎ ｅｌｅｍｅｎｔ）にある他の有機物のみならず、結合剤は、２６０℃での脱バインダー後、９４０℃で２時間焼結された。外部入力・出力電極はＡｇペーストをスクリ-ン印刷し、７８０℃で焼き付けた。入力部分は４５０ＶＤＣの分極電圧で、出力部分は２５ｋＶＤＣの分極電圧で１３０℃のシリコンオイル槽で分極処理を行った。
【００３５】
圧電セラミックトランスは、その大きさが２６．０ｍｍ×５．０ｍｍ×１．３ｍｍであり、１５個の圧電活性層（ｐｉｅｚｏ−ａｃｔｉｖｅ ｌａｙｅｒ）を有し、１６個の内部電極を持っている。Ａｇペーストは、本発明に係る組成物サンプル＃６３からなるＰＺＴマトリックス（ｍａｔｒｉｘ）と９４０℃で同時焼結時にほぼ反応が無い。Ａｇ内部電極は電極面を１００％被覆されており、層間剥離（ｄｅｌａｍｉｎａｔｉｏｎ）がなく、かつ共振インピーダンス（ｒｅｓｏｎａｎｃｅ ｉｍｐｅｄａｎｃｅ）がそれほど高くなく、圧電特性に優れている。表５に圧電セラミックトランスの特性を示す。図２には動作の特性に示す。９３％以上の変換効率（ｃｏｎｖｅｒｓｉｏｎ ｅｆｆｉｃｉｅｎｃｙ）が測定された。
【００３６】
本発明に係る低温焼結可能な圧電セラミック組成物は圧電セラミックトランスの適用に限定されるものではなく、単層圧電トランスはもとより多層アクチュエーター、多層センサー、バイモルフ（ｂｉｍｏｒｐｈ）に適用することもできる。
【００３７】
【表５】
Figure 0004804709
【００３８】
【発明の効果】
以上説明したように、本発明に係る圧電セラミック組成物は、低い誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ）及び高い圧電定数（ｐｉｅｚｏｅｌｅｃｔｒｉｃ ｐａｒａｍｅｔｅｒ）を有し、低下した温度、特にＡｇの融点である９６２℃以下で純Ａｇと同時焼結を行うことができる。
【００３９】
また、本発明に係る圧電セラミック装置は、圧電セラミックトランス、多層圧電セラミックアクチュエーターなどのように連続動作を行う応用に適したものであり、優秀な変換効率（ｃｏｎｖｅｒｓｉｏｎ ｅｆｆｉｃｉｅｎｃｙ）を有する。
【図面の簡単な説明】
【図１】本発明の圧電セラミック装置の一実施例に係る圧電セラミックトランス内の圧電セラミックの斜視図である。
【図２】本発明の圧電セラミック装置の一実施例に係る圧電セラミックトランスの動作特性のうち、出力電圧の周波数の特性を示すグラフである。
【図３】本発明の圧電セラミック装置の一実施例に係る圧電セラミックトランスの動作特性のうち、オープンロード（ｏｐｅｎ−ｌｏａｄ）１００ＭＯｈｍ及び２００ｋＯｈｍに対する周波数の特性を示すグラフでである。
【図４】本発明の圧電セラミック装置の一実施例に係る圧電セラミックトランスの動作特性のうち、出力電流及び出力電圧の特性を示すグラフである。
【符号の説明】
Ｉ 入力部分（Ｉｎｐｕｔ ｓｅｃｔｉｏｎ）
Ｏ 出力部分（Ｏｕｔｐｕｔ ｓｅｃｔｉｏｎ）
Ｐ 分極（Ｐｏｌａｒｉｚａｔｉｏｎ）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a low-temperature sinterable PZT ceramic composition and a piezoelectric ceramic device using the same. More specifically, the present invention can sinter at a low temperature of 1050 ° C. or lower, and at the same time, simultaneously sintered with an Ag electrode at a low temperature of 940 ° C. The present invention relates to a low-loss piezoelectric ceramic material and a piezoelectric ceramic device using the same.
