JP2003012369A - Piezoelectric compact of ceramic composition - Google Patents
Piezoelectric compact of ceramic compositionInfo
- Publication number
- JP2003012369A JP2003012369A JP2001199031A JP2001199031A JP2003012369A JP 2003012369 A JP2003012369 A JP 2003012369A JP 2001199031 A JP2001199031 A JP 2001199031A JP 2001199031 A JP2001199031 A JP 2001199031A JP 2003012369 A JP2003012369 A JP 2003012369A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic composition
- piezoelectric ceramic
- piezoelectric
- perovskite structure
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は圧電体磁器組成物、
特に積層型圧電素子の材料として有用な圧電体磁器組成
物に関する。TECHNICAL FIELD The present invention relates to a piezoelectric ceramic composition,
In particular, it relates to a piezoelectric ceramic composition useful as a material for a laminated piezoelectric element.
【０００２】[0002]
【従来の技術】近年、圧電体磁器組成物を用いた電子デ
バイスの応用分野は益々広がりを見せており、通信やメ
カトロニクス等の分野では、小型化及び低電圧駆動への
要求が高まっている。この要求に応えるため、圧電磁器
組成物を含む薄層グリーンシート上に内部電極用の導体
ペーストを印刷し、積層一体化した後、同時焼成した積
層型素子が種々開発され実用化されてきている。2. Description of the Related Art In recent years, application fields of electronic devices using a piezoelectric ceramic composition have been expanding more and more, and in fields such as communication and mechatronics, there is an increasing demand for miniaturization and low voltage driving. In order to meet this demand, various laminated type elements have been developed and put into practical use by printing a conductor paste for internal electrodes on a thin green sheet containing a piezoelectric ceramic composition, laminating and integrating them, and then cofiring them. .
【０００３】これらの電子デバイス用の圧電体磁器組成
物の特性としては電気機械結合係数（ｋｒ）、機械的品
質係数（Ｑｍ）が大きいことが望ましい。この目的に合
致する圧電体磁器組成物としては、ＰＺＴ（ＰｂＺｒＯ
3−ＰｂＴｉＯ3固溶体）系やＰＴ（正方晶系ＰｂＴｉＯ
3）系等のペロブスカイト構造を有する強誘電体がよく
知られている。It is desirable that the piezoelectric ceramic composition for these electronic devices has large electromechanical coupling coefficient (kr) and mechanical quality coefficient (Qm). A piezoelectric ceramic composition that meets this purpose is PZT (PbZrO 2
3- PbTiO 3 solid solution) or PT (tetragonal PbTiO 3 )
Ferroelectrics having a perovskite structure such as 3 ) are well known.
【０００４】しかしながら、ＰＺＴ系やＰＴ系の圧電磁
器組成物は、一般に焼結温度が1200〜1400℃と高温であ
る。このため、圧電磁器組成物を電極と同時焼成して一
体化するためには、電極材料が、上記の焼成温度に耐え
得る高価なＰｔやＰｄ等に限定される。また、高い焼成
温度に対応した設備も必要となる。この結果、安価な製
品を提供することができなかった。However, the PZT-based or PT-based piezoelectric ceramic composition generally has a high sintering temperature of 1200 to 1400 ° C. Therefore, in order to co-fire the piezoelectric ceramic composition with the electrode to integrate them, the electrode material is limited to expensive Pt, Pd, or the like that can withstand the firing temperature. In addition, equipment corresponding to high firing temperature is also required. As a result, an inexpensive product could not be provided.
【０００５】この問題を解決するため、ＰＺＴ系組成物
に他の金属化合物を加えて焼結温度を下げる努力がなさ
れている。例えば、特開平2-303081号公報には、Ｐｂ
（Ｎｉ 1/3Ｎｂ2/3）Ｏ3−ＰｂＺｒＯ3−ＰｂＴｉＯ3に
Ｐｂ（Ｃｕ1/2Ｗ1/2）Ｏ3を添加した組成物が記載され
ている。しかし、上記の系では電気機械結合定数等の圧
電特性が劣化する。そこで、低温焼結性と圧電特性を両
立させる系も検討され、Ｐｂ（Ｔｉ，Ｚｒ）Ｏ3に、Ｍ
ｎまたはＣｒのいずれか、及びＷを加えた磁器組成物
（特開平9-169566号公報）、ＰｂＺｒＯ3−ＰｂＴｉＯ3
−Ｐｂ（Ｚｎ1/3Ｓｂ2 /3）Ｏ3にＢｉ及びＦｅを添加し
た組成物（特開2000-86341号公報）等が提案されてい
る。しかし、前者の焼成温度は1100℃以上であり、後者
でも９６０℃での長時間焼成を必要とする。このため、
安価なＡｇ（融点：９６０℃）を電極材料として用い同
時焼成により積層圧電体を形成することは未だ困難であ
った。In order to solve this problem, a PZT composition
No effort was made to lower the sintering temperature by adding other metal compounds to
Has been. For example, Japanese Patent Laid-Open No. 2-303081 discloses Pb.
