WO2005021461A1 - Composition de solution solide de perovskite et ceramiques piezo-electriques produites a partir de cette composition - Google Patents

Composition de solution solide de perovskite et ceramiques piezo-electriques produites a partir de cette composition Download PDF

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WO2005021461A1
WO2005021461A1 PCT/JP2004/012354 JP2004012354W WO2005021461A1 WO 2005021461 A1 WO2005021461 A1 WO 2005021461A1 JP 2004012354 W JP2004012354 W JP 2004012354W WO 2005021461 A1 WO2005021461 A1 WO 2005021461A1
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perovskite
document
solid solution
oxide
international
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PCT/JP2004/012354
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Japanese (ja)
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Ruiping Wang
Yoshiro Shimojo
Tadashi Sekiya
Kunio Matsuzaki
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National Institute Of Advanced Industrial Science And Technology
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Definitions

  • the present invention relates to a perovskite toy conjugate, sodium niobate (NaNbO) and potassium niobate (KNbO), which are composed mainly of different perovskite compounds such as BaTiO, SrTiO, and CaTiO.
  • the present invention relates to a perovskite solid solution composition having a composition in which an oxide is added in an amount of about several mol%, and a piezoelectric ceramic obtained by sintering the composition.
  • Piezoelectric ceramics undergo elongation deformation when a voltage is applied, and as an actuator such as an ultrasonic vibrator, an ultrasonic motor, a precision positioning element, or a piezoelectric transformer, a voltage is generated when a piezoelectric ceramic is deformed. It has a wide range of applications as sensors, sensors for piezoelectric gyros for car navigation systems, sonars, ultrasonic diagnostic devices, etc. In recent years, there has been a growing trend to make various machine systems intelligent, which has increased the importance of factories in particular. At present, the mainstream of piezoelectric ceramics widely used is mainly composed of lead zirconate titanate (PZT).
  • PZT lead zirconate titanate
  • the piezoelectricity of this PZT ceramic is brought about by the combination of antiferroelectric lead zirconate (PbZrO) with a rhombohedral structure and ferroelectric lead titanate (PbTiO) with a tetragonal structure.
  • PbZrO antiferroelectric lead zirconate
  • PbTiO ferroelectric lead titanate
  • MPB tetragonal phase boundary
  • many PZT-based piezoelectric ceramics are used with a composition near the MPB. The reason for this is that the instability is introduced into the perovskite structure, and the electrical sensitivity is increased, resulting in high electrical displacement.
  • Patent Document 1 a NaNbO-KNbO-PbTiO-based piezoelectric ceramic material as a low-lead-based piezoelectric ceramic
  • this piezoelectric ceramic material has excellent characteristics such as extremely high electric displacement, despite its lead content being significantly reduced as compared with conventional ones, it still has a composition containing lead. Met.
  • an actuator material can be obtained that is completely lead-free rather than low-lead and exhibits properties equal to or better than PZT ceramics, it is expected to improve the environmental pollution problem and have an immeasurable economic ripple effect. it can.
  • Patent Document 1 Japanese Patent Application No. 2003-040125
  • the present invention is a further development of the proposal of the above-mentioned Japanese Patent Application No. 2003-040125, which is completely lead-free and has been used in a conventional piezoelectric device mainly made of PZT ceramics. It is an object of the present invention to provide a novel environmentally friendly solid solution composition exhibiting a displacement characteristic significantly higher than that of a material and a piezoelectric ceramic obtained from the composition.
  • M1M20 is a divalent Ml metal ion (excluding lead) and a tetravalent M2 metal ion
  • a trivalent Ml metal ion that can selectively enter the alobskite-type oxide or perovskite-type oxide A site and a trivalent M2 metal ion that can selectively enter the perovskite-type oxide B site Represents a lobskite-type oxide.
  • Perovskite solid solution composition containing l 3 2 3 (l-z) (K Na) NbO _z M3 O
  • M3 represents a trivalent metal ion that can selectively enter the perovskite A or B site.
  • X and z represent numerical values in the range of 0.4 ⁇ x ⁇ 0.6 and 0 ⁇ z ⁇ 0.1, respectively.
