JP3802611B2 - Piezoelectric material - Google Patents
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- JP3802611B2 JP3802611B2 JP18545496A JP18545496A JP3802611B2 JP 3802611 B2 JP3802611 B2 JP 3802611B2 JP 18545496 A JP18545496 A JP 18545496A JP 18545496 A JP18545496 A JP 18545496A JP 3802611 B2 JP3802611 B2 JP 3802611B2
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- 239000000463 material Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 15
- 229910010293 ceramic material Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、例えば、各種超音波振動子、セラミックフィルター、圧電発音体、圧電アクチュエーター等の圧電磁器製造物に利用される圧電磁器材料に関する。
【０００２】
【従来の技術】
近年、圧電磁器材料としては、ＰｂＴｉＯ3やＰｂＺｒＯ3を主成分として含む圧電セラミック（以下、ＰＺＴ系圧電セラミックと略する）が汎用的に用いられている。一般に、この種の圧電セラミックでは、その製造に要する焼結温度が、二成分系では約１２６０℃であり、さらに特性改善のために、複合ペロブスカイト類を第三、第四成分として固溶させた多成分ＰＺＴ系圧電セラミックでは、焼結温度が多少低下して、１２００℃近辺となっている。
【０００３】
【発明が解決しようとする課題】
ところで、ＰＺＴ系圧電セラミックの焼結過程において、ＰｂＯの蒸発が１０００℃近辺から急激に増加することが知られている。従って、上記の焼結温度領域では、多量のＰｂＯの蒸発が起こるという問題がある。ＰｂＯが蒸発すると、焼結体の組成ずれを引き起こし、特性のばらつきや劣化を招く上、蒸発したＰｂ成分は環境汚染の原因となる可能性がある。
【０００４】
そこで、ＰｂＯの蒸発を制御することは、ＰＺＴ系圧電セラミックの製造上、非常に有用なこととなっており、このためには、焼結温度を１０００℃以下にすることが望ましい。焼結温度の低下は、省エネルギーの点でも有益である。更に、一体焼成で製造される積層型圧電素子の場合、焼結温度が低下できれば内部電極の構成においてパラジウムを減らし、銀の比率を増大させることが可能であり、製造コスト面で有利になると期待される。このように、圧電磁器材料の焼結温度を低下させることは、製造コスト面で長所を奏する他、省エネルギーを具現化する点でも有益である。
【０００５】
上述した従来のＰＺＴ系圧電セラミックに用いる圧電磁器材料の場合、一般に、焼成温度が通常１２００℃以上であるため、ＰｂＯの蒸発を回避したり、あるいは製造コストを低減化させることが 困難になっている。
【０００６】
本発明は、このような問題点を解決すべくなされたもので、その技術的課題 は、ＰｂＯの蒸発を回避できる低温（１０００℃以下）で焼成可能であるとともに、製造コストを低減化しうる圧電磁器材料を提供することにある。
【０００７】
【課題を解決するための手段】
本発明によれば、組成をａＰｂＴｉＯ3＋ｂＰｂＺｒＯ3＋ｃＰｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3＋ｄＰｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3＋ｅＣｏＯ＋ｆＰｂＯで表わした時に、このうち主成分に相当するａＰｂＴｉＯ3＋ｂＰｂＺｒＯ3＋ｃＰｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3＋ｄＰｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3の比が、ａ＝２２〜５０ｍｏｌ％、ｂ＝１８〜５５ｍｏl％、ｃ＝２〜４０ｍｏｌ％、ｄ＝０〜５４ｍｏｌ％（ただし、ｄ＝０を除く、またａ＋ｂ＋ｃ＋ｄ＝１００）であり、副成分に相当するｅＣｏＯ＋ｆＰｂＯが、前記主成分の重量に対してｅ＝０.１〜２.５ｗｔ％、ｆ＝０〜８ｗｔ％である圧電磁器材料が得られる。