(Ni 1/3Nb2/3) O3-PbZrO3-PbTiO3To
Pb (Cu1/2W1/2) O3The composition with the addition of
ing. However, in the above system, pressure such as electromechanical coupling constant is
The electrical characteristics deteriorate. Therefore, both low temperature sinterability and piezoelectric characteristics are
A system for standing up is also considered, and Pb (Ti, Zr) O3To M
Porcelain composition containing either n or Cr and W
(JP-A-9-169566), PbZrO3-PbTiO3
-Pb (Zn1/3Sb2 / 3) O3Bi and Fe are added to
And other compositions (Japanese Patent Laid-Open No. 2000-86341) have been proposed.
It However, the firing temperature of the former is 1100 ° C or higher, and the firing temperature of the latter is
However, it requires long-term firing at 960 ° C. For this reason,
Inexpensive Ag (melting point: 960 ° C) is used as an electrode material.
It is still difficult to form a laminated piezoelectric material by firing.
It was.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、従来
技術における上述の問題点を解消することにあり、具体
的には、比較的安価なＡｇまたはＡｇリッチなＡｇ／Ｐ
ｄを内部電極材料として利用可能とする、低温焼結性を
有し、なおかつ、電気機械結合係数（ｋｒ）、機械的品
質係数（Ｑｍ）等の圧電特性に優れた圧電体磁器組成物
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art. Specifically, it is relatively inexpensive Ag or Ag-rich Ag / P.
Provided is a piezoelectric ceramic composition having low-temperature sinterability, which enables the use of d as an internal electrode material, and which is excellent in piezoelectric characteristics such as electromechanical coupling coefficient (kr) and mechanical quality coefficient (Qm). To do.
【０００７】[0007]
【課題を解決するための手投】上記目的を達成するた
め、本発明者らは、少なくともＰｂ，Ｚｒ，Ｔｉ，Ｎｂ
及びＺｎの５種の金属元素を含むペロブスカイト構造を
有する複合酸化物を主成分とした系について検討した。
その結果、副成分としてＭｎ及びＣｄ元素を添加するこ
とにより、低温焼成と良好な圧電特性とを同時に実現し
得ることを見出し、本発明を完成するに至った。[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have at least Pb, Zr, Ti, Nb.
A system containing a complex oxide having a perovskite structure containing five metal elements of Zn and Zn as a main component was examined.
As a result, they have found that by adding Mn and Cd elements as sub-components, low temperature firing and good piezoelectric properties can be realized at the same time, and the present invention has been completed.
【０００８】すなわち、本発明は以下の圧電体磁器組成
物を提供する。
（１） 少なくともＰｂ，Ｚｒ，Ｔｉ，Ｎｂ及びＺｎの
５種の金属元素を含むペロブスカイト構造を有する複合
酸化物を主成分とし、副成分としてＭｎ元素を含む圧電
体磁器組成物において、Ｃｄ元素を含有することを特徴
とする圧電体磁器組成物。
（２） ＣｄＯに換算して0.3〜1.5質量％のＣｄを含有
する前記１に記載の圧電体磁器組成物。
（３） ＭｎＯ2に換算して0.05〜0.75質量％のＭｎを
含有する前記１または２に記載の圧電体磁器組成物。
（４） 前記複合酸化物を一般式ＡＢＯ3（Ａ、Ｂはペ
ロブスカイト構造を構成する金属元素）で表したとき、
化学量論的に該複合酸化物のＡサイトに含まれるべき値
を超える量のＰｂ元素を含むことを特徴とする前記１〜
３のいずれかに記載の圧電体磁器組成物。
（５） 前記金属元素を含む原料粉末として平均粒子径
が0.7μｍ以下である微粉末を用いる前記１〜４のうち
いずれかに記載の圧電体磁器組成物。That is, the present invention provides the following piezoelectric ceramic composition. (1) In a piezoelectric ceramic composition containing, as a main component, a complex oxide having a perovskite structure containing at least five metal elements of Pb, Zr, Ti, Nb, and Zn, and a Mn element as a subcomponent, a Cd element is added. A piezoelectric ceramic composition characterized by containing the same. (2) The piezoelectric ceramic composition as described in 1 above, which contains 0.3 to 1.5% by mass of Cd in terms of CdO. (3) The piezoelectric ceramic composition as described in 1 or 2, which contains 0.05 to 0.75 mass% of Mn in terms of MnO 2 . (4) When the complex oxide is represented by the general formula ABO 3 (A and B are metal elements constituting the perovskite structure),
1-characterized in that the Pb element is contained stoichiometrically in an amount exceeding the value to be contained in the A site of the composite oxide.