  • the piezoelectric ceramic according to the present invention is a new environmentally friendly high-performance piezoelectric ceramic material because it has a significantly improved electrical displacement than conventional materials represented by the PZT system and does not contain lead. It opens the way for expanding applications.
  • the ceramics of the present invention include actuators such as ultrasonic vibrators, ultrasonic motors, precision positioning elements, piezoelectric transformers, acceleration sensors, piezoelectric gyros for car navigation systems, sonars, ultrasonic diagnostic elements, etc. Used in aircraft, automobiles, railway vehicles, ships It is also expected to have new applications as an actuator for vibration control of ships and vibration isolation of civil engineering buildings.
  • the oxide added to NaNbO-KNbO is not particularly limited to PbTiO but its ion size or valence power SNa + , KNb 5+
  • the perovskite solid solution composition according to the present invention contains (i) perovskite-type potassium sodium niobate Na) NbO and perovskite-type oxide M1M20, and has a general formula
  • the main component is (l-z) (K Na) NbO 2 -zM 3 O.
  • M1M20 is a divalent Ml metal ion (except for lead and lead) and a tetravalent M2 metal ion
  • Trivalent Ml metal ions that can selectively enter the perovskite-type oxide or perovskite-type oxide B site, and trivalent M2 metal ion forces that can selectively enter the perovskite-type oxide B site Represents a perovskite oxide.
  • x, y, and z represent numerical values in the range of 0.4 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.1, and 0 ⁇ 0.1.
  • the y range is 0 ⁇ y ⁇ 0.05.
  • Ml include divalent or trivalent metal ions (excluding lead) that can selectively enter the perovskite A site.
  • Mg, Ca, Sr, Ba, Bi, La , Y, Ce, Pr and the like are exemplified, and among them, Ba, Sr, Ca and the like are preferable.
  • M2 include tetravalent or trivalent metal ions that can selectively enter the perovskite B site.
  • examples include Ti, Zr, Sc, Ga, In, Zn, and Fe. Among them, Ti and Zr are preferable.
  • M3 include trivalent metal ions that can selectively enter the perovskite A or B site, and examples thereof include Bi, La, Y, Ce, Pr, Nd, and Fe. , La and Y are preferred.
  • ⁇ represents a numerical value in the range of 0 ⁇ 4 ⁇ 0.6.
  • the perovskite oxide M1M20 or the acid of a trivalent metal in the above (i) and (ii), the perovskite oxide M1M20 or the acid of a trivalent metal
  • the use ratio of the compound M30 is ⁇ potassium sodium niobate (K Na) Nb ⁇
  • the perovskite solid solution composition according to the present invention comprises potassium sodium niobate.
  • M1M20 a trivalent simple metal oxide (M30).
  • raw materials various forms such as carbonates, oxalates, nitrates, hydroxides and oxides can be used, and these raw materials are mixed into a predetermined composition to obtain a final composition. It may be prepared as follows.
  • the perovskite solid solution composition of the present invention can be made into a piezoelectric ceramic by densely sintering the perovskite solid solution composition preferably at a relative density of 95% or more.
  • Such sintering means is not limited, but if it can be sintered under normal pressure, it would be better than that. However, since sintering of KNbO-NaNbO-based materials is difficult, it is desirable to adopt a pressure and heat sintering method that can sinter under pressure in order to obtain a high-density sintered body efficiently.
  • Examples of such pressure heating and sintering methods include a spark plasma sintering method (hereinafter, referred to as an SPS method), a hot press method (hereinafter, referred to as an HP method), an anvil method, and a HIP method. (Hot isostatic method) and the like, and the methods preferably used in the present invention are the SPS method and the HP method.
  • the SPS method is a technique in which a DC pulse current is applied to a sample in a pressurized state, and grain boundary diffusion and particle bonding are caused by using the high energy of high-temperature plasma instantaneously generated by spark discharge. Recently, it has attracted attention as a high-speed sintering method for ceramics.
  • the main raw materials of KCO, NaCO and Nb0 and the oxides as additives are blended so as to have a desired perovskite composition, and calcined until a perovskite solid solution single phase is obtained.
  • the calcination conditions vary depending on the type and composition of the raw materials. Normally, the temperature is 850 1000 ° C and the time is 210 hours. The thus obtained ceramic powder is subjected to the SPS method or the HP method.
