JP5281782B2 - (Li, Na, K) (Nb, Ta) O3 piezoelectric material manufacturing method - Google Patents

(Li, Na, K) (Nb, Ta) O3 piezoelectric material manufacturing method Download PDF

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JP5281782B2
JP5281782B2 JP2007274763A JP2007274763A JP5281782B2 JP 5281782 B2 JP5281782 B2 JP 5281782B2 JP 2007274763 A JP2007274763 A JP 2007274763A JP 2007274763 A JP2007274763 A JP 2007274763A JP 5281782 B2 JP5281782 B2 JP 5281782B2
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和之 海川
修一 小澤
浩文 山口
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    • H10N30/00—Piezoelectric or electrostrictive devices
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    • H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
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Description

本発明は、アクチュエータやセンサーに用いられる（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料の製造方法に関する。 The present invention relates to a method for producing a (Li, Na, K) (Nb, Ta) O 3 piezoelectric material used for actuators and sensors.

圧電／電歪アクチュエータは、サブミクロンのオーダーで変位を精密に制御することができるという利点を有する。特に、圧電／電歪磁器組成物の焼結体を圧電／電歪体として用いた圧電／電歪アクチュエータは、変位を精密に制御することができる他にも、電気機械変更効率が高く、発生力が大きく、応答速度が速く、耐久性が高く、消費電力が少ないという利点も有し、これらの利点を生かして、インクジェットプリンタのヘッドやディーゼルエンジンのインジェクタ等に採用されている。   Piezoelectric / electrostrictive actuators have the advantage that displacement can be precisely controlled on the order of submicrons. In particular, a piezoelectric / electrostrictive actuator using a sintered body of a piezoelectric / electrostrictive porcelain composition as a piezoelectric / electrostrictive body can precisely control displacement, and has high electromechanical change efficiency. It has the advantages of high power, fast response speed, high durability, and low power consumption. Taking advantage of these advantages, it is employed in inkjet printer heads, diesel engine injectors, and the like.

圧電／電歪アクチュエータ用の圧電／電歪磁器組成物としては、従来、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ３（ＰＺＴ）系の圧電／電歪磁器組成物が用いられていたが、焼結体からの鉛の溶質が地球環境に与える影響が強く懸念されるようになってからは、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系の圧電／電歪磁器組成物も検討されている。 As a piezoelectric / electrostrictive ceramic composition for a piezoelectric / electrostrictive actuator, a Pb (Zr, Ti) O 3 (PZT) -based piezoelectric / electrostrictive ceramic composition has been conventionally used. (Li, Na, K) (Nb, Ta) O 3 -based piezoelectric / electrostrictive porcelain compositions have been studied since the influence of lead solutes on the global environment is strongly concerned. .

（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料は、一般的に１０２０〜１２５０℃で０．１５〜４ｈｒ、大気中若しくは酸素雰囲気中で焼結される（例えば、非特許文献１〜３）。焼結温度に達するまでの昇温速度については、２００℃／ｈｒ又は３００℃／ｈｒで、室温から焼結温度まで一定速度で昇温している（例えば、特許文献１）。昇温中に６００〜６５０℃の範囲で１〜５ｈｒキープする事により、粉末の成形性を良くする為に添加した有機バインダーを除去（脱バインダー工程）している研究例もある（例えば、特許文献１）。 (Li, Na, K) (Nb, Ta) O 3 based piezoelectric materials are generally sintered at 1020 to 1250 ° C. for 0.15 to 4 hours in the air or in an oxygen atmosphere (for example, non-patent literature). 1-3). About the temperature increase rate until it reaches the sintering temperature, the temperature is increased at a constant rate from room temperature to the sintering temperature at 200 ° C./hr or 300 ° C./hr (for example, Patent Document 1). There is also a research example in which the organic binder added to improve the moldability of the powder is removed (debinding process) by keeping it in the range of 600 to 650 ° C. during the temperature rise for 1 to 5 hours (for example, patent) Reference 1).

