WO2009113535A1 - 非鉛系圧電材料 - Google Patents
非鉛系圧電材料 Download PDFInfo
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Definitions
- the present invention relates to a lead-free piezoelectric material that does not contain harmful elements such as Pb.
- Piezoelectric materials have the effect of expanding and contracting (electrostrictive effect) when a voltage is applied, and generating a voltage (piezoelectric effect) when a force is applied, so a very important substance that carries the conversion between mechanical energy and electrical energy.
- These materials are widely applied in the field of energy conversion, such as actuators and sensors, and have penetrated from state-of-the-art technology to daily life, making them indispensable for modern society.
- PZT Pb (Ti, Zr) O 3 polycrystal
- This material system has the best piezoelectric properties so far (the highest value of the piezoelectric coefficient d 33 of undoped PZT is about 220 pC / N, and the improved soft PZT by addition is about 400-580 pC / N), Since half a century, it has become a “pronoun” for piezoelectric materials. However, since PZT contains a large amount of toxic lead, it has been severely regulated in recent years from the viewpoint of environmental problems. Therefore, the development of high performance lead-free piezoelectric materials comparable to PZT has become a pressing issue worldwide.
- the present invention has an object to provide a lead-free piezoelectric material that can have a high piezoelectric coefficient (d 33 > 500 pC / N) that surpasses that of soft PZT.
- Invention 1 is a lead-free piezoelectric material that does not contain harmful elements such as Pb, and ⁇ [(Ba 1-x1 M1 x1 ) ((Ti 1-x Zr x ) 1-y1 N1 y1 ) O 3 ] ⁇ ⁇ % [(Ba 1 ⁇ y Ca y ) 1 ⁇ x2 M2 x2 ) (Ti 1 ⁇ y2 N2 y2 ) O 3 ] ⁇ (M1, N1, M2, N2 are additive elements) pseudo binary solid solution (abbreviated as BZT) ⁇ % BCT).
- BZT pseudo binary solid solution
- Invention 2 is the lead-free piezoelectric material of Invention 1, wherein the quasi-binary solid solution has a crystal phase boundary (MPB).
- MPB crystal phase boundary
- BZT- ⁇ % BCT has a morphotropic phase boundary (MPB)
- FIG. 1 shows [Ba (Ti 0.8 Zr 0.2 ) O 3 ] ⁇ %
- Example of (Ba 0.7 Ca 0.3 ) TiO 3 it was found that the composition near MPB has very high piezoelectric properties (d 33 > 580 pC / N) that surpass PZT (FIG. 2, FIG. 2). 3).
- a material using the pseudo binary solid solution having the MPB is invented.
- the two terminal compositions used in the present invention are Ba (Ti 1-x Zr x ) O 3 having a rhomboboral (R) structure and (Ba 1-y Ca y ) TiO 3 having a tetragonal (T) structure.
- R rhomboboral
- Ba 1-y Ca y TiO 3 having a tetragonal
- the present invention includes a quasi-binary lead-free piezoelectric material shown in the following examples that is partially substituted with an element having the same valence as the composition ion. Therefore, in the present invention, ⁇ [(Ba 1 ⁇ x1 M1 x1 ) ((Ti 1 ⁇ x Zr x ) 1 ⁇ y1 N1 y1 ) O 3 ] ⁇ % [(Ba 1 ⁇ y Ca y ) 1 ⁇ x2 M2 x2) (Ti 1-y2 N2 y2) O 3] ⁇ (M1, N1, M2, N2 showed additive element) and.
- BZT-BCT has an A 2+ B 4+ O 3 type perovskite structure
- Ba 2+ and Ca 2+ occupy the A 2+ site
- Ti 4+ and Zr 4+ occupy the B 4+ site.
- “An element having the same valence as the composition ion” means a 2 + -valent element (for example, Sr 2+ ) in the case of an element that substitutes for an A 2+ site, and a 4 + -valent element (for example, Hf in the case of an element that substitutes for a B 4+ site). 4+ , Sn 4+ ).