[0002]
[Prior art]
Applications for multi-layer piezoelectric salamic devices such as piezoelectric transformers and piezoelectric actuators have recently increased. However, in an existing multilayer piezoelectric ceramic device made of Pb (Zr, Ti) O 3 (lead zirconate titanate, hereinafter referred to as “PZT”) material, platinum (Pt), palladium ( Both Pd) or silver (Ag) -palladium (Pd) paste had to be sintered together. The high cost of such internal electrodes has limited the wide use of multilayer piezoelectric devices. Therefore, various efforts have been made to develop PZT materials that can be sintered at low temperatures, particularly below 962 ° C., which is the melting point of Ag.
[0003]
In a continuously driven application such as a piezoceramic transformer, in order to achieve high efficiency, a high piezoelectric constant (d ij , piezo modulus), a high electrical coupling coefficient k p (electro-mechanical coupling coefficient), high A low loss hard piezoelectric ceramic material having a dielectric constant has been sought. However, it has been difficult to reduce the sintering temperature without deteriorating the piezoelectric characteristics of the hard piezoelectric ceramic.
[0004]
In order to accelerate densification at low temperature by liquid phase sintering, the sintering temperature of the PZT material can be lowered by simply adding a glass frit having a low melting point. However, this method has a problem of lowering the piezoelectric constant.
[0005]
US patent application no. No. 579379 relates to a PZT ceramic composition having a sintering temperature of 900 ° C. or less and capable of being sintered simultaneously with Ag as an internal electrode material. Use a sintering aid composed of B 2 O 3 , Bi 2 O 3 , MeO and CuO (where Me is one metal selected from the group consisting of Ca, Sr, Ba and Zn). To lower the sintering temperature. However, when the sintering temperature is lowered, the K p is reduced to 0.55 or less as compared with a hard piezoelectric ceramic having a K p (electromechanical coupling coefficient) of 0.60 or more.
[0006]
US patent application no. 5433917 relates to a PZT composition having a low sintering temperature of about 1,000 ° C. using a eutectic mixture of CuO and an alkaline earth metal oxide. However, there are no reports on other detailed piezoelectric constants except for the dielectric constant and the dielectric loss. Gui et al also describe a method for reducing the sintering temperature of PZT by using a small amount of B 2 O 3 , Bi 2 O 3 , and CdO. However, there is a problem that the sintering temperature in both prior arts is still high for sintering simultaneously with the Ag electrode.
[0007]
In such prior art, a glass frit having a low melting point is used as a sintering aid, but all elements in the glass frit, such as boron, are perovskite in a PZT matrix during sintering. Not substituted with crystal lattice structure. However, after sintering, they remain in the glass phase along the grain boundaries, which becomes a problem that degrades the piezoelectric properties.
[0008]
[Patent Literature]
US patent application no. 579379
[Patent Literature]
US patent application no. 5433917
[0009]
[Problems to be solved by the invention]
The present invention has been made to solve such a problem, and an object of the present invention is to provide a piezoelectric ceramic composition having a low dielectric loss and a high piezoelectric constant and capable of being sintered at a low temperature. Is to provide.
[0010]
Another object of the present invention is to provide a low-temperature sintered piezoelectric ceramic composition that can be sintered simultaneously with pure Ag at a melting point of Ag of 962 ° C. or lower.
[0011]
Another object of the present invention is to provide a piezoelectric ceramic device suitable for continuous driving, such as a multilayer piezoelectric ceramic transformer and a multilayer piezoelectric ceramic actuator, using the piezoelectric ceramic composition according to the present invention. .