M. Matsubara et. al., Jpn. J. Appl. Phys. 44 (2005) pp.6136-6142.M. Matsubara et. Al., Jpn. J. Appl. Phys. 44 (2005) pp.6136-6142. E. Hollenstein et. al., Appl. Phys. Lett. 87 (2005) 182905.E. Hollenstein et. Al., Appl. Phys. Lett. 87 (2005) 182905. Y. Guo et. al., App. Phys. Lett. 85 (2004) 4121Y. Guo et. Al., App. Phys. Lett. 85 (2004) 4121 特開２００６−２８００１号公報JP 2006-280001 A

しかしながら、以上の従来技術では、焼結温度や脱バインダーの検討はされているが、焼結温度に近い温度でのキープ工程や昇温速度の検討はなされていない。   However, in the above prior art, the sintering temperature and the binder removal have been studied, but the keep process and the temperature increase rate at temperatures close to the sintering temperature have not been studied.

また、上記した従来技術においては、次の問題点があった。
（１）焼結体内部に気孔（粒界、粒内）が多く、緻密化度が不十分である（相対密度９０〜９５％、例えば非特許文献２、Ｋ＝Ｎａ＝０．４８、Ｌｉ＝０．０４、Ｎｂ＝０．９、Ｔａ＝０．１で相対密度９４％）。 Further, the above-described prior art has the following problems.
(1) There are many pores (grain boundaries, intragrains) inside the sintered body, and the degree of densification is insufficient (relative density 90 to 95%, for example, Non-Patent Document 2, K = Na = 0.48, Li = 0.04, Nb = 0.9, Ta = 0.1, and a relative density of 94%).

（２）緻密化度が低い為、材料本来の特性を出せていない可能性がある。
（３）緻密化度が低い為、機械的強度に劣る。 (2) Since the degree of densification is low, the original characteristics of the material may not be achieved.
(3) Since the degree of densification is low, the mechanical strength is inferior.

（４）緻密化度を上げる為、ＣｕやＭｎ等の添加剤（焼結助剤）を加える研究例（例えば、非特許文献１）もあるが、添加元素が（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料に固溶しており、本来の特性を変えている可能性がある。
（５）添加元素が加わる事により、制御すべき組成が増える。 (4) There is a research example (for example, Non-Patent Document 1) in which an additive (sintering aid) such as Cu or Mn is added to increase the degree of densification, but the additive element is (Li, Na, K) ( It is a solid solution in the Nb, Ta) O 3 -based piezoelectric material, which may change the original characteristics.
(5) The composition to be controlled increases by adding the additive element.

本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、比誘電率や電界誘起歪を向上させることが可能な（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料の製造方法を提供することにある。 The present invention has been made in view of such problems of the prior art, and the problem is that the relative permittivity and electric field induced strain can be improved (Li, Na, K). An object of the present invention is to provide a method for producing a (Nb, Ta) O 3 -based piezoelectric material.

本発明者は、添加元素といった焼結助剤を加えるのでは無く、焼成スケジュールを変更する事により緻密化度を上げ、特性向上を目指した。具体的には、先ず（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３の成形体から焼結体に至るまでの焼成収縮カーブを測定し、焼成収縮が発生する温度域を調べた。その結果、焼成収縮が発生する温度域内で、一定温度でキープする定温キープ工程を焼成スケジュールに挿入することにより、緻密化度に優れ、高い電界誘起歪を有する焼結体（圧電材料）が得られることを見出した。 The present inventor aimed to improve characteristics by increasing the degree of densification by changing the firing schedule instead of adding a sintering aid such as an additive element. Specifically, first, the firing shrinkage curve from the (Li, Na, K) (Nb, Ta) O 3 compact to the sintered body was measured, and the temperature range where firing shrinkage occurred was examined. As a result, a sintered body (piezoelectric material) with excellent densification and high electric field induced strain can be obtained by inserting a constant temperature keeping process that keeps at a constant temperature within the temperature range where firing shrinkage occurs. I found out that