【０００８】
【実施例】
以下に、実施例を挙げ、本発明の圧電磁器材料について、図面を参照して詳細に説明する。
【０００９】
最初に、本発明の圧電磁器材料の概要、並びにその具現に至る背景を簡単に説明する。この圧電磁器材料は、組成がａＰｂＴｉＯ3＋ｂＰｂＺｒＯ3＋ｃＰｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3＋ｄＰｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3＋ｅＣｏＯ＋ｆＰｂＯで表されるとともに、ａ＝２２〜５０ｍｏｌ％、ｂ＝１８〜５５ｍｏl％、ｃ＝２〜４０ｍｏｌ％、ｄ＝０〜５４ｍｏｌ％ （ただし、ａ＋ｂ＋ｃ＋ｄ＝１００）である主成分と、この主成分重量（主成分を重量で１００％としたとき）に対して、ｅ＝０.１〜２.５ｗｔ％、ｆ＝０〜８ｗｔ％である副成分とを含むものである。このような組成により、ＰｂＯの蒸発を回避可能な低温（１０００℃以下）で焼成可能となる。
【００１０】
一般に、ＰｂＴｉＯ3及びＰｂＺｒＯ3の固溶体に、ＡサイトにＰｂを有する複合ペロブスカイト類を第三成分として固溶させる場合、この比率が多いほど焼結温度は低下する。しかしながら、これらの含有率が高くなるに従って、強誘電性を有する組成範囲では、キュリー温度が低下することが多い。
【００１１】
多成分のＰＺＴ系圧電セラミックは、ＰｂＴｉＯ3−ＰｂＺｒＯ3に複合ペロブスカイト類を一種もしくは複数種固溶させることにより、二成分系では得られなかった誘電特性、圧電特性の改善がなされて、実用に供されている。又、ＰｂＴｉＯ3 −ＰｂＺｒO3−Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3系圧電セラミックは、Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3を固溶させることで、数百〜数千の機械的品質係数、及び高い誘電特性、圧電特性が得られているが、実用的な組成範囲は、Ｐｂ（Ｍｎ1/3Nb2/3）Ｏ3の比率が４０ｍｏｌ％以下となる。これは、この値を越えると、キュリー温度が２００℃以下となり、誘電特性及び圧電特性における温度安定性が低下するためである。
【００１２】
本発明では、ＰｂＴｉＯ3−ＰｂＺｒＯ3−Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3系に、さらに第四の複合ペロブスカイト類として、強誘電性であるＰｂ（Ｃｏ１/3Ｎｂ2/3）Ｏ3を固溶させることで、比較的機械的品質係数が高く、かつ１０００℃以下の低温で焼結できる組成を見い出している。
【００１３】
しかしながら、ＰｂＴｉＯ3−ＰｂＺｒＯ3−Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3−Ｐｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3の組成のみでは、焼結体に巨大ボイドが生じ易く、実用面で問題があることが明らかとなった。
そこで、一定量のＣｏＯを添加することで、巨大ボイドの発生が著しく抑制され、実用的な誘電圧電特性を有する組成となることが判明した。又、ＣｏＯは、Ｐｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3の存在しない条件下でも、単独で焼結温度の低下を可能にすることが明らかとなった。さらに、ＣｏＯに加えてＰｂＯを添加すると、焼結温度を一層低下させ得ることが確認された。
【００１４】
以下は、本発明の圧電磁器材料をその製造工程を含めて具体的な実施例（比較例を含む）に基づいて説明する。
【００１５】
最初に、主成分及び副成分の原料として、ＰｂＯ、ＴｉＯ2、ＺｒＯ2、ＭｎＣＯ3、Ｎｂ2Ｏ5、ＣｏＯをそれぞれ表１に示す各試料の組成となるように調整し、これらの原料紛をジルコニアボールとともにアクリルポット中に入れ、２０時間湿式混合した。
【００１６】
【表１】
次に、これらの混合粉を脱水乾燥後、アルミナこう鉢中で８００℃の条件下で２時間予焼を行ってから、各予焼粉をアクリルポット中ジルコニアボールにて１５時間湿式粉砕した。
【００１８】