[0012]
[Means for Solving the Problems]
To achieve the above object, the present invention is, [(Pb 1-m- n over p Sr m Ba n Cd p) (Zr x Ti 1-x) 1-k (Bi a Mn b) k] O 3 (In the formula, molar ratios m, n, p, x, a, b and k are 0.00 ≦ m <0.15, 0.00 ≦ n <0.15, 0.00 <m + n <0.21. 0.00 <p <0.04, 0.50 ≦ x <0.56, 0.00 <a ≦ 1.00, 0.00 <b ≦ 1.00, 0.00 <k <0.04 A piezoelectric ceramic composition comprising a ceramic.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The piezoelectric ceramic composition according to the present invention, as an essential component [(Pb 1-m-n over p Sr m Ba n Cd p) (Zr x Ti 1-x) 1-k (Bi a Mn b) k] O 3 (molar ratios m, n, p, x, a, b and k are 0.00 ≦ m <0.15, 0.00 ≦ n <0.15, 0.00 <m + n <0.21, 0 0.00 <p <0.04, 0.50 ≦ x <0.56, 0.00 <a ≦ 1.00, 0.00 <b ≦ 1.00, 0.00 <k <0.04. .) Contains ceramic. The ceramic is obtained by alloying a solid solution of PZT (lead zirconate titanate) together with strontium, barium, cadmium, bismuth and manganese ions. In order to lower the sintering temperature without deteriorating the piezoelectric constant, highly reactive Cd and Bi are added. Zr 4+ or Ti 4+ is replaced with Bi 3+ . The charge balance due to the substitution of alien ions is maintained by the generation of oxygen vacancies that increase the diffusion process during sintering, and thus firing. Effectively lowers the setting temperature. The Pb 2+ in such materials system was replaced with Cd 2+, high activity of Cd 2+ while accelerating the diffusion process in the sintering process, effectively lowering the sintering temperature. The Cd content p is preferably 0 <p <0.04. If the amount of Cd is out of this range, the electromechanical coupling coefficient K p (electromechanical coupling coefficient) and the piezoelectric constant d 33 (piezo modulus) decrease until reaching a non-practical level, which is not preferable.
[0014]
Bi is added together with Mn expressed in Bi a Mn b . Mn, along with increasing the mechanical quality factor Q m (mechanical quality factor), is added to control the size of the crystal grains of the sintered body (sintered element). A or b, which is the relative amount of Bi and Mn, is preferably in the range of 0 <a or b ≦ 1, and more preferably 3a + 4b = 4.
[0015]
For example, a = 1, 2/3, 1/2, or 1/3, and b = 1/4, 1/2, 5/8, or 3/4, respectively. If Zr 4+ and Ti 4+ are replaced with Bi 3+ or Mn 4+ under the above conditions, k (a / 4) mole amount of Bi 3+ or Mn 4+ ions will be excessive per mole of matrix. Therefore, an excessive amount of Bi 3+ or Mn 4+ ions not substituted by the PZT matrix (matrix) forms a liquid phase during sintering, which is useful for densification. The maximum amount (k) of Bi a Mn b is preferably 0 <k <0.04. Outside this range, K p and d 33 decrease rapidly, which is not preferable. Further, k preferably satisfies k = p.
[0016]
In order to increase the dielectric constant and at the same time improve the densification without apparently adverse effects on the piezoelectric constant, Sr or Ba is added. The maximum amount of Sr or Ba that can replace Pb is about 15 mol% in PZT when added alone. However, when added together, the maximum amount of Sr + Ba can be extended to 18-20 mol%. As a result, a higher dielectric constant can be obtained. In addition, in the case of mixed substitution, if it is added at the same atomic ratio, it shows better sintering characteristics than single substitution. The amount of Sr or Ba (m or n) is preferably 0.0 <m or n <0.15 and 0 <m + n <0.21. If it is out of such a range, the sintering temperature becomes very high, which is not preferable.
[0017]
The piezoelectric ceramic composition according to the present invention preferably further includes 0.001 to 1% by weight of Bi 2 O 3 in order to improve the sinterability or the mechanical quality factor.
[0018]
The piezoelectric ceramic composition according to the present invention further comprises a LiF or MgF 2. Fluorine (F) improves the piezoelectric characteristics at high electric fields and increases the dielectric constant. Therefore, when such a fluorine compound is included, high mechanical adaptability or high piezoelectric characteristics at high electric fields can be obtained. Improved and preferred. The amount of LiF or MgF 2 which is a fluorine compound is 0.001 to 1% by weight.