本発明によれば、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３の組成からなる粉末粒子の成形体を焼成することにより、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料を製造する方法であって、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料は、構成する全ての金属元素のモル数を１ｍｏｌとした場合のモル比で、Ｌｉが０．００９〜０．１０９、Ｎａが０．０７５〜０．４２７、Ｋが０．０７５〜０．４２７、Ｎｂが０．２２７〜０．５００、Ｔａが０．０２２〜０．２６３を含むものであって、粉末粒子の粒成長が生じる直前の温度、あるいは異相が僅かながら存在している温度である８５０〜１０００℃の範囲内の、一定温度で少なくとも１時間維持するキープ工程を行った後、さらに昇温して１１００℃未満の焼結温度にて焼結する、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料の製造方法、が提供される。 According to the present invention, (Li, Na, K) (Nb, Ta) by firing a compact of powder particles having the composition O 3, (Li, Na, K) (Nb, Ta) O 3 based A method of manufacturing a piezoelectric material, wherein (Li, Na, K) (Nb, Ta) O 3 based piezoelectric material has a molar ratio in which the number of moles of all constituent metal elements is 1 mol, and Li is Including 0.009 to 0.109, Na 0.075 to 0.427, K 0.075 to 0.427, Nb 0.227 to 0.500, Ta 0.022 to 0.263 After performing a keeping step for maintaining at a constant temperature for at least 1 hour within a range of 850 to 1000 ° C., which is a temperature immediately before the occurrence of grain growth of powder particles or a temperature at which a heterogeneous phase is slightly present. , baked further at Atsushi Nobori to less than 1100 ° C. the sintering temperature To, (Li, Na, K) (Nb, Ta) METHOD FOR PRODUCING O 3 based piezoelectric material, is provided.

本発明の製造方法において、キープ温度の範囲が８５０〜９５０℃であることが好ましく、キープ時間としては１〜２０時間であることが好ましい。また、焼成雰囲気が酸素雰囲気であることが好ましい。   In the production method of the present invention, the range of the keep temperature is preferably 850 to 950 ° C., and the keep time is preferably 1 to 20 hours. Further, the firing atmosphere is preferably an oxygen atmosphere.

なお、上記（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料としては、下記一般式（１）で表される組成を有するものが好ましい。 Note that the (Li, Na, K) (Nb, Ta) as O 3 based piezoelectric material is preferably one having a composition represented by the following general formula (1).

｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ}ａ（Ｎｂ１−ｚＴａｚ）Ｏ３ （１）
（但し、前記一般式（１）中、ａ＝０．９０〜１．２、ｘ＝０．２〜０．８、ｙ＝０．０２〜０．２、及びｚ＝０．０５〜０．５である。） {Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (1)
(However, in said general formula (1), a = 0.90-1.2, x = 0.2-0.8, y = 0.02-0.2, and z = 0.05-0. 5)

上記した本発明に係る（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料の製造方法は、焼成工程において、粒成長が生じる直前の温度、又は、異相が僅かながら存在している温度でキープする工程を加える事により、焼結助剤を用いることなく緻密化度の向上を達成し、高い電界誘起歪を得られるという効果がもたらされる。又、この工程を付加する事により結晶粒径が、より均一となる作用効果もあり、高い電界誘起歪が得られる。本発明の効果は、焼結方法に依存しない。即ち、加圧の無い焼結方法だけでなく、加圧機構のある焼結方法〔例えば、ホットプレス（ＨＰ）やホットアイソスタティックプレス（ＨＩＰ）〕においても効果がある。本発明の効果は、雰囲気に依存しない。即ち、大気雰囲気や酸素雰囲気、及び、ＡｒやＮ２雰囲気といった還元雰囲気においても効果がある。 In the method for producing a (Li, Na, K) (Nb, Ta) O 3 piezoelectric material according to the present invention described above, a temperature just before grain growth or a heterogeneous phase slightly exists in the firing step. By adding the step of keeping at the temperature, an effect of achieving a high degree of densification without using a sintering aid and obtaining a high electric field induced strain is brought about. In addition, by adding this step, there is an effect that the crystal grain size becomes more uniform, and a high electric field induced strain can be obtained. The effect of the present invention does not depend on the sintering method. That is, it is effective not only in a sintering method without pressing but also in a sintering method having a pressing mechanism [for example, hot pressing (HP) or hot isostatic pressing (HIP)]. The effect of the present invention does not depend on the atmosphere. That is, it is also effective in a reducing atmosphere such as an air atmosphere, an oxygen atmosphere and an Ar or N 2 atmosphere.