3. The piezoelectric ceramic composition according to any one of 3 above. (5) The piezoelectric ceramic composition as described in any one of 1 to 4 above, wherein a fine powder having an average particle diameter of 0.7 μm or less is used as the raw material powder containing the metal element.
【０００９】[0009]
【発明の実施の形態】以下、本発明の圧電体磁器組成物
について説明する。本発明の圧電体磁器組成物は、少な
くともＰｂ，Ｚｒ，Ｔｉ，Ｎｂ及びＺｎの５種の金属元
素を含むペロブスカイト構造を有する複合酸化物を主成
分とし、副成分としてＭｎ元素を含む圧電体磁器組成物
においてＣｄ元素を含有させたものである。ペロブスカ
イト型酸化物は、一般にＡＢＯ3の結晶構造で表現され
る。Ｐｂ，Ｚｒ，Ｔｉ，Ｎｂ及びＺｎを含む系では、基
本的には、ＡサイトがＰｂ（Ｐｂ2+）によって、Ｂサイ
トがＺｒ（Ｚｒ4+），Ｔｉ（Ｔｉ4+），Ｎｂ（Ｎｂ5+）
及びＺｎ（Ｚｎ2+）によって占められる。上記の各元素
を含むペロブスカイト型複合酸化物は、典型的には、α
Ｐｂ（Ｚｎ1/3Ｎｂ2/3）Ｏ3−βＰｂＴｉＯ3−γＰｂＺ
ｒＯ3（但し、係数α，β，γはモル分率であり、α＋
β＋γ＝１）であるが、Ｍｎを含加えた組成において９
００℃〜１１００℃で焼結可能であれば他のペロブスカ
イト型複合酸化物の組合せでもよい。α，β及びγの好
適範囲は、例えば、αが0.01〜0.5、βが0〜0.9、γが0
〜0.9程度の範囲（より好適な各成分の比は特公昭44-17
344号公報参照）である。BEST MODE FOR CARRYING OUT THE INVENTION The piezoelectric ceramic composition of the present invention will be described below. The piezoelectric ceramic composition of the present invention is mainly composed of a complex oxide having a perovskite structure containing at least five metal elements of Pb, Zr, Ti, Nb, and Zn, and a Mn element as a subcomponent. The composition contains a Cd element. The perovskite type oxide is generally represented by the crystal structure of ABO 3 . In a system containing Pb, Zr, Ti, Nb and Zn, basically, the A site is Pb (Pb 2+ ) and the B site is Zr (Zr 4+ ), Ti (Ti 4+ ), Nb (Nb 5+ )
And Zn (Zn 2+ ). The perovskite type composite oxide containing each of the above elements is typically α
Pb (Zn 1/3 Nb 2/3 ) O 3 -βPbTiO 3 -γPbZ
rO 3 (However, the coefficients α, β, γ are molar fractions, and α +
β + γ = 1), but 9 in the composition containing Mn
Other perovskite type complex oxides may be combined as long as they can be sintered at 00 ° C to 1100 ° C. Suitable ranges of α, β and γ are, for example, α is 0.01 to 0.5, β is 0 to 0.9, and γ is 0.
~ 0.9 (a more preferable ratio of each component is
No. 344).
【００１０】副成分として含有させるＭｎ元素は、主と
して上に挙げた主構成元素の一部を置換するものである
が、結晶粒界等に存在してもよい。Ｍｎの含有量は、通
常、ＭｎＯ2に換算して組成物全体の0.05〜0.75質量％
程度である。Ｍｎ含有量がこの範囲から外れると低温で
の焼成と良好な圧電特性を両立させることができない。The Mn element contained as a sub-component mainly replaces a part of the above-mentioned main constituent elements, but may be present at a crystal grain boundary or the like. The content of Mn is usually 0.05 to 0.75 mass% of the entire composition in terms of MnO 2.
It is a degree. If the Mn content deviates from this range, it is not possible to achieve both low temperature firing and good piezoelectric properties.
【００１１】本発明の圧電体磁器組成物では、さらにＣ
ｄ元素を含有させる。これにより、圧電特性の劣化を招
くことなく９００〜９５０℃程度での焼成が可能とな
る。Ｃｄの含有量は、好ましくは組成物全体の0.3〜1.5
質量％の範囲である。Ｃｄ含有量がこの範囲を外れる
と、圧電特性の改善において十分な効果が得られない。In the piezoelectric ceramic composition of the present invention, C
d element is contained. This enables firing at about 900 to 950 ° C. without causing deterioration of piezoelectric characteristics. The content of Cd is preferably 0.3 to 1.5 of the total composition.
It is in the range of mass%. If the Cd content is out of this range, a sufficient effect cannot be obtained in improving the piezoelectric characteristics.
