JP2001068754A - Actuator piezoelectric member and its manufacture - Google Patents
Actuator piezoelectric member and its manufactureInfo
- Publication number
- JP2001068754A JP2001068754A JP24264199A JP24264199A JP2001068754A JP 2001068754 A JP2001068754 A JP 2001068754A JP 24264199 A JP24264199 A JP 24264199A JP 24264199 A JP24264199 A JP 24264199A JP 2001068754 A JP2001068754 A JP 2001068754A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- less
- zirconate titanate
- lead zirconate
- void
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超音波モーター、
インクジェットプリンタヘッド等に用いられるチタン酸
ジルコン酸鉛系焼結体からなるアクチュエータ用圧電部
材及びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to an ultrasonic motor,
The present invention relates to a piezoelectric member for an actuator made of a lead zirconate titanate-based sintered body used for an inkjet printer head or the like, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来、超音波モーターやインクジェット
プリンタヘッドには圧電型のアクチュエータが用いられ
ている。この圧電型のアクチュエータの基本原理は、分
極処理した圧電セラミックスからなるアクチュエータ用
圧電部材の相対する面に電極を形成して電圧を印加する
と、圧電セラミックス中の結晶に歪みが発生して変形す
ることを利用したもので、このようなアクチュエータ用
圧電部材としてチタン酸ジルコン酸鉛系焼結体が用いら
れていた。2. Description of the Related Art Conventionally, a piezoelectric actuator is used for an ultrasonic motor or an ink jet printer head. The basic principle of this piezoelectric actuator is that, when electrodes are formed on opposing surfaces of an actuator piezoelectric member made of polarized piezoelectric ceramics and a voltage is applied, the crystals in the piezoelectric ceramics are deformed due to distortion. A piezoelectric zirconate titanate-based sintered body has been used as such a piezoelectric member for an actuator.
【０００３】チタン酸ジルコン酸鉛系焼結体を製造する
には、アルコキシド法、蓚酸法、水熱合成法等の化学的
方法や仮焼合成法等で合成したチタン酸ジルコン酸鉛系
合成粉体を、周知のプレス成形法、テープ成形法等にて
成形し、大気雰囲気（酸素濃度が２０体積％程度）にて
焼成して製作されていた。In order to