  • the SPS treatment can be performed using, for example, an apparatus such as an SPS-1030 apparatus manufactured by Sumitomo Coal Mining.
  • an apparatus such as an SPS-1030 apparatus manufactured by Sumitomo Coal Mining.
  • the desired sintered body can be obtained. Is obtained.
  • the sample reaches a predetermined temperature in about 5 minutes, and is sintered by holding that temperature for about 5 minutes.
  • the sintering temperature varies depending on the composition, but is in the range of 1020-1100 ° C.
  • the obtained sintered body has a diameter of 15 mm and a thickness of 34 mm, and the relative density reaches 96% or more.
  • the HP method may be performed using an apparatus such as a PRESS-VAC-2 type apparatus manufactured by Tokyo Vacuum Co., Ltd.
  • the sample is placed in a graphite die and pressed with upper and lower punches.
  • the force S is the same as in the SPS method, and heating is performed by an external heater mounted around the die.
  • an appropriate amount of the calcined ceramic powder is filled in a graphite die, and then the air is evacuated.
  • the external heater is energized and heated while applying pressure from above and below with a graphite punch.
  • the temperature reaches a predetermined temperature (1100 ° C) in about 2 hours.
  • a sintered body with a relative density of 95% or more can be obtained.
  • the perovskite solid solution composition of the present invention was sintered using the above-described SPS device and HP device.
  • the obtained ceramic was cut out into a plate of 5 mm X 5 mm X 0.5 mm size, mirror-polished on both sides, and a gold sputtered film was applied.
  • the polarization was performed at room temperature under the condition of 111, and the relationship between applied voltage and electric displacement was examined using a laser displacement meter.
  • Table 1 shows the composition, manufacturing method, and sintering density of the perovskite ceramics of the present invention.
  • Table 2 shows the phase transition temperature t, relative dielectric constant, dielectric loss, and electromechanical c of the perovskite ceramics of the present invention.
  • BaTiO was added to (Na K) NbO composition.
  • the displacements at 80 kV m are 0.9%, 0.6%, and 0.6%, respectively, which are high values, and high-performance piezoelectric materials are produced even with the NaNbO-KNbO-BaTiO system.
  • BaTiO is used for (Na K) NbO or (Na K) NbO composition.
  • Ceramics obtained by subjecting (Na K) NbO composition with BaZrO or SrZrO to SPS treatment.
  • the maximum strain is in the range of 0.2-0.4%, which is somewhat lower than NaNb ⁇ -KNbO-BaTiO or NaNb ⁇ -KNbO-SrTiO system.
  • trivalent metal oxides La 0 and Bi 0 capable of selectively substituting a viscous A-site with respect to the composition of (Na K) NbO were added, and a ceramic was prepared by HP.
  • the electric displacement of the obtained ceramics was in the range of 0.15 to 0.25%, which was almost comparable to that of the PZT system.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)

Abstract

Cette invention se rapporte à une solution solide de pérovskite qui comprend du niobate de potassium-sodium (K1-xNax)NbO3 et un oxyde de type pérovskite M1M2O3 ou un oxyde simple M32O3, où M1 représente un ion de métal, tel que Mg, Ca, Sr, Ba, Bi, La, Y, Ce ou Pr, capable d'entrer sélectivement dans un site de pérovskite A et qui exclut le plomb, M2 représente un ion de métal trivalent ou tétravalent, tel que Ti, Zr, Ga, In, Ni, Mn ou Fe, capable d'entrer sélectivement dans un site de pérovskite B, M3 représente un ion de métal trivalent, tel que Bi, La, Y, Ce, Pr, Nd ou Fe, capable d'entrer sélectivement dans un site de pérovskite A ou B, et x représente un nombre tel que 0,4 ≤ x ≤ 0,6. Cette solution solide de pérovskite est complètement exempte de plomb et elle est par conséquent respectueuse de l'environnement, et une céramique piézo-électrique composée de cette solution solide présente des caractéristiques de déplacement considérablement supérieures à celles des matériaux piézo-électriques traditionnels utilisés dans la pratique, qui sont essentiellement des céramiques de type PZT.