【００１２】本発明の圧電体磁器組成物は、例えば、各
元素を含む原料粉末を目的組成から計算される適正な量
比で混合して焼成することにより製造できる。この際、
Ｐｂを過剰に添加することが好ましい。例えば、前記の
αＰｂ（Ｚｎ1/3Ｎｂ2/3）Ｏ 3−βＰｂＴｉＯ3−γＰｂ
ＺｒＯ3において、Ｚｎ：（１／３）αモル、Ｎｂ：
（２／３）αモル、Ｔｉ：βモル、Ｚｒ：γモルに対
し、Ｐｂの化学量論からの必要量（ｍ0）は１モルであ
るが、この値よりも過剰量（ｍ1）を添加する。これに
より圧電特性がさらに改善される。The piezoelectric ceramic composition of the present invention is, for example,
Proper amount calculated from the target composition of raw material powder containing elements
It can be manufactured by mixing and firing in a ratio. On this occasion,
It is preferable to add Pb in excess. For example, above
αPb (Zn1/3Nb2/3) O 3-ΒPbTiO3-ΓPb
ZrO3In, Zn: (1/3) α mol, Nb:
(2/3) pair with α mole, Ti: β mole, Zr: γ mole
The required amount from the stoichiometry of Pb (m0) Is 1 mol
However, an excess amount (m1) Is added. to this
The piezoelectric characteristics are further improved.
【００１３】各元素を含む原料としては、例えば、それ
ぞれの酸化物、焼成温度以下で熱分解する炭酸塩等を用
いることができる。２以上の元素を含有する複合酸化物
を用いてよい。複合酸化物の例としては、ＰｂＴｉ
Ｏ3，ＰｂＺｒＯ3，Ｐｂ（Ｚｎ1/ 3Ｎｂ2/3）Ｏ3等の主
要構成成分からなるペロブスカイト型酸化物のほかに、
Ｃｄ（Ｍｎ1/3Ｎｂ2/3）Ｏ3のような副成分を含む複合
酸化物の形態で添加しても同様の効果が得られる。圧電
特性を、一層、改善することから原料の平均粒子径は0.
7μｍ以下とすることが好ましい。As the raw material containing each element, for example, respective oxides, carbonates which are thermally decomposed at a firing temperature or lower can be used. A composite oxide containing two or more elements may be used. As an example of the complex oxide, PbTi
The O 3, PbZrO 3, Pb ( Zn 1/3 Nb 2/3) other perovskite type oxide consisting of major constituent of O 3 or the like,
Similar effects can be obtained even when added in the form of a composite oxide containing a subcomponent such as Cd (Mn 1/3 Nb 2/3 ) O 3 . The average particle size of the raw material is 0 because the piezoelectric characteristics are further improved.
It is preferably 7 μm or less.
【００１４】以上においては、ペロブスカイト構造を有
する主成分がＰｂ，Ｚｒ，Ｔｉ，Ｎｂ及びＺｎの５種の
金属元素のみを含む場合について説明したが、本発明は
これに限定されるものではない。すなわち、Ｐｂ，Ｚ
ｒ，Ｔｉ，Ｎｂ及びＺｎの５種の金属元素に加えて、そ
の他の金属元素を含んでもよい。このような金属元素の
例としては、Ｎｉ，Ｍｇ，Ｆｅ，Ｓｃ，Ｓｂ等が挙げら
れる。Although the case where the main component having the perovskite structure contains only five kinds of metal elements of Pb, Zr, Ti, Nb and Zn has been described above, the present invention is not limited to this. That is, Pb, Z
In addition to the five metal elements of r, Ti, Nb and Zn, other metal elements may be included. Examples of such metal elements include Ni, Mg, Fe, Sc, Sb and the like.
【００１５】[0015]
【実施例】以下、実施例及び比較例を挙げて本発明をよ
り具体的に説明する。
実施例１：出発原料として化学的に高純度（99.5％以
上）であるＰｂＯ，ＴｉＯ2，ＺｒＯ2，ＺｎＯ，Ｎｂ2
Ｏ5，ＭｎＯ2，ＣｄＯを用意した。これら各粉末を、ペ
ロブスカイト構造を有する複合酸化物としての0.17Ｐｂ
（Ｚｎ1/3Ｎｂ2/3）Ｏ3−0.39ＰｂＴｉＯ3−0.44ＰｂＺ
ｒＯ3（但し、係数はモル分率）に、表１に示す割合の
ａＭｎＯ2＋ｂＣｄＯ（但し、ａ、ｂは質量％であ
る。）を含有する組成の磁器材料が得られるように秤量
し、ボールミル中でメタノールを加えて湿式粉砕した
後、７００〜９００℃の温度で２時間仮焼した。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. Example 1: chemically as a starting material of high purity (over 99.5%) PbO, TiO 2, ZrO 2, ZnO, Nb 2
O 5 , MnO 2 , and CdO were prepared. Each of these powders was mixed with 0.17 Pb as a complex oxide having a perovskite structure.