- the “equivalent additive element” can be created by a combination of elements having different valences (for example, by replacing A 2+ sites with 1 / 2Bi 3+ 1 ⁇ 2Na + (average valence is 2+). Good).
- Acceptor additive element Additive elements (M1, M2) having a valence of +2 or less substituted at the position of A 2+ : Additive elements of +4 valence or less substituted at the position of B 4+ such as K + , Na + , Li + , Ag + N2): Mn 3+ , Fe 3+ , Co 3+ , Ni 2+ , Cu 2+ and the like.
- Acceptor element addition is an improved method often used to reduce the loss of the piezoelectric material. Also in the present invention, an improved material by “Addition of acceptor element” using BZT-BCT is within the scope of the present invention.
- Donor additive elements +2 or more valence of the additive element to be replaced to the position of A 2+: La 3+, Bi 3+ , Y 3+, Ce 3+, +4 valence or more additive elements substituting the position of the Rh 3+, etc.
- B 4+ Nb 5+, Ta 5+
- Donor element addition is an improved method often used to improve the piezoelectric characteristics of piezoelectric materials. Also in the present invention, an improved material by “adding a donor element” while using BZT-BCT is within the scope of the present invention.
- a material of the above-mentioned material formed into a known shape such as a polycrystal, a single crystal, a thin film, or a multilayer film is also within the scope of the present invention. Furthermore, the use of these in composite materials, parts, apparatuses, devices, etc. is in a category that can be easily recalled from conventionally known techniques.
- phase diagram of the [Ba (Ti 0.8 Zr 0.2 ) O 3 ] - ⁇ % [(Ba 0.7 Ca 0.3 ) TiO 3 ] pseudo binary system is shown in FIG.
- Sample preparation method Raw material: BaZrO 3 (99.9%), CaCO 3 (99.9%) BaCO 3 (99.9%) and TiO 2 (99.9%) How to make: Standard solid phase sintering. Synthesis is 1350 ° C. for 2 hours, sintering is 1450 ° C. for 3 hours. (The synthesis temperature is 1200 °C -1400 °C and the sintering temperature is 1300 °C -1500 °C) Electrode: Ag electrode Polarization condition: The sample is slowly cooled to room temperature while applying an electric field about twice as large as the coercive field at a temperature equal to or higher than the Curie temperature (110 ° C.).
- piezoelectric coefficient d 33 is measured according to ZJ-6B type d 33 meter. Electric field-Displacement measurements were taken with Radiant Technologies' Workstation and MTI2000 optical displacement sensor.
- FIG. 2 is based on measured values (Table 1) showing the relationship (room temperature) between the piezoelectric coefficient d 33 and the composition ⁇ %.
- Table 1 shows the relationship (room temperature) between the piezoelectric coefficient d 33 and the composition ⁇ %.
- FIG. 2 shows that the piezoelectric coefficient is large in the vicinity of the MPB.
- the present invention proposes a lead-free piezoelectric material using this MPB.
- the lead-free piezoelectric material of the present invention has not only two to several times more piezoelectric properties than other lead-free piezoelectric materials, but also has piezoelectric properties that surpass most PZT. ing. This figure well represents the inventiveness of the present invention.
- the electric field-displacement relationship represents the piezoelectric characteristics under a large electric field. From this figure, it can be seen that the piezoelectric characteristics of the lead-free piezoelectric material of the present invention under a large electric field greatly exceed all PZT.