PCT/JP2004/012354 2003-08-28 2004-08-27 Composition de solution solide de perovskite et ceramiques piezo-electriques produites a partir de cette composition WO2005021461A1 (fr)

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JP2007022854A (ja) * 2005-07-15 2007-02-01 Toyota Motor Corp ニオブ酸カリウムナトリウム系無鉛圧電セラミック及びその製造方法
EP2006263A1 (fr) * 2006-04-13 2008-12-24 Murata Manufacturing Co. Ltd. Poudre de céramique et procédé de production de poudre de céramique
JP2010095404A (ja) * 2008-10-16 2010-04-30 National Institute Of Advanced Industrial Science & Technology 非鉛圧電セラミックス及びこれを用いた圧電・誘電・焦電素子
US20100187466A1 (en) * 2007-05-16 2010-07-29 National Institute Of Advanced Industrial Science Piezoelectric ceramic, and piezoelectric, dielectric or pyroelectric element using the same
CN101857436A (zh) * 2010-06-12 2010-10-13 中国地质大学（武汉） 一类铌酸钾钠基无铅压电陶瓷粉体及其制备方法
CN101935213A (zh) * 2010-09-07 2011-01-05 聊城大学 弛豫型铌酸钾钠基压电陶瓷复合物及其制备方法和应用
JP2012162407A (ja) * 2011-02-03 2012-08-30 Fdk Corp 圧電材料
WO2012141105A1 (fr) * 2011-04-15 2012-10-18 株式会社村田製作所 Elément de film mince piézoélectrique
JP5444714B2 (ja) * 2006-09-08 2014-03-19 コニカミノルタ株式会社 液滴吐出ヘッド
JP2014065317A (ja) * 2014-01-17 2014-04-17 Seiko Epson Corp 圧電素子及び液体噴射ヘッド
WO2014084265A1 (fr) * 2012-11-27 2014-06-05 富山県 Procédé de production d'une céramique piézoélectrique, céramique piézoélectrique, et élément piézoélectrique
JP2014179609A (ja) * 2013-03-14 2014-09-25 Tdk Corp 圧電素子、圧電アクチュエータ、及び圧電センサ、並びにハードディスクドライブ、及びインクジェットプリンタ装置
WO2015012344A1 (fr) * 2013-07-25 2015-01-29 日立金属株式会社 Céramique piézoélectrique à cristaux orientés, élément piézoélectrique et procédé pour la fabrication de céramique piézoélectrique à cristaux orientés
WO2015033791A1 (fr) * 2013-09-09 2015-03-12 株式会社村田製作所 Élément à couche mince piézoélectrique et son procédé de fabrication
US20150194592A1 (en) * 2012-11-28 2015-07-09 Tdk Corporation Piezoelectric element, piezoelectric actuator, piezoelectric sensor, hard disk drive, and inkjet printer device
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CN113429205A (zh) * 2021-07-16 2021-09-24 桂林电子科技大学 一种透明下转换光致发光陶瓷材料及其制备方法和应用
WO2023090249A1 (fr) * 2021-11-19 2023-05-25 住友化学株式会社 Matériau de cible de pulvérisation et cible de pulvérisation
EP3660183B1 (fr) * 2018-03-01 2023-07-19 JX Nippon Mining & Metals Corporation Cible de pulvérisation de sodium niobate de potassium et son procédé de production
JP7406876B2 (ja) 2018-10-17 2023-12-28 キヤノン株式会社 圧電トランス、および電子機器

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JP2002137966A (ja) * 2000-10-31 2002-05-14 Kyocera Corp 圧電磁器および圧電素子
JP2002338351A (ja) * 2001-05-10 2002-11-27 Tdk Corp 圧電磁器組成物、圧電磁器焼結体および電子部品
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EP2006263A1 (fr) * 2006-04-13 2008-12-24 Murata Manufacturing Co. Ltd. Poudre de céramique et procédé de production de poudre de céramique
US7838453B2 (en) * 2006-04-13 2010-11-23 Murata Manufacturing Co., Ltd. Ceramic powder and method for producing ceramic powder