引き続き、蒸発乾燥して得られた予焼粉砕粉にバインダを混合して加圧し、 φ１５×３ｍｍ厚に成形した。この成形体を７５０〜１０５０℃で２時間焼成し、各焼結体を１ｍｍの厚さに加工した後、両面に銀ペーストを塗布して４５０℃で焼き付けて電極を形成することにより、表１に示すような、それぞれ組成の異なる試料とした。
【００１９】
そこで、このようにして得られた各試料を１００℃、４ｋＶ／ｍｍ、１５分で分極処理をし、比誘電率εｒ、電気機械結合係数Ｋｐ、機械的品質係数Ｑｍを測定した。測定結果は、各試料の組成と共に表１に示す。なお、表１において、Ｔ.Ｓ.は、焼結温度を表し、焼結体密度ρが７.５ｇ／ｃｍ3以上となるのに必要な最低の焼結温度を用いた。図１に、代表的な４つの試料の焼結温度と焼結体密度の関係について代表的な例を示す。又、Ｔｃはキュリー温度である。
【００２０】
本発明において、圧電磁器材料に関してその組成範囲を限定する理由として、εｒ＜４００、Ｋｐ＜２５、Ｑｍ＜５００、Ｔｃ＜２００℃の場合、実用性に乏しいため、本発明から除外する必要がある。従って、表１の結果より、
▲１▼ＰｂＴｉＯ3量ａが２２ｍｏｌ％未満では、Ｔｃが低い値となるため、好ましくない（試料Ｎｏ.１１参照）。又、５０ｍｏｌ％を越えると、Ｋｐが低い値となるため、好ましくない（試料Ｎｏ.１４参照）。
▲２▼ＰｂＺｒＯ3量ｂが１８ｍｏｌ％未満では、Ｋｐが低下するため、好ましくない（試料Ｎｏ.７参照）。又、５５ｍｏｌ％を越えると、εｒが低い値となるため、好ましくない（試料Ｎｏ.１０参照）。
▲３▼Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3量ｃが２ｍｏｌ％未満では、Ｑｍが低下するため、好ましくない（試料Ｎｏ.１参照）。又、４０ｍｏｌ％を越えると、Ｋｐ、Ｔｃが低い値となるため、好ましくない（試料Ｎｏ.４参照）。
▲４▼Ｐｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3量ｄが５４ｍｏｌ％を越えると、Ｔｃが低い値となるため、好ましくない（試料Ｎｏ.６参照）。
▲５▼ＣｏＯ量ｅが主成分全重量に対して０.１ｗｔ％未満では、焼結体に巨大ボ イドが生じて組織が不均質となるため、好ましくない（試料Ｎｏ.１５参照）。又、２.５ｗｔ％を越えても、同様に組織が不均質となるため、やはり好ましくない（試料Ｎｏ.１８参照）。
▲６▼ＰｂＯ量ｆが８ｗｔ％を越えると、巨大ボイドが生じるため好ましくない（試料Ｎｏ.２１参照）。
【００２１】
上記の理由により、本発明の求める特性を有し、かつ、低温で焼結が可能な圧電磁器材料として、ａＰｂＴｉＯ3＋ｂＰｂＺｒＯ3＋ｃＰｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3 ＋ｄＰｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3 ＋ｅＣｏＯ＋ｆＰｂＯの組成において、ａが２２〜５５ｍｏｌ％、ｂ＝１８〜５５ｍｏl％、ｃ＝２〜４０ｍｏｌ％、ｄ＝０〜５４ｍｏｌ％（ただし、ａ＋ｂ＋ｃ＋ｄ＝１００）の範囲からなる主成分に、副成分として、主成分重量に対してｅを０.１〜２.５ｗｔ％、ｆを０〜８ｗｔ％の範囲で添加された材料に限定した。
【００２２】
【発明の効果】
以上に述べた通り、本発明によれば、主成分及び副成分としてのＰｂＴｉＯ3、ＰｂＺｒＯ3、Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ3、Ｐｂ（Ｃｏ1/3Ｎｂ2/3）Ｏ3、ＣｏＯ、ＰｂＯを所定範囲で用いることにより、ＰｂＯの蒸発を回避できる１０００℃以下の低温で焼成可能とし、εｒ４００以上、Ｋｐ２５以上、Ｑｍ５００以上、Ｔｃ２００℃以上の優れた特性を有する圧電磁器材料を少ないエネルギーで安価に製造することが可能となり、工業的に有益となる。
【図面の簡単な説明】
【図１】本発明の実施例における代表的な試料の焼結温度と焼結密度の関係を示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a piezoelectric ceramic material used for piezoelectric ceramic products such as various ultrasonic vibrators, ceramic filters, piezoelectric sounding bodies, piezoelectric actuators, and the like.