以下、本発明の実施の最良の形態について説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し適宜変更、改良等が加えられたものも本発明の範囲に入ることが理解されるべきである。   BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

本発明の製造方法は、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３の組成からなる粉末粒子の成形体を焼成するにあたり、８５０〜１０００℃の範囲、好ましくは８５０〜９５０℃の範囲内の一定温度で一定時間キープすることに特徴を有する。８５０〜１０００℃の範囲は、粉末粒子の粒成長が生じる直前の温度、あるいは異相が僅かながら存在している温度であり、この温度範囲内の一定温度で一定時間でキープすることにより、焼結助剤を用いずに、得られる焼結体の緻密化度が向上し、高い電界誘起歪が得られる。 In the production method of the present invention, a powder particle compact having a composition of (Li, Na, K) (Nb, Ta) O 3 is fired in the range of 850 to 1000 ° C., preferably in the range of 850 to 950 ° C. It is characterized by keeping for a certain time at a certain temperature. The range of 850 to 1000 ° C. is a temperature immediately before the grain growth of the powder particles occurs, or a temperature at which a different phase is slightly present, and sintering is performed by keeping at a constant temperature within this temperature range for a certain time. Without using an auxiliary agent, the densification degree of the obtained sintered body is improved, and a high electric field induced strain is obtained.

上記したキープ温度が８５０℃より低い場合には、得られる焼結体の緻密化度はそれほど向上せず、電界誘起歪も低くなる。一方、キープ温度が１０００℃を超える場合、焼結温度である１０５０℃に近くなり過ぎ、事実上、焼結を行っている事と同じとなり、キープ工程の意味がなくなる。   When the above-mentioned keep temperature is lower than 850 ° C., the densification degree of the obtained sintered body is not improved so much and the electric field induced strain is also lowered. On the other hand, when the keep temperature exceeds 1000 ° C., it becomes too close to the sintering temperature of 1050 ° C., which is practically the same as the sintering, and the meaning of the keep step is lost.

また、８５０〜１０００℃の範囲にキープする時間としては、１〜２０ｈｒであることが好ましい。キープ時間が１ｈｒより短いと、効果が低く、得られる焼結体の緻密化度が向上せず、電界誘起歪も低い。一方、キープ時間が２０ｈｒを超えても、特性はこれ以上向上しない。   Moreover, as time to keep in the range of 850-1000 degreeC, it is preferable that it is 1-20 hr. When the keep time is shorter than 1 hr, the effect is low, the densification degree of the obtained sintered body is not improved, and the electric field induced strain is also low. On the other hand, even if the keep time exceeds 20 hours, the characteristics are not improved further.

本発明の焼成工程においては、酸素雰囲気であることが好ましいが、これに限定されない。即ち、大気雰囲気や酸素雰囲気に限らず、ＡｒやＮ２雰囲気といった還元雰囲気においても所定の効果を有する。 In the firing step of the present invention, an oxygen atmosphere is preferable, but the present invention is not limited to this. That is, it has a predetermined effect not only in an air atmosphere and an oxygen atmosphere but also in a reducing atmosphere such as an Ar or N 2 atmosphere.

さらに、本発明の製造方法においては、焼結手法に依存しない。即ち、加圧の無い焼結方法だけでなく、加圧機構のある焼結方法〔例えば、ホットプレス（ＨＰ）やホットアイソスタティックプレス（ＨＩＰ）〕においても、同様に本発明の効果を奏するものである。   Furthermore, the manufacturing method of the present invention does not depend on the sintering technique. That is, not only the sintering method without pressurization but also the sintering method with a pressurization mechanism [for example, hot press (HP) or hot isostatic press (HIP)] has the same effect as the present invention. It is.

本発明に用いる（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料としては、下記一般式（１）で表される組成を有するものが好ましい。 As the (Li, Na, K) (Nb, Ta) O 3 based piezoelectric material used in the present invention, one having a composition represented by the following general formula (1) is preferable.

｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ}ａ（Ｎｂ１−ｚＴａｚ）Ｏ３ （１）
（但し、前記一般式（１）中、ａ＝０．９０〜１．２、ｘ＝０．２〜０．８、ｙ＝０．０２〜０．２、及びｚ＝０．０５〜０．５である。） {Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (1)
(However, in said general formula (1), a = 0.90-1.2, x = 0.2-0.8, y = 0.02-0.2, and z = 0.05-0. 5)

本発明においては、Ｌｉ、Ｎａ、Ｋ、Ｎｂ、及びＴａからなる酸化物を含む圧電材料であれば、適用することができる。その中でも、一般式（１）において、ａ＝０．９０〜１．２、ｘ＝０．２〜０．８、ｙ＝０．０２〜０．２、及びｚ＝０．０５〜０．５であることが好ましいが、さらに好ましくは、ａ＝１．００５〜１．１０、ｘ＝０．４〜０．６、ｙ＝０．０５〜０．１、及びｚ＝０．０８〜０．２５である。   In the present invention, any piezoelectric material containing an oxide composed of Li, Na, K, Nb, and Ta can be applied. Among them, in the general formula (1), a = 0.90 to 1.2, x = 0.2 to 0.8, y = 0.02 to 0.2, and z = 0.05 to 0.5. More preferably, a = 1.005-1.10, x = 0.4-0.6, y = 0.05-0.1, and z = 0.08-0. 25.

ここで、Ａ／Ｂ比（＝ａ）に関し、ａ≦１．２としたのは、この範囲を上回ると、誘電損失が増加し、高電界印加時の電界誘起歪が小さくなる傾向があるからである。誘電損失の増加は、高電界を印加するアクチュエータ用の圧電／電歪磁器組成物では問題が大きい。一方、０．９０≦ａとしたのは、粒成長を促進させ、緻密化させるためである。この範囲を下回ると、粒成長を促進させるために１１００℃以上の加熱が必要となる。この場合、アルカリ成分の蒸発が起こり易くなり、組成が変動することで特性が不安定になる。本発明では、特に１．００５≦ａ≦１．１０とすることが好ましく、この場合、緻密化と粒成長をさせる上で効果が高く、焼結温度を１１００℃未満とすることができ、組成の変動を回避することができる。 Here, with respect to the A / B ratio (= a), the reason why a ≦ 1.2 is exceeded is that if it exceeds this range, the dielectric loss increases and the electric field induced strain when applying a high electric field tends to decrease. It is. The increase in dielectric loss is a serious problem in a piezoelectric / electrostrictive ceramic composition for an actuator that applies a high electric field. On the other hand, 0.90 ≦ a is set to promote grain growth and densify. Below this range, heating at 1100 ° C. or higher is required to promote grain growth. In this case, evaporation of the alkali component is likely to occur, and the characteristics become unstable due to fluctuations in the composition. In the present invention, it is particularly preferable that 1.005 ≦ a ≦ 1.10. In this case, the effect is high in densification and grain growth, and the sintering temperature can be less than 1100 ° C. Fluctuations can be avoided.

Ｋ、Ｌｉ及びＴａ量をそれぞれ０．２≦ｘ≦０．８、０．０２≦ｙ≦０．２及び０．０５≦ｚ≦０．５としたのは、この範囲でアクチュエータ用として好適な圧電／電歪磁器組成物を得る事ができるからである。   The K, Li, and Ta amounts are set to 0.2 ≦ x ≦ 0.8, 0.02 ≦ y ≦ 0.2, and 0.05 ≦ z ≦ 0.5, respectively. This is because a piezoelectric / electrostrictive ceramic composition can be obtained.

例えば、ｘがこの範囲を下回ると、圧電／電歪特性が急激に低下する。一方、ｘがこの範囲を上回ると、焼結が困難になり、焼結温度を高くしなければならなくなる。焼結温度を高くすることが望ましくないのは、焼結温度を高くすると、圧電／電歪磁器組成物に含まれるアルカリ成分が蒸発し、圧電／電歪特性を安定して得ることができなくなるからである。   For example, when x is less than this range, the piezoelectric / electrostrictive characteristics are rapidly lowered. On the other hand, if x exceeds this range, sintering becomes difficult and the sintering temperature must be increased. It is not desirable to increase the sintering temperature. When the sintering temperature is increased, the alkali component contained in the piezoelectric / electrostrictive porcelain composition evaporates, and the piezoelectric / electrostrictive characteristics cannot be obtained stably. Because.