[0019]
The piezoelectric ceramic composition according to the present invention preferably further includes 0.001 to 0.50 wt% of MnO 2 in order to improve the sinterability or the mechanical quality factor.
[0020]
The present invention also provides a piezoelectric ceramic device comprising a piezoelectric ceramic obtained by sintering the piezoelectric ceramic composition at 1075 ° C. or lower.
[0021]
The present invention also provides a multilayer piezoelectric ceramic device comprising a piezoelectric ceramic layer obtained by simultaneously sintering the piezoelectric ceramic composition together with an Ag internal electrode at 960 ° C. or less.
[0022]
The present invention also provides a multilayer piezoelectric ceramic device comprising a piezoelectric ceramic layer obtained by simultaneously sintering the piezoelectric ceramic composition together with an Ag—Pd internal electrode. The amount of Pd is preferably 0.001 to 20% by weight with respect to 100% by weight of Ag and Pd.
[0023]
The present invention also provides a piezoelectric ceramic device comprising a piezoelectric ceramic layer obtained by co-sintering the piezoelectric ceramic composition together with an Ag internal electrode at 960 ° C. or less and including a multilayer portion and a single layer portion. To do.
[0024]
The present invention also includes a piezoelectric ceramic layer comprising a piezoelectric ceramic layer obtained by simultaneously sintering the piezoelectric ceramic composition together with an Ag—Pd internal electrode at 1050 ° C. or less, and including a multilayer portion and a single layer portion. I will provide a. The amount of Pd is preferably 0.001 to 20% by weight with respect to 100% by weight of Ag and Pd.
[0025]
The present invention will be readily understood by the following examples relating to a piezoelectric ceramic composition and a piezoelectric ceramic transformer using the same. However, these examples are only for explaining the present invention and do not limit the scope of the present invention.
[0026]
[Example 1]
Piezoelectric ceramic compositions PbO, ZrO 2 , TiO 2 , SrCO 3 , BaCO 3 , CdO, Bi 2 O 3 , MnO 2 and LiF or MgF 2 are used as starting materials. After the starting materials are weighed in the quantitative ratios shown in Table 1, deionized water is added, wet mixing is performed using an attrition mill for 2 hours, and the slurry is vacuum filtered. The filtered material is dried in an oven at 120 ° C. and calcined at 700-875 ° C. for 2 hours. The obtained calcined product is pulverized again using an attrition mill until the average particle size becomes about 0.8 μm. The slurry obtained by pulverization is dried, and a small amount (about 2% by weight) of 10% PVA (Poly Vinyl Alcohol) is added to the dried powder and granulated. The obtained granulated powder, a green disk having a diameter of 25 mm and a thickness of about 2.5 mm (meaning an unfired disk, the same applies hereinafter) (green disk), was formed by applying a pressure of 1000 kg / cm 2. Get a molding. The green disk is sintered at 920-1000 ° C. for 2 hours. Ag paste is printed on both surfaces of the sintered disk and baked at 700-770 ° C. for 15 minutes. The disk on which the electrode is formed is subjected to polarization treatment by applying a voltage of 3 to 4 kV / mm for 15 minutes in a 120 to 140 ° C. silicon oil bath. The dielectric constant and the dielectric loss factor are measured using an LCR meter at an input level of 1 Vrms and 1 kHz. The piezoelectric constant d 33 is measured using a Berlinlin d 33 meter. The planar coupling coefficient (planar coupling coefficient) and mechanical quality factor Qm (mechanical qualityfactor), the resonance frequency f r (resonant frequency), the anti-resonance frequency f a (antiresonant frequency), the capacitance C 0 and the impedance measured at LCR meter The resonance impedance Z r (resonant impedance) measured by an analyzer (Impedance / Gain-Phase analyzer) is calculated by the following equation.