EP2006263A4 (fr) * 2006-04-13 2012-02-22 Murata Manufacturing Co Poudre de céramique et procédé de production de poudre de céramique
JP5444714B2 (ja) * 2006-09-08 2014-03-19 コニカミノルタ株式会社 液滴吐出ヘッド
US8354038B2 (en) * 2007-05-16 2013-01-15 National Institute Of Advanced Industrial Science And Technology Piezoelectric ceramic, and piezoelectric, dielectric or pyroelectric element using the same
US20100187466A1 (en) * 2007-05-16 2010-07-29 National Institute Of Advanced Industrial Science Piezoelectric ceramic, and piezoelectric, dielectric or pyroelectric element using the same
JP2010095404A (ja) * 2008-10-16 2010-04-30 National Institute Of Advanced Industrial Science & Technology 非鉛圧電セラミックス及びこれを用いた圧電・誘電・焦電素子
CN101857436A (zh) * 2010-06-12 2010-10-13 中国地质大学（武汉） 一类铌酸钾钠基无铅压电陶瓷粉体及其制备方法
CN101935213A (zh) * 2010-09-07 2011-01-05 聊城大学 弛豫型铌酸钾钠基压电陶瓷复合物及其制备方法和应用
JP2012162407A (ja) * 2011-02-03 2012-08-30 Fdk Corp 圧電材料
WO2012141105A1 (fr) * 2011-04-15 2012-10-18 株式会社村田製作所 Elément de film mince piézoélectrique
JP5418725B2 (ja) * 2011-04-15 2014-02-19 株式会社村田製作所 圧電体薄膜素子
US9437805B2 (en) 2011-04-15 2016-09-06 Murata Manufacturing Co., Ltd. Piezoelectric thin film element
WO2014084265A1 (fr) * 2012-11-27 2014-06-05 富山県 Procédé de production d'une céramique piézoélectrique, céramique piézoélectrique, et élément piézoélectrique
JPWO2014084265A1 (ja) * 2012-11-27 2017-01-05 富山県 圧電セラミックスの製造方法、圧電セラミックス、および圧電素子
US20150194592A1 (en) * 2012-11-28 2015-07-09 Tdk Corporation Piezoelectric element, piezoelectric actuator, piezoelectric sensor, hard disk drive, and inkjet printer device
US9147827B2 (en) * 2012-11-28 2015-09-29 Tdk Corporation Piezoelectric element, piezoelectric actuator, piezoelectric sensor, hard disk drive, and inkjet printer device
JP2014179609A (ja) * 2013-03-14 2014-09-25 Tdk Corp 圧電素子、圧電アクチュエータ、及び圧電センサ、並びにハードディスクドライブ、及びインクジェットプリンタ装置
WO2015012344A1 (fr) * 2013-07-25 2015-01-29 日立金属株式会社 Céramique piézoélectrique à cristaux orientés, élément piézoélectrique et procédé pour la fabrication de céramique piézoélectrique à cristaux orientés
JP6044719B2 (ja) * 2013-09-09 2016-12-14 株式会社村田製作所 圧電薄膜素子及びその製造方法
WO2015033791A1 (fr) * 2013-09-09 2015-03-12 株式会社村田製作所 Élément à couche mince piézoélectrique et son procédé de fabrication
JP2014065317A (ja) * 2014-01-17 2014-04-17 Seiko Epson Corp 圧電素子及び液体噴射ヘッド
CN107056290A (zh) * 2016-11-04 2017-08-18 西安交通大学 一种调控铁电陶瓷居里温度的方法
EP3660183B1 (fr) * 2018-03-01 2023-07-19 JX Nippon Mining & Metals Corporation Cible de pulvérisation de sodium niobate de potassium et son procédé de production
JP7406876B2 (ja) 2018-10-17 2023-12-28 キヤノン株式会社 圧電トランス、および電子機器
CN113429205A (zh) * 2021-07-16 2021-09-24 桂林电子科技大学 一种透明下转换光致发光陶瓷材料及其制备方法和应用
CN113429205B (zh) * 2021-07-16 2022-04-01 桂林电子科技大学 一种透明下转换光致发光陶瓷材料及其制备方法和应用
WO2023090249A1 (fr) * 2021-11-19 2023-05-25 住友化学株式会社 Matériau de cible de pulvérisation et cible de pulvérisation

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