また、ｙがこの範囲を下回ると、やはり、焼結が困難になり、焼結温度を高くしなければならなくなる。一方、ｙがこの範囲を上回ると、異相の析出が多くなり、絶縁性が低下する。   If y is less than this range, sintering becomes difficult, and the sintering temperature must be increased. On the other hand, when y exceeds this range, precipitation of heterogeneous phases increases, and the insulation properties decrease.

さらに、ｚがこの範囲を下回ると、圧電／電歪特性が低下する。一方、ｚがこの範囲を上回ると、やはり、焼結が困難になり、焼結温度を高くしなければならなくなる。   Furthermore, when z is below this range, the piezoelectric / electrostrictive characteristics are degraded. On the other hand, if z exceeds this range, sintering becomes difficult, and the sintering temperature must be increased.

次に、本発明の具体的な実施結果である実施例及び比較例を示す。   Next, examples and comparative examples, which are specific implementation results of the present invention, are shown.

（比較例１）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．０１）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。得られた焼結体について、アルキメデス法による嵩密度、ペレット寸法変化による焼成収縮を測定した。また、得られた焼結体の表面微構造から、粒径はばらつきが大きく、不均一である事が分かる（図１のＳＥＭ写真を参照）。この焼結体を短冊状に加工した後、比誘電率、圧電定数ｄ31、誘電損失（ｔａｎδ）、電界誘起歪Ｓ４０００（４ｋＶ／ｍｍの電界を加えた時の３１方向、即ち、電界印加方向に対して垂直方向の歪量）を評価した。その結果を表１と表２に示した。 (Comparative Example 1)
{Li y (Na 1-x K x) 1-y} a (Nb 1-z Ta z) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.01 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet sample was heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr in the atmosphere. After holding at 1050 ° C. for 3 hours, the furnace was cooled. About the obtained sintered compact, the firing density by the bulk density by the Archimedes method and the pellet size change was measured. Moreover, it can be seen from the surface microstructure of the obtained sintered body that the particle size varies widely and is not uniform (see the SEM photograph in FIG. 1). After processing this sintered body into a strip shape, the relative permittivity, the piezoelectric constant d 31 , the dielectric loss (tan δ), the electric field induced strain S4000 (31 directions when an electric field of 4 kV / mm is applied, that is, the electric field application direction) The amount of strain in the vertical direction) was evaluated. The results are shown in Tables 1 and 2.

（比較例２）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で８００℃まで昇温し、８００℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表１に示した。 (Comparative Example 2)
The pellet-like sample shown in Comparative Example 1 was heated to 800 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 800 ° C. for 3 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

（実施例１）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で８５０℃まで昇温し、８５０℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表１に示した。 Example 1
The pellet-like sample shown in Comparative Example 1 was heated to 850 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 850 ° C. for 3 hours, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

（実施例２）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表１と表２に示した。 (Example 2)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 3 hours, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Tables 1 and 2.

（実施例３）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９５０℃まで昇温し、９５０℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表１に示した。 (Example 3)
The pellet-like sample shown in Comparative Example 1 was heated to 950 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 950 ° C. for 3 hours, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

（実施例４）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で１０００℃まで昇温し、１０００℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表１に示した。 Example 4
The pellet-like sample shown in Comparative Example 1 was heated to 1000 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 1000 ° C. for 3 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

（実施例５）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表２に示した。 (Example 5)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 1 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2.

（実施例６）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で６ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表２に示した。 (Example 6)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 6 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2.

（実施例７）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。得られた焼結体の表面微構造から、比較例１より粒径はばらつきが小さく、均一になっている事が分かる（図２のＳＥＭ写真を参照）。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表２と表４に示した。 (Example 7)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. From the surface microstructure of the obtained sintered body, it can be seen that the particle size is smaller and uniform than Comparative Example 1 (see the SEM photograph in FIG. 2). The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Tables 2 and 4.

（実施例８）
比較例１で示したペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で２０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表２に示した。 (Example 8)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 20 hr, and then increased to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. Warm up. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 2.

（比較例３）
比較例１で示したペレット状試料を、管状炉を用いた酸素フロー下で２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表３に示した。 (Comparative Example 3)
The pellet-like sample shown in Comparative Example 1 was heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr under an oxygen flow using a tubular furnace. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 3.