[0027]
1 / k p = 0.395 f r / (f a −f r ) +0.574
Q m = 1 / 2πf r Z r C o (1- (f r / f a) 2)
[0028]
The compositions marked with * in Table 1 and the compositions of Samples # 6, # 8 and # 13-15 are comparative samples and are outside the scope of the present invention. The properties of the samples sintered at 1050 ° C., 965 ° C. and 950 ° C. are shown in Table 2. As shown in the table, a useful piezoelectric constant can also be obtained when sintered at 1050 ° C. and thus 950 ° C. When p of the Cd amount became 0.04 (sample # 4), k p rapidly decreased. When the total amount of Ba + Sr is 22 mol% (Sample # 1 and Sample # 2), due to the slow diffusion rate of Ba and Sr in comparison with Pb, k p also decreases rapidly at such a sintering temperature. According to sample # 10 and sample # 11, it can be seen that F can be added in a range of 1 wt% or less without significantly affecting kp. In Table 1 and Table 3 below, y represents the amount (% by weight) of Bi 2 O 3 further contained, and z represents the amount (% by weight) of LiF or MgF 2 . Although it is possible to use MgF 2 , the parameters of the sample made of MgF 2 are less preferred than those of the sample made of LiF.
[0029]
More diverse characteristics can be obtained by changing the Zr / Ti composition ratio. As shown in Table 3, piezoelectric ceramic compositions capable of being sintered at low temperature with varying Zr / Ti composition ratios according to the present invention were prepared. The compositions of # 61 and # 65 listed in Table 3 are comparative samples and are outside the scope of the present invention. Table 4 shows the characteristics of a piezoelectric disk prepared by sintering at 940 ° C. All compositions are easily sintered at 940 ° C. and have good piezoelectric properties, low dielectric loss of 0.2-0.4%, high dielectric constant of 1470-1850. constant), a d 33 of 310-396, and a mechanical quality factor of 610-730. By changing the Zr / Ti composition ratio, as shown in samples # 61 to # 64, the temperature coefficient of the resonance frequency and the dielectric constant can be adjusted. Further, by adding LiF, as shown in sample # 63 and sample # 65, it is possible to increase the dielectric constant without deteriorating the temperature coefficient of the resonant frequency (temporal coefficient). it can. Such a low sintering temperature makes it possible to use pure Ag paste as an internal electrode in multilayer piezoelectric ceramic parts such as piezoelectric ceramic transformers and piezoelectric actuators. A high dielectric constant and a low temperature coefficient of the resonant frequency can be usefully applied to an application that operates in a resonant mode, such as a piezoelectric ceramic transformer.
[0030]
[Table 1]
Figure 0004804709
[0031]
[Table 2]
Figure 0004804709
Figure 0004804709
[0032]
[Table 3]
Figure 0004804709
[0033]
[Table 4]
Figure 0004804709
[0034]
[Example 2]
Piezoelectric ceramic transformer having a pure Ag internal electrode A piezoelectric ceramic transformer having a pure Ag internal electrode was produced using the composition according to the present invention. Take composition sample # 63 as an example. The produced Rosen-type piezoceramic transformer is shown in FIG. As shown in FIG. 1, the input portion I has a multilayer structure, and each layer of the multilayer structure is alternately polarized up and down in the thickness direction. The output portion O is a single layer and is polarized P in the length direction of the transformer. Fabrication of the piezoelectric ceramic transformer begins with the preparation of a green sheet of PZT material. The calcined product is combined with a ball using polyvinyl butyral (PVB), dibutyl phthalate (DBP), fish oil, fish oil, methyl ethyl ketone (MEK) and toluene (toluene). Mix for 36 hours. The ground slurry is vacuum degassed, and then a 95 μm-thick tape is formed on the PET film using a doctor blade casting machine. A green tape is cut into a 150 mm × 150 mm sheet having alignment holes. The alternating internal piezoelectrics are printed on a green sheet of Ag paste and dried in a continuous oven. The printed green sheets are stacked using the alignment holes, and the internal piezoelectric elements are arranged in a uniform manner, and are heated and pressure bonded at 85 ° C. under vacuum. A hot-laminated green bar is cut into each green element. The binder, as well as other organics in the green element, were sintered at 940 ° C. for 2 hours after debinding at 260 ° C. The external input / output electrodes were screen-printed with Ag paste and baked at 780 ° C. The input portion was a polarization voltage of 450 VDC, the output portion was a polarization voltage of 25 kVDC, and the polarization treatment was performed in a silicon oil bath at 130 ° C.