(Zn 1/3 Nb 2/3 ) O 3 −0.39PbTiO 3 −0.44PbZ
rO 3 (however, the coefficient is a mole fraction) is weighed so that a porcelain material having a composition containing a ratio of aMnO 2 + bCdO shown in Table 1 (where a and b are mass%) is obtained, Methanol was added in a ball mill and wet-milled, and then calcined at a temperature of 700 to 900 ° C. for 2 hours.
【００１６】この仮焼済み粉末にポリビニルアルコール
系のバインダを１〜２質量％加え、混合粉砕し整粒した
後、５００〜2000ｋｇ／ｃｍ2の圧力でプレス成形して
直経３０ｍｍ、厚み1.5ｍｍの円板状成形体を得た。次
いで、得られた円板状成形体を９００℃、９５０℃及び
１１００℃で２時間焼成して円板状磁器の作成を試み
た。To the calcined powder, 1 to 2% by mass of a polyvinyl alcohol-based binder is added, mixed and pulverized to adjust the particle size, and then press-molded at a pressure of 500 to 2000 kg / cm 2 to obtain a surface length of 30 mm and a thickness of 1.5 mm. A disk-shaped molded body of was obtained. Then, the obtained disk-shaped compact was fired at 900 ° C., 950 ° C. and 1100 ° C. for 2 hours to try to make a disk-shaped porcelain.
【００１７】その後、この円板状磁器の両面に銀電極を
焼き付けし、１００〜１５０℃の絶縁油中で１〜３ｋＶ
／ｍｍの電界を１０〜６０分間印加し、分極処理をおこ
なった。上記のようにして得た円板状試料について、比
誘電率（εｒ）、電気機械結合係数（ｋｒ）、及び機械
的品質係数（Ｑｍ）を求めた。なお、比誘電率（εｒ）
は静電容量を測定し計算により求め、電気機械結合係数
（ｋｒ）及び機械的品質係数（Ｑｍ）は電子工業会規格
ＥＭＡＳ−６１００に基づきインピーダンス測定器によ
り測定し計算により求めた。これらの結果を表１に示
す。なお、表１では、各組成物について、９００℃、９
５０℃及び１１００℃のうち十分に焼結が進行した最も
低い温度の試料について結果を示した。但し、ＣｄもＭ
ｎも含まない試料（試料番号１６）は１１００℃以下で
焼成しなかったため、１２００℃で焼成した例を示し
た。＊印を付したものは本発明の範囲外のものであり、
その他は本発明の範囲内のものである。Thereafter, silver electrodes are baked on both sides of the disk-shaped porcelain, and 1-3 kV in insulating oil at 100-150 ° C.
An electric field of / mm was applied for 10 to 60 minutes to perform polarization treatment. The dielectric constant (εr), electromechanical coupling coefficient (kr), and mechanical quality coefficient (Qm) of the disk-shaped sample obtained as described above were determined. The relative permittivity (εr)
Was calculated and the electromechanical coupling coefficient (kr) and the mechanical quality coefficient (Qm) were measured by an impedance measuring device based on the Electronic Industry Association standard EMAS-6100 and calculated. The results are shown in Table 1. In Table 1, for each composition, 900 ° C, 9
The result was shown about the sample of the lowest temperature of 50 degreeC and 1100 degreeC which fully advanced sintering. However, Cd is also M
The sample containing no n (Sample No. 16) was not fired at 1100 ° C. or lower, so an example of firing at 1200 ° C. was shown. Those marked with * are outside the scope of the present invention,
Others are within the scope of the invention.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１に示す通り、0.17Ｐｂ（Ｚｎ1/3Ｎｂ
2/3）Ｏ3−0.39ＰｂＴｉＯ3−0.44ＰｂＺｒＯ3（但し、
係数はモル分率）を主成分とし、Ｍｎ元素を副成分とし
て含むセラミックスに、Ｃｄ元素を含有させた本発明の
範囲内の試料は、９００℃で焼結する。これに対して、
Ｃｄ元素を含まない試料は、１１００℃で焼成する必要
があり（試料番号１及び１５）、これ以下では電気機械
結合係数（ｋｒ）や機械的品質係数（Ｑｍ）が大幅に低
下するか、焼結不十分（試料番号１４）となる。また、
Ｃｄ元素の含有量の好ましい範囲は、ＣｄＯに換算して
0.3〜1.5質量％である。すなわち、ＣｄＯ含有量が0.3
〜1.5質量％の範囲内においては、１１００℃での焼成
例である試料番号１やＣｄＯの含有量が1.5質量％以上
である試料番号９等と比較して明らかなように、低温
（９００℃）の焼成でも電気機械結合係数（ｋｒ）及び
機械的品質係数（Ｑｍ）の低下が抑えられ、優れた圧電
材料が得られる。As shown in Table 1, 0.17 Pb (Zn 1/3 Nb
2/3 ) O 3 -0.39PbTiO 3 -0.44PbZrO 3 (however,
A sample within the scope of the present invention, in which the Cd element is contained in the ceramic containing the Mn element as a sub ingredient, whose coefficient is the mole fraction) is sintered at 900 ° C. On the contrary,
The sample containing no Cd element needs to be fired at 1100 ° C. (Sample Nos. 1 and 15). Below this, the electromechanical coupling coefficient (kr) and the mechanical quality coefficient (Qm) will be significantly reduced, or The binding is insufficient (Sample No. 14). Also,
The preferable range of the content of Cd element is converted into CdO.