[0002]
[Prior art]
In recent years, piezoelectric ceramics containing PbTiO 3 or PbZrO 3 as main components (hereinafter abbreviated as PZT piezoelectric ceramics) have been widely used as piezoelectric ceramic materials. Generally, in this type of piezoelectric ceramic, the sintering temperature required for its production is about 1260 ° C. in a two-component system, and composite perovskites are dissolved as third and fourth components for further improvement of characteristics. In the multi-component PZT-based piezoelectric ceramic, the sintering temperature is somewhat lowered and is around 1200 ° C.
[0003]
[Problems to be solved by the invention]
Incidentally, it is known that the evaporation of PbO increases rapidly from around 1000 ° C. during the sintering process of the PZT-based piezoelectric ceramic. Therefore, there is a problem that a large amount of PbO evaporates in the above sintering temperature region. When PbO evaporates, it causes a composition shift of the sintered body, leading to variations in characteristics and deterioration, and the evaporated Pb component may cause environmental pollution.
[0004]
Therefore, controlling the evaporation of PbO is very useful in the production of PZT-based piezoelectric ceramics. For this purpose, it is desirable to set the sintering temperature to 1000 ° C. or lower. Lowering the sintering temperature is also beneficial in terms of energy saving. Furthermore, in the case of a laminated piezoelectric element manufactured by integral firing, if the sintering temperature can be lowered, it is possible to reduce palladium in the internal electrode configuration and increase the silver ratio, which is expected to be advantageous in terms of manufacturing cost. Is done. Thus, lowering the sintering temperature of the piezoelectric ceramic material is advantageous in terms of realizing energy saving as well as having advantages in terms of manufacturing cost.
[0005]
In the case of the piezoelectric ceramic material used for the above-described conventional PZT-based piezoelectric ceramic, since the firing temperature is generally 1200 ° C. or higher, it is difficult to avoid evaporation of PbO or reduce the manufacturing cost. Yes.
[0006]
The present invention has been made to solve such problems, and its technical problem is that it can be fired at a low temperature (1000 ° C. or less) that can avoid evaporation of PbO, and can reduce the manufacturing cost. It is to provide a porcelain material.
[0007]
[Means for Solving the Problems]
According to the present invention, when the composition is expressed by aPbTiO 3 + bPbZrO 3 + cPb (Mn 1/3 Nb 2/3 ) O 3 + dPb (Co 1/3 Nb 2/3 ) O 3 + eCoO + fPbO, this corresponds to the main component. The ratio of aPbTiO 3 + bPbZrO 3 + cPb (Mn 1/3 Nb 2/3 ) O 3 + dPb (Co 1/3 Nb 2/3 ) O 3 is such that a = 22-50 mol%, b = 18-55 mol%, c = 2-40 mol%, d = 0-54 mol% (where d = 0 is excluded and a + b + c + d = 100), and eCoO + fPbO corresponding to the subcomponent is e = 0.1 with respect to the weight of the main component. A piezoelectric ceramic material with ~ 2.5 wt% and f = 0-8 wt% is obtained.
[0008]
【Example】
Hereinafter, examples will be given and the piezoelectric ceramic material of the present invention will be described in detail with reference to the drawings.