[0035]
The piezoelectric ceramic transformer has a size of 26.0 mm × 5.0 mm × 1.3 mm, has 15 piezoelectric-active layers, and has 16 internal electrodes. The Ag paste has almost no reaction when co-sintered at 940 ° C. with a PZT matrix made of composition sample # 63 according to the present invention. The Ag internal electrode is 100% coated on the electrode surface, has no delamination, does not have a very high resonance impedance, and has excellent piezoelectric characteristics. Table 5 shows the characteristics of the piezoelectric ceramic transformer. FIG. 2 shows the operation characteristics. A conversion efficiency of 93% or more was measured.
[0036]
The low-temperature sinterable piezoelectric ceramic composition according to the present invention is not limited to the application of a piezoelectric ceramic transformer, but can be applied not only to a single-layer piezoelectric transformer but also to a multilayer actuator, a multilayer sensor, and a bimorph.
[0037]
[Table 5]
Figure 0004804709
[0038]
【The invention's effect】
As described above, the piezoelectric ceramic composition according to the present invention has a low dielectric loss and a high piezoelectric constant, and is pure at a reduced temperature, particularly at or below 962 ° C., which is the melting point of Ag. Simultaneous sintering with Ag can be performed.
[0039]
In addition, the piezoelectric ceramic device according to the present invention is suitable for applications in which continuous operation is performed, such as a piezoelectric ceramic transformer, a multilayer piezoelectric ceramic actuator, and the like, and has excellent conversion efficiency.
[Brief description of the drawings]
FIG. 1 is a perspective view of a piezoelectric ceramic in a piezoelectric ceramic transformer according to an embodiment of the piezoelectric ceramic device of the present invention.
FIG. 2 is a graph showing a frequency characteristic of an output voltage among operating characteristics of a piezoelectric ceramic transformer according to an embodiment of the piezoelectric ceramic device of the present invention.
FIG. 3 is a graph showing frequency characteristics for open-load 100 MOhm and 200 kOhm among operating characteristics of a piezoelectric ceramic transformer according to an embodiment of the piezoelectric ceramic device of the present invention;
FIG. 4 is a graph showing output current and output voltage characteristics among operating characteristics of a piezoelectric ceramic transformer according to an embodiment of the piezoelectric ceramic device of the present invention;
[Explanation of symbols]
I Input part (Input section)
O Output section (Output section)
P Polarization

Claims (12)

下記一般式（１）
［（Ｐｂ１−ｍ−ｎ-ｐＳｒｍＢａｎＣｄｐ）（Ｚｒ x Ｔｉ１−x）１−ｋ（ＢｉａＭｎｂ）ｋ］Ｏ３・・・（Ｉ）
（ 但し、一般式（Ｉ）中、モル比ｍ，ｎ，ｐ，ｘ，ａ，ｂ及びｋは０．００≦ｍ＜０．１５、０．００≦ｎ＜０．１５、０．００＜ｍ＋ｎ＜０．２１、０．００＜ｐ＜０．０４、０．５０≦ｘ＜０．５６、０．００＜ａ≦１．００、０．００＜ｂ≦１．００、０．００＜ｋ＜０．０４である）で表されるセラミックを含み；０．００１〜１重量％のＬｉＦ又はＭｇＦ２をさらに含むことを特徴とする圧電セラミック組成物。The following general formula (1)
[(Pb 1-m-n -p Sr m Ba n Cd p) (Zr x Ti 1-x) 1-k (Bi a Mn b) k] O 3 ··· (I)