It is 0.3 to 1.5 mass%. That is, the CdO content is 0.3
In the range of up to 1.5% by mass, as can be seen by comparison with Sample No. 1 which is an example of firing at 1100 ° C. and Sample No. 9 in which the content of CdO is 1.5% by mass or more, at low temperature (900 ° C. ), The decrease of the electromechanical coupling coefficient (kr) and the mechanical quality coefficient (Qm) can be suppressed, and an excellent piezoelectric material can be obtained.
【００２０】実施例２：出発原料として化学的に高純度
であるＰｂＯ，ＴｉＯ2，ＺｒＯ2，ＺｎＯ，Ｎｂ2Ｏ5，
ＭｎＯ2，ＣｄＯを用意した。これら各粉末を0.17Ｐｂ
（Ｚｎ1/3Ｎｂ2/ 3）Ｏ3−0.39ＰｂＴｉＯ3−0.44ＰｂＺ
ｒＯ3（但し、係数はモル分率）を主成分とし、表２に
示す換算量比でＭｎＯ2、ＣｄＯ及びＰｂＯを含有する
組成となるように秤量し、ボールミル中でメタノールを
加えて湿式粉砕した後、７００〜９００℃の温度で２時
間仮焼した。これを実施例１と同様に焼結して円板状試
料を形成し、電極を付与して比誘電率（εｒ）、電気機
械結合係数（ｋｒ）及び機械的品質係数（Ｑｍ）を求め
た。これらの結果を表２に示す。Example 2: Chemically highly pure PbO, TiO 2 , ZrO 2 , ZnO, Nb 2 O 5 , as starting materials
MnO 2 and CdO were prepared. 0.17 Pb of each of these powders
(Zn 1/3 Nb 2/3) O 3 -0.39PbTiO 3 -0.44PbZ
Wet milling was carried out by weighing so as to have a composition containing rO 3 (however, the coefficient is a mole fraction) as a main component and containing MnO 2 , CdO and PbO in a conversion amount ratio shown in Table 2, and adding methanol in a ball mill. After that, it was calcined at a temperature of 700 to 900 ° C. for 2 hours. This was sintered in the same manner as in Example 1 to form a disk-shaped sample, and electrodes were provided to determine the relative permittivity (εr), electromechanical coupling coefficient (kr) and mechanical quality coefficient (Qm). . The results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】表２に示す通り、ペロブスカイト構造を有
する複合酸化物である0.17Ｐｂ（Ｚｎ1/3Ｎｂ2/3）Ｏ3
−0.39ＰｂＴｉＯ3−0.44ＰｂＺｒＯ3（但し、係数はモ
ル分率）を主成分とし、Ｍｎ及びＣｄ元素を含むセラミ
ックスにおいて、試料番号１８，２０，２１に示すよう
に一般式ＡＢＯ3で表した場合のＡサイトに入る化学量
論量のＰｂ量を超えて過剰のＰｂ元素を含有する場合に
は、過剰のＰｂ元素を含有しない試料番号１７，１９と
比載して電気機械結合係数（ｋｒ）の値が大きくなり、
圧電特性が向上する。As shown in Table 2, 0.17Pb (Zn 1/3 Nb 2/3 ) O 3 which is a complex oxide having a perovskite structure.
-0.39PbTiO 3 -0.44PbZrO 3 (where the coefficients mole fraction) as a main component, the ceramics containing Mn and Cd element, when represented by the general formula ABO 3 as shown in sample numbers 18, 20 and 21 When an excess amount of Pb element is contained in excess of the stoichiometric amount of Pb entering the A site, the electromechanical coupling coefficient (kr) is compared with Sample Nos. 17 and 19 containing no excess Pb element. Becomes larger,
The piezoelectric characteristics are improved.