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Abstract
Description
50年間の間、殆どの圧電応用はPZT(Pb(Ti,Zr)O3多結晶体)に支配されている。この材料系は、これまで最高の圧電特性(無添加のPZTの圧電係数d33の最高値は約220pC/Nで、添加による改良されたソフトPZTは約400-580pC/N)を持つため、半世紀以来、圧電材料の“代名詞”となっている。しかし、PZTは有毒な鉛が大量に含むため、環境問題の観点から近年厳しく規制されつつある。そのため、PZTに匹敵する高性能非鉛の圧電材料の開発は世界的に緊迫した課題になっている。
この背景の中、近年非鉛圧電材料は数多く研究されてきたが、しかし、圧電・電歪特性はPZTに遠く及ばない(殆どの材料のd33は200pC/N以下)。最近開発されたKNN-LT((K,Na)NbO3-LiTaO3)及びKNN-LN((K,Na)NbO3-LiNbO3)系非鉛圧電材料の圧電係数d33は約150-300pC/Nと比較的に良いが、ソフトPZTまでは及んでいない。
更にKNN-LT及びKNN-LN系は合成困難、コスト高い(高価な元素Ta,Laを大量に含むため)など重要な欠点を持っている。
殆どのMPB組成において、室温から70℃の温度範囲で高い圧電特性(d33>350pC/N)を確認しており(図5)、室温付近での応用は十分適している。また、この材料を添加元素で特性を更に改善する可能性がある。
この材料系は非常に安定な酸化物からできた材料であるため、KNN系や(Bi0.5Na0.5)TiO3のような揮発問題は持っていない、大変良い焼結性を持ち、製造は非常に容易である。また、NbやTaなど高価な原料を使用しないため、原料コストと製造コストが低い。更に、KNN系のような潮解性或いは湿気に敏感する問題もない。
以上の特徴から、本発明で提案した材料系は室温付近(或いは室温以下)の応用でPZTを代替できる有力候補である。
図2、図3より、δ%=50%において最も良い特性(d33=584pC/N)を持つことが分かる。
図4は分極したδ%=50%試料の電歪と電場の関係(室温)を示す。この材料の圧電特性はソフトPZTの最高峰であるPZT-5Hを含むすべてのPZTを凌駕することが分かる。
図5は、δ%=40%,45%,50%試料の圧電係数d33の温度依存性を示すグラフである。MPB付近のこの三組成は70℃まで大きな圧電係数を維持していることがわかる(δ%=45%,50%試料この温度範囲ではd33>350pC/N)。従って、本発明の非鉛圧電材料は室温付近の応用に適している。
それ故に、本発明では、{[(Ba1-x1M1x1)((Ti1-xZrx)1-y1N1y1)O3]―δ%[(Ba1-yCay)1-x2M2x2)(Ti1-y2N2y2)O3]}(M1,N1,M2, N2は添加元素)と示した。
BZT-BCTはA2+B4+O3型perovskite構造を持っているため、A2+サイトにBa2+とCa2+が占有し、B4+サイトにTi4+とZr4+が占有している。「組成イオンと同価数の元素」とは、A2+サイトに置換する元素の場合は2+価の元素(例えばSr2+)、B4+サイトに置換する元素の場合は4+価の元素(例えばHf4+、Sn4+)である。また、「同価の添加元素」は異なる価数の元素の組み合わせで作り出すことも可能である(例えばA2+サイトに1/2Bi3+1/2Na+(平均価数は2+)で置換してもよい)。
Acceptor添加元素:
A2+の位置に置換する+2以下の価数を持つ添加元素(M1,M2):K+、Na+、Li+、Ag+など
B4+の位置に置換する+4価以下の添加元素(N1, N2):Mn3+、Fe3+、Co3+、Ni2+、Cu2+など。
「Acceptor元素添加」は圧電材料のロスを低減するために良く使われる改良法である。本発明においても、BZT-BCTを利用しながら、「Acceptor元素添加」による改良した材料が本発明の範囲である。
Donor添加元素:
A2+の位置に置換する+2以上の価数の添加元素:La3+、Bi3+、Y3+、Ce3+、Rh3+など
B4+の位置に置換する+4価以上の添加元素:Nb5+、Ta5+など。
「Donor元素添加」は圧電材料の圧電特性を向上するために良く使われる改良法である。本発明においても、BZT-BCTを利用しながら、「donor元素添加」による改良した材料が本発明の範囲である。
原料:BaZrO3 (99.9%), CaCO3 (99.9%) BaCO3(99. 9%) and TiO2 (99.9%)
作り方:標準固相焼結法。合成は1350℃2時間、焼結は1450℃3時間。(合成温 度は1200℃―1400℃、焼結温度は1300℃―1500℃が必要)
電極:Ag電極
分極条件:Curie温度以上の温度(110℃)で試料にcoercive fieldより2倍程度の電場をかけながら試料を室温までゆっくり冷やす。
試料の形状とサイズ:試料の厚みは6.5mm、直径は8mmのディスクである。
圧電特性の測定方法: 圧電係数d33はZJ-6B型d33メーターによる測定。電場― 変位測定はRadiant Technologies社Workstation及びMTI2000光学変位センサーによる測定。