[0009]
First, the outline of the piezoelectric ceramic material of the present invention and the background leading to its implementation will be briefly described. This piezoelectric ceramic material has a composition represented by aPbTiO 3 + bPbZrO 3 + cPb (Mn 1/3 Nb 2/3 ) O 3 + dPb (Co 1/3 Nb 2/3 ) O 3 + eCoO + fPbO, and a = 22 to 50 mol %, B = 18 to 55 mol%, c = 2 to 40 mol%, d = 0 to 54 mol% (provided that a + b + c + d = 100) and the main component weight (when the main component is 100% by weight) ) And subcomponents with e = 0.1 to 2.5 wt% and f = 0 to 8 wt%. With such a composition, it becomes possible to perform firing at a low temperature (1000 ° C. or lower) that can avoid evaporation of PbO.
[0010]
In general, when a composite perovskite having Pb at the A site is dissolved as a third component in a solid solution of PbTiO 3 and PbZrO 3 , the higher the ratio, the lower the sintering temperature. However, as their content increases, the Curie temperature often decreases in a composition range having ferroelectricity.
[0011]
Multi-component PZT-based piezoelectric ceramics have been improved by improving the dielectric and piezoelectric properties that could not be obtained with two-component systems by dissolving one or more composite perovskites in PbTiO 3 -PbZrO 3. It is provided. In addition, PbTiO 3 —PbZrO 3 —Pb (Mn 1/3 Nb 2/3 ) O 3 piezoelectric ceramics can be made from several hundred to several by dissolving Pb (Mn 1/3 Nb 2/3 ) O 3. A mechanical quality factor of 1,000, high dielectric properties, and piezoelectric properties have been obtained, but the practical composition range is such that the ratio of Pb (Mn 1/3 Nb 2/3 ) O 3 is 40 mol% or less. This is because if this value is exceeded, the Curie temperature becomes 200 ° C. or lower, and the temperature stability in the dielectric characteristics and the piezoelectric characteristics decreases.
[0012]
In the present invention, PbTiO 3 -PbZrO 3 -Pb (Mn 1/3 Nb 2/3) O 3 system, further as a fourth complex perovskite compound is a ferroelectric Pb (
[0013]
However, with only the composition of PbTiO 3 —PbZrO 3 —Pb (Mn 1/3 Nb 2/3 ) O 3 —Pb (Co 1/3 Nb 2/3 ) O 3 , giant voids are likely to occur in the sintered body, It became clear that there was a problem in practical use.
Thus, it has been found that by adding a certain amount of CoO, the generation of giant voids is remarkably suppressed and the composition has practical dielectric piezoelectric characteristics. It has also been clarified that CoO alone can lower the sintering temperature even in the absence of Pb (Co 1/3 Nb 2/3 ) O 3 . Furthermore, it was confirmed that the sintering temperature can be further reduced by adding PbO in addition to CoO.
[0014]
Hereinafter, the piezoelectric ceramic material of the present invention will be described based on specific examples (including comparative examples) including the manufacturing process.
[0015]
First, PbO, TiO 2 , ZrO 2 , MnCO 3 , Nb 2 O 5 , and CoO were adjusted as the raw materials of the main component and the subcomponent so as to have the compositions of the respective samples shown in Table 1, and these raw material powders were adjusted. Was placed in an acrylic pot together with zirconia balls and wet mixed for 20 hours.
[0016]
[Table 1]
Next, these mixed powders were dehydrated and dried, and then pre-fired in an alumina pot for 2 hours at 800 ° C., and then each pre-fired powder was wet-ground with zirconia balls in an acrylic pot for 15 hours.
[0018]
Subsequently, the pre-fired pulverized powder obtained by evaporation and drying was mixed with a binder and pressed to form a φ15 × 3 mm thickness. This molded body was fired at 750 to 1050 ° C. for 2 hours, and each sintered body was processed to a thickness of 1 mm. Then, a silver paste was applied on both sides and baked at 450 ° C. to form electrodes. Samples having different compositions as shown in FIG.
[0019]
Therefore, each sample thus obtained was subjected to polarization treatment at 100 ° C. and 4 kV / mm for 15 minutes, and the relative dielectric constant εr, electromechanical coupling coefficient Kp, and mechanical quality coefficient Qm were measured. The measurement results are shown in Table 1 together with the composition of each sample. In Table 1, TS represents a sintering temperature, and the lowest sintering temperature necessary for the sintered body density ρ to be 7.5 g / cm 3 or more was used. FIG. 1 shows a typical example of the relationship between the sintering temperature and sintered body density of four typical samples. Tc is the Curie temperature.