【００２３】実施例３：出発原料として化学的に高純度
であるＰｂＯ，ＴｉＯ2，ＺｒＯ2，ＺｎＯ，Ｎｂ2Ｏ5，
ＭｎＯ2，ＣｄＯを用意した。これら各粉末を、0.17Ｐ
ｂ（Ｚｎ1/3Ｎｂ 2/3）Ｏ3−0.39ＰｂＴｉＯ3−0.44Ｐｂ
ＺｒＯ3（但し、係数はモル分率）に対し、0.5質量％Ｍ
ｎＯ2＋1.0質量％ＣｄＯを含有する組成の磁器材料が得
られるように秤量し、ボールミル中でメタノールを加え
て湿式粉砕した後、７００〜９００℃の温度で２時間仮
焼した。その後、直径５ｍｍのジルコニアボールと共
に、有機系の分散剤及びメタノールを加え、平均粒子径
が0.7μｍ以下（島津製作所製レーザー回折式粒度分析
装置を用いて測定）になるまで粉砕した後、これを乾操
させ焼結前の原料微粉末を得た。Example 3: Chemically high purity as starting material
PbO, TiO2, ZrO2, ZnO, Nb2OFive，
MnO2, CdO were prepared. 0.17P of each of these powders
b (Zn1/3Nb 2/3) O3-0.39 PbTiO3-0.44Pb
ZrO3(However, the coefficient is the mole fraction), 0.5 mass% M
nO2A porcelain material having a composition containing +1.0 mass% CdO is obtained.
And add methanol in a ball mill.
And wet pulverize for 2 hours at 700-900 ℃
Baked After that, coexist with a zirconia ball with a diameter of 5 mm.
Add an organic dispersant and methanol to
Is 0.7 μm or less (laser diffraction particle size analysis manufactured by Shimadzu Corporation
Crushed to dryness)
Then, raw material fine powder before sintering was obtained.
【００２４】これを実施例１と同様に焼結して円さいｓ
板状試料を形成し、電極を付与して比誘電率（εｒ）、
電気機械結合係数（ｋｒ）及び機械的品質係数（Ｑｍ）
を求めた。これらの結果を表３に示す。This was sintered in the same manner as in Example 1 to form a cone
A plate-shaped sample is formed, an electrode is attached, and a relative dielectric constant (εr),
Electromechanical coupling coefficient (kr) and mechanical quality coefficient (Qm)
I asked. The results are shown in Table 3.
【００２５】[0025]
【表３】 [Table 3]
【００２６】表３に示す通り、使用する粉末の平均粒子
径が0.8μｍ以上である試料番号２２，２３と比較する
と、使用する粉末の平均粒子径が0.7μｍ以下である試
料番号２４〜２６のほうが電気機械結合係数（ｋｒ）の
値が大きくなり、圧電特性が向上している。As shown in Table 3, as compared with Sample Nos. 22 and 23 in which the powder used has an average particle size of 0.8 μm or more, Sample Nos. 24 to 26 in which the powder used has an average particle size of 0.7 μm or less. The larger the value of the electromechanical coupling coefficient (kr), the better the piezoelectric characteristics.
【００２７】以上の例では、0.17Ｐｂ（Ｚｎ1/3Ｎ
ｂ2/3）Ｏ3−0.39ＰｂＴｉＯ3−0.44ＰｂＺｒＯ3を主成
分とする系について本発明の効果を示したが、Ｐｂ，Ｚ
ｒ，Ｔｉ，Ｚｎ及びＮｂを含みペロブスカイト構造を有
する他の複合酸化物を主成分とする圧電体磁器組成物に
おいても同様の効果を得ることが期待できる。In the above example, 0.17 Pb (Zn 1/3 N
b 2/3 ) O 3 −0.39PbTiO 3 −0.44PbZrO 3 The effect of the present invention was shown for the system as a main component.
The same effect can be expected to be obtained in a piezoelectric ceramic composition containing r, Ti, Zn, and Nb as a main component, which is another complex oxide having a perovskite structure.