この図で明らかになったように、本発明の非鉛圧電材料は他の非鉛圧電材料より2倍から数倍以上の圧電特性を持つだけでなく、殆どのPZTも凌駕する圧電特性を持っている。この図は本発明の先進性をよく表す。
電場―変位関係は大きい電場下の圧電特性を表す。この図より、本発明の非鉛圧電材料の大電場下の圧電特性はすべてのPZTより大きく上回ることが分かる。
MPB付近のこの三組成は70℃まで大きな圧電係数を維持していることがわかる。従って、本発明の非鉛圧電材料は室温付近の応用に適している。
家電製品や時計の電子音源
魚群探知機やソナーなどの水中探査源
ガスライターの着火源
金属、コンクリート、地殻など固体中の探査源
加湿器や吸入器の霧化源
各種洗浄機の超音波源
自動車のバック、コーナーセンサ
インクジェットプリンターのポンプ源
液晶モニタのインバータトランス
電子顕微鏡の走査微動源
医用診断装置やマッサージ器の超音波源
電話機やリモコンのクロック信号源
歩数計のカウント源
PCモニターのタッチセンサ
Claims (2)
- Pb等の有害元素を含まない非鉛系圧電材料であって、{[(Ba1-x1M1x1)((Ti1-xZrx)1-y1N1y1)O3]―δ%[(Ba1-yCay)1-x2M2x2)(Ti1-y2N2y2)O3]}(M1,N1,M2,N2は添加元素)の擬二元系固溶体(略称BZT-δ%BCT)からなることを特徴とする。
- 請求項1に記載の非鉛系圧電材料において、擬二元系固溶体は、結晶相境界(morphotrophic phase boundary、MPB)が存在することを特徴とする。
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CN2009801088731A CN101970374B (zh) | 2008-03-11 | 2009-03-10 | 非铅类压电材料 |
US12/921,465 US8182713B2 (en) | 2008-03-11 | 2009-03-10 | Lead-free piezoelectric material |
KR1020107022502A KR101251745B1 (ko) | 2008-03-11 | 2009-03-10 | 비연계 압전 재료 |
EP09718943.5A EP2251313B1 (en) | 2008-03-11 | 2009-03-10 | Non-lead-type piezoelectric material |
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JP2008-061044 | 2008-03-11 | ||
JP2008061044A JP5344456B2 (ja) | 2008-03-11 | 2008-03-11 | 非鉛系圧電材料 |
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WO2009113535A1 true WO2009113535A1 (ja) | 2009-09-17 |
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PCT/JP2009/054540 WO2009113535A1 (ja) | 2008-03-11 | 2009-03-10 | 非鉛系圧電材料 |
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US (1) | US8182713B2 (ja) |
EP (1) | EP2251313B1 (ja) |
JP (1) | JP5344456B2 (ja) |
KR (1) | KR101251745B1 (ja) |
CN (1) | CN101970374B (ja) |
WO (1) | WO2009113535A1 (ja) |
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Also Published As
Publication number | Publication date |
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EP2251313B1 (en) | 2014-07-30 |
CN101970374B (zh) | 2013-11-06 |
US8182713B2 (en) | 2012-05-22 |
EP2251313A4 (en) | 2012-11-21 |
EP2251313A1 (en) | 2010-11-17 |
CN101970374A (zh) | 2011-02-09 |
US20110037015A1 (en) | 2011-02-17 |
JP2009215111A (ja) | 2009-09-24 |
KR20110016864A (ko) | 2011-02-18 |
KR101251745B1 (ko) | 2013-04-05 |
JP5344456B2 (ja) | 2013-11-20 |
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