（実施例９）
比較例１で示したペレット状試料を、管状炉を用いた酸素フロー下で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で３ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表３に示した。 Example 9
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr under an oxygen flow using a tubular furnace, held at 900 ° C. for 3 hours, and then baked at a rate of 200 ° C./hr. The temperature was raised to 1050 ° C. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 3.

（実施例１０）
比較例１で示したペレット状試料を、管状炉を用いた酸素フロー下で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で６ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表３に示した。 (Example 10)
The pellet-like sample shown in Comparative Example 1 was heated to 900 ° C. at a rate of 200 ° C./hr under an oxygen flow using a tubular furnace, held at 900 ° C. for 6 hours, and then baked at a rate of 200 ° C./hr. The temperature was raised to 1050 ° C. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 3.

（実施例１１）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝０．８５）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 11)
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 0.85) ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１２）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝０．９０）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 12)
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 0.90) ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１３）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝０．９５）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 13)
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 0.95) ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１４）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．００）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 14)
{Li y (Na 1-x K x) 1-y} a (Nb 1-z Ta z) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.00 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１５）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．００５）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 15)
{Li y (Na 1-x K x) 1-y} a (Nb 1-z Ta z) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.005 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１６）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．１０）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 16)
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (x = 0.458, y = 0.57, z = 0.082, a = 1.10) ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１７）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．１５）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 17)
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.15 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１８）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．２０）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 18)
{Li y (Na 1-x K x) 1-y} a (Nb 1-z Ta z) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.20 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

（実施例１９）
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ｝ａ（Ｎｂ１−ｚＴａｚ）Ｏ３（ｘ＝０．４５８、ｙ＝０．０５７、ｚ＝０．０８２、ａ＝１．２５）の組成から成る仮焼／粉砕紛（粒径０．２〜０．５μｍ、粒形状は球状）をペレット状に成形した（ペレット状試料）。このペレット状試料を、大気中で２００℃／ｈｒの速度で９００℃まで昇温し、９００℃で１０ｈｒ保持した後、２００℃／ｈｒの速度で焼結温度１０５０℃まで昇温した。１０５０℃で３ｈｒ保持した後、炉冷した。比較例１と同様にして、得られた焼結体の特性を評価した。その結果を表４に示した。 (Example 19)
{Li y (Na 1-x K x) 1-y} a (Nb 1-z Ta z) O 3 (x = 0.458, y = 0.057, z = 0.082, a = 1.25 ) Calcined / ground powder (particle size 0.2 to 0.5 μm, particle shape is spherical) was formed into pellets (pellet sample). The pellet-like sample was heated to 900 ° C. at a rate of 200 ° C./hr in the atmosphere, held at 900 ° C. for 10 hours, and then heated to a sintering temperature of 1050 ° C. at a rate of 200 ° C./hr. After holding at 1050 ° C. for 3 hours, the furnace was cooled. The characteristics of the obtained sintered body were evaluated in the same manner as in Comparative Example 1. The results are shown in Table 4.

以上の結果からわかるように、焼成スケジュールにキープ工程を焼成収縮が生じる温度域に入れる事により、密度だけでなく、比誘電率や電界誘起歪（Ｓ４０００）も向上した。特に、粒成長が生じないぎりぎりの温度、又は異相が僅かながら存在できる温度（この実施例の組成の場合、８５０〜９５０℃）でのキープが電界誘起歪を向上させる上で最も効果が高い事が分かる。   As can be seen from the above results, not only the density but also the relative permittivity and the electric field induced strain (S4000) were improved by putting the keep process in the temperature range where the firing shrinkage occurs in the firing schedule. In particular, keeping at a marginal temperature at which grain growth does not occur, or a temperature at which a heterogeneous phase can exist slightly (in the case of the composition of this example, 850 to 950 ° C.) is most effective in improving the electric field induced strain. I understand.

又、キープ工程を焼成スケジュールに入れる事で、焼結体中の結晶粒のばらつきがより小さくなる効果もあり、これにより電界誘起歪の向上がもたらされた。この効果は、キープ時間を長くする事でさらに顕著となる。粒径のばらつきが小さくなる事は機械的特性の向上にもつながる。   In addition, putting the keep process in the firing schedule also has the effect of reducing the variation in crystal grains in the sintered body, resulting in an improvement in the electric field induced strain. This effect becomes more prominent by increasing the keep time. Smaller variations in particle size lead to improved mechanical properties.