【００２８】[0028]
【発明の効果】以上のように、Ｐｂ，Ｚｒ，Ｔｉ，Ｚｎ
及びＮｂの各元素を含むペロブスカイト構造を有する複
合酸化物を主成分としＭｎ元素を副成分として含む圧電
体磁器組成物に、Ｃｄ元素を含有させることにより、９
００℃程度の低温で焼成しても圧電特性の劣化が抑えら
れた圧電体磁器組成物を得ることができる。上記組成物
において、一般式ＡＢＯ3で表される複合酸化物のＡサ
イトに入る化学量論量のＰｂ量を超えて過剰のＰｂを含
ませることにより、更に、圧電特性に優れて低温焼結が
可能な圧電体磁器組成物を得ることができる。さらに、
上記組成物において、焼結前の平均粒子径を0.7μｍ以
下にすることにより、より一層、圧電特性を改善させる
ことができる。従って、本発明の圧電体磁器組成物を用
いることにより、比較的安価なＡｇもしくはＡｇリッチ
なＡｇ−Ｐｔを内部電極とした、圧電特性に優れた、積
層高調波共振子、積層高調波フィルタ、積層圧電トラン
ス、アクチュエータ等の積層型の圧電体デバイスを得る
ことができる。As described above, Pb, Zr, Ti, Zn
By incorporating a Cd element into a piezoelectric ceramic composition containing a complex oxide having a perovskite structure containing each element of Nb and Nb as a main component and an Mn element as an accessory component, 9
It is possible to obtain a piezoelectric ceramic composition in which the deterioration of piezoelectric characteristics is suppressed even when fired at a low temperature of about 00 ° C. In the above composition, by containing an excessive amount of Pb in excess of the stoichiometric amount of Pb contained in the A site of the complex oxide represented by the general formula ABO 3 , the piezoelectric property is further improved, and low temperature sintering is achieved. It is possible to obtain a piezoelectric ceramic composition capable of further,
In the above composition, when the average particle size before sintering is 0.7 μm or less, the piezoelectric characteristics can be further improved. Therefore, by using the piezoelectric ceramic composition of the present invention, a laminated harmonic resonator, a laminated harmonic filter, which has excellent piezoelectric characteristics, using relatively inexpensive Ag or Ag-rich Ag-Pt as an internal electrode, A laminated piezoelectric device such as a laminated piezoelectric transformer or an actuator can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤本 久和 石川県松任市相木町383番地 ニッコー株 式会社内 (72)発明者 水島 清 石川県松任市相木町383番地 ニッコー株 式会社内 Ｆターム(参考） 4G031 AA11 AA12 AA14 AA19 AA24 AA26 AA32 BA10 CA01 GA03 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hisakazu Fujimoto Nikko Co., Ltd. 383 Aikicho, Matsuto City, Ishikawa Prefecture Inside the company (72) Inventor Kiyoshi Mizushima Nikko Co., Ltd. 383 Aikicho, Matsuto City, Ishikawa Prefecture Inside the company F-term (reference) 4G031 AA11 AA12 AA14 AA19 AA24 AA26 AA32 BA10 CA01 GA03
Claims (5)
Ｚｎの５種の金属元素を含むペロブスカイト構造を有す
る複合酸化物を主成分とし、副成分としてＭｎ元素を含
む圧電体磁器組成物において、Ｃｄ元素を含有すること
を特徴とする圧電体磁器組成物。1. A piezoelectric ceramic composition containing, as a main component, a complex oxide having a perovskite structure containing at least five metal elements of Pb, Zr, Ti, Nb, and Zn, and containing a Mn element as a subcomponent, Cd A piezoelectric ceramic composition characterized by containing an element.
を含有する請求項１に記載の圧電体磁器組成物。2. 0.3 to 1.5% by mass of Cd converted to CdO
The piezoelectric ceramic composition according to claim 1, which comprises:
Ｍｎを含有する請求項１または２に記載の圧電体磁器組
成物。3. The piezoelectric ceramic composition according to claim 1, which contains 0.05 to 0.75 mass% of Mn in terms of MnO 2 .
Ｂはペロブスカイト構造を構成する金属元素）で表した
とき、化学量論的に該複合酸化物のＡサイトに含まれる
べき値を超える量のＰｂ元素を含むことを特徴とする請
求項１〜３のいずれかに記載の圧電体磁器組成物。4. The composite oxide is represented by the general formula ABO 3 (A,
B is a metal element forming a perovskite structure), and contains a Pb element in an amount stoichiometrically exceeding the value to be contained in the A site of the composite oxide. 2. A piezoelectric ceramic composition according to any one of 1.
粒子径が0.7μｍ以下である微粉末を用いる請求項１〜
４のうちいずれかに記載の圧電体磁器組成物。5. A fine powder having an average particle diameter of 0.7 μm or less is used as the raw material powder containing the metal element.
4. The piezoelectric ceramic composition according to any one of 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001199031A JP2003012369A (en) | 2001-06-29 | 2001-06-29 | Piezoelectric compact of ceramic composition |
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|---|---|
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ID=19036377
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323073B2 (en) * | 2002-06-05 | 2008-01-29 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric porcelain composition, laminated piezoelectric device therefrom and process for producing the same |
| CN100385697C (en) * | 2003-01-24 | 2008-04-30 | 中国科学院上海硅酸盐研究所 | Piezoelectric multiplayer micro displacement parts and its creation method |
| KR100846052B1 (en) | 2006-06-26 | 2008-07-11 | 재단법인서울대학교산학협력재단 | Multilayer Type 2-2 Piezo-Composite Ultrasonic Transducer and Method for the same |
| WO2023067986A1 (en) * | 2021-10-18 | 2023-04-27 | 太陽誘電株式会社 | Piezoelectric element, and ultrasonic vibrator and ultrasonic motor comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323073B2 (en) * | 2002-06-05 | 2008-01-29 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric porcelain composition, laminated piezoelectric device therefrom and process for producing the same |
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| WO2023067986A1 (en) * | 2021-10-18 | 2023-04-27 | 太陽誘電株式会社 | Piezoelectric element, and ultrasonic vibrator and ultrasonic motor comprising same |
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