[0020]
In the present invention, the reason why the composition range of the piezoelectric ceramic material is limited is that when εr <400, Kp <25, Qm <500, and Tc <200 ° C., since the practicality is poor, it is necessary to exclude from the present invention. . Therefore, from the results in Table 1,
{Circle around (1)} If the PbTiO 3 amount a is less than 22 mol%, Tc becomes a low value, which is not preferable (see Sample No. 11). On the other hand, if it exceeds 50 mol%, Kp becomes a low value, which is not preferable (see Sample No. 14).
{Circle around (2)} If the amount b of PbZrO 3 is less than 18 mol%, Kp decreases, which is not preferable (see sample No. 7). On the other hand, if it exceeds 55 mol%, εr becomes a low value, which is not preferable (see Sample No. 10).
{Circle around (3)} When the amount c of Pb (Mn 1/3 Nb 2/3 ) O 3 is less than 2 mol%, Qm decreases, which is not preferable (see sample No. 1). On the other hand, if it exceeds 40 mol%, Kp and Tc are low, which is not preferable (see Sample No. 4).
{Circle around (4)} When the amount of Pb (Co 1/3 Nb 2/3 ) O 3 exceeds 54 mol%, Tc becomes a low value, which is not preferable (see sample No. 6).
(5) If the amount of CoO e is less than 0.1 wt% with respect to the total weight of the main component, huge voids are formed in the sintered body and the structure becomes inhomogeneous (see Sample No. 15). Moreover, even if it exceeds 2.5 wt%, the structure is similarly inhomogeneous, which is also not preferable (see Sample No. 18).
{Circle around (6)} If the PbO amount f exceeds 8 wt%, huge voids are generated (see Sample No. 21).
[0021]
For the above reasons, as a piezoelectric ceramic material having the characteristics required by the present invention and capable of being sintered at a low temperature, aPbTiO 3 + bPbZrO 3 + cPb (Mn 1/3 Nb 2/3 ) O 3 + dPb (Co 1 / 3 Nb 2/3 ) In the composition of O 3 + eCoO + fPbO, a is in the range of 22-55 mol%, b = 18-55 mol%, c = 2-40 mol%, d = 0-54 mol% (however, a + b + c + d = 100) The main component is limited to a material added as a subcomponent in the range of 0.1 to 2.5 wt% e and 0 to 8 wt% with respect to the main component weight.
[0022]
【The invention's effect】
As described above, according to the present invention, PbTiO 3 , PbZrO 3 , Pb (Mn 1/3 Nb 2/3 ) O 3 , Pb (Co 1/3 Nb 2/3 ) as main components and subcomponents are used. By using O 3 , CoO, and PbO within a predetermined range, a piezoelectric ceramic that can be fired at a low temperature of 1000 ° C. or less that can avoid evaporation of PbO, and has excellent characteristics of εr 400 or more, Kp 25 or more, Qm 500 or more, Tc 200 ° C. or more. It becomes possible to manufacture the material at low cost with less energy, which is industrially beneficial.
[Brief description of the drawings]
FIG. 1 is a graph showing a relationship between a sintering temperature and a sintering density of a representative sample in an example of the present invention.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
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| JP18545496A JP3802611B2 (en) | 1996-06-25 | 1996-06-25 | Piezoelectric material |
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| JP18545496A JP3802611B2 (en) | 1996-06-25 | 1996-06-25 | Piezoelectric material |
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| JP3802611B2 true JP3802611B2 (en) | 2006-07-26 |
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| AU2003241724A1 (en) | 2002-06-05 | 2003-12-22 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric porcelain composition, laminated piezoelectric device therefrom and process for producing the same |
| KR20040049383A (en) * | 2002-12-05 | 2004-06-12 | 주식회사 스마텍 | A piezo ceramic composition |
| JP2005154238A (en) | 2003-11-28 | 2005-06-16 | Matsushita Electric Ind Co Ltd | Manufacturing method of piezoelectric porcelain composition |
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