(In the general formula (I), the molar ratios m, n, p, x, a, b and k are 0.00 ≦ m <0.15, 0.00 ≦ n <0.15, 0.00 < m + n <0.21, 0.00 <p <0.04, 0.50 ≦ x <0.56, 0.00 <a ≦ 1.00, 0.00 <b ≦ 1.00, 0.00 < k <0.04); a piezoelectric ceramic composition characterized by further comprising 0.001 to 1% by weight of LiF or MgF 2 . 前記ａ及びｂにおいて、３ａ＋４ｂ＝４であることを特徴とする請求項１記載の圧電セラミック組成物。  2. The piezoelectric ceramic composition according to claim 1, wherein a and b are 3a + 4b = 4. ０．００１〜１重量％のＢｉ２Ｏ３をさらに含むことを特徴とする請求項１記載の圧電セラミック組成物。  The piezoelectric ceramic composition according to claim 1, further comprising 0.001 to 1 wt% Bi2O3. 前記ｐ及びｋにおいて、ｐ＝ｋであることを特徴とする請求項１記載の圧電セラミック組成物。  2. The piezoelectric ceramic composition according to claim 1, wherein, in p and k, p = k. ０．００１〜０．５０重量％のＭｎＯ２をさらに含むことを特徴とする請求項１記載の圧電セラミック組成物。  The piezoelectric ceramic composition according to claim 1, further comprising 0.001 to 0.50% by weight of MnO2. 前記請求項１または請求項２の圧電セラミック組成物を１０７５℃以下で焼結して得た圧電セラミックを含んで構成されることを特徴とする圧電セラミック装置。  A piezoelectric ceramic device comprising a piezoelectric ceramic obtained by sintering the piezoelectric ceramic composition of claim 1 or 2 at 1075 ° C. or lower. 前記請求項１または請求項２の圧電セラミック組成物を銀（Ａｇ）内部電極と共に９６０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成されることを特徴とする多層圧電セラミック装置。  A multilayer piezoelectric ceramic comprising a piezoelectric ceramic layer obtained by co-sintering the piezoelectric ceramic composition of claim 1 or 2 with a silver (Ag) internal electrode at 960 ° C. or lower. apparatus. 前記請求項１または請求項２の圧電セラミック組成物を銀（Ａｇ）−パラジウム（Ｐｄ）内部電極と共に同時焼結を行って得た圧電セラミック層を含んで構成されることを特徴とする多層圧電セラミック装置。  A multilayer piezoelectric material comprising a piezoelectric ceramic layer obtained by co-sintering the piezoelectric ceramic composition of claim 1 or 2 together with a silver (Ag) -palladium (Pd) internal electrode. Ceramic equipment. 前記Ｐｄの量は、前記Ａｇ及びＰｄの１００重量％に対して０．００１〜２０重量％であることを特徴とする請求項８記載の多層圧電セラミック装置。  9. The multilayer piezoelectric ceramic device according to claim 8, wherein the amount of Pd is 0.001 to 20% by weight with respect to 100% by weight of Ag and Pd. 前記請求項１または請求項２の圧電セラミック組成物をＡｇ内部電極と共に９６０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成され、多層部分及び単層部分を含むことを特徴とする圧電セラミック装置。  A piezoelectric ceramic layer obtained by co-sintering the piezoelectric ceramic composition according to claim 1 or 2 together with an Ag internal electrode at 960 ° C. or less and including a multilayer portion and a single layer portion. A piezoelectric ceramic device. 前記請求項１または請求項２の圧電セラミック組成物をＡｇ−Ｐｄ内部電極と共に１０５０℃以下で同時焼結を行って得た圧電セラミック層を含んで構成され、多層部分及び単層部分を含むことを特徴とする圧電セラミック装置。  A piezoelectric ceramic layer obtained by co-sintering the piezoelectric ceramic composition according to claim 1 or 2 together with an Ag—Pd internal electrode at 1050 ° C. or less and including a multilayer portion and a single layer portion. A piezoelectric ceramic device characterized by the above. 前記Ｐｄの量は、前記Ａｇ−Ｐｄの１００重量％に対して、０．００１〜２０重量％であることを特徴とする請求項１１記載の圧電セラミック装置。The piezoelectric ceramic device according to claim 11 , wherein the amount of Pd is 0.001 to 20% by weight with respect to 100% by weight of the Ag—Pd.
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