本発明では、比誘電率や電界誘起歪が向上した優れた（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料を製造することができるので、アクチュエータ、センサー等に好ましく適用することができる。 In the present invention, an excellent (Li, Na, K) (Nb, Ta) O 3 -based piezoelectric material with improved relative permittivity and electric field induced strain can be produced, and therefore it is preferably applied to actuators, sensors, and the like. Can do.

比較例１で得られた焼結体の表面微構造を示すＳＥＭ写真である。4 is a SEM photograph showing a surface microstructure of a sintered body obtained in Comparative Example 1. 実施例７で得られた焼結体の表面微構造を示すＳＥＭ写真である。6 is a SEM photograph showing a surface microstructure of a sintered body obtained in Example 7.

Claims (5)

（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３の組成からなる粉末粒子の成形体を焼成することにより、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料を製造する方法であって、
該（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料は、構成する全ての金属元素のモル数を１ｍｏｌとした場合のモル比で、Ｌｉが０．００９〜０．１０９、Ｎａが０．０７５〜０．４２７、Ｋが０．０７５〜０．４２７、Ｎｂが０．２２７〜０．５００、Ｔａが０．０２２〜０．２６３を含むものであって、
粉末粒子の粒成長が生じる直前の温度、あるいは異相が僅かながら存在している温度である８５０〜１０００℃の範囲内の、一定温度で少なくとも１時間維持するキープ工程を行った後、さらに昇温して１１００℃未満の焼結温度にて焼結する、（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料の製造方法。 (Li, Na, K) ( Nb, Ta) by firing a compact of powder particles having the composition O 3, a method for producing a (Li, Na, K) ( Nb, Ta) O 3 based piezoelectric material Because
The (Li, Na, K) (Nb, Ta) O 3 based piezoelectric material has a molar ratio in which the number of moles of all constituent metal elements is 1 mol, and Li is 0.009 to 0.109, Na Is 0.075 to 0.427, K is 0.075 to 0.427, Nb is 0.227 to 0.500, Ta is 0.022 to 0.263,
After performing a keeping step of maintaining at a constant temperature for at least 1 hour within a range of 850 to 1000 ° C., which is a temperature immediately before the occurrence of particle growth of powder particles or a temperature at which a heterogeneous phase is slightly present, the temperature is further increased. And (Li, Na, K) (Nb, Ta) O 3 based piezoelectric material manufacturing method for sintering at a sintering temperature of less than 1100 ° C. 前記キープ温度の範囲が８５０〜９５０℃である請求項１記載の製造方法。   The manufacturing method according to claim 1, wherein a range of the keep temperature is 850 to 950 ° C. 前記キープ時間が１〜２０時間である請求項１又は２記載の製造方法。   The manufacturing method according to claim 1, wherein the keep time is 1 to 20 hours. 焼成雰囲気が酸素雰囲気である請求項１〜３のいずれか１項に記載の製造方法。   The manufacturing method according to claim 1, wherein the firing atmosphere is an oxygen atmosphere. 前記（Ｌｉ，Ｎａ，Ｋ）（Ｎｂ，Ｔａ）Ｏ３系圧電材料が、下記一般式（１）で表される組成を有するものである請求項１〜４のいずれか１項に記載の製造方法。
｛Ｌｉｙ（Ｎａ１−ｘＫｘ）１−ｙ}ａ（Ｎｂ１−ｚＴａｚ）Ｏ３ （１）
（但し、前記一般式（１）中、ａ＝０．９０〜１．２、ｘ＝０．２〜０．８、ｙ＝０．０２〜０．２、及びｚ＝０．０５〜０．５である。） The production according to any one of claims 1 to 4, wherein the (Li, Na, K) (Nb, Ta) O 3 piezoelectric material has a composition represented by the following general formula (1). Method.
{Li y (Na 1-x K x ) 1-y } a (Nb 1-z Ta z ) O 3 (1)
(However, in said general formula (1), a = 0.90-1.2, x = 0.2-0.8, y = 0.02-0.2, and z = 0.05-0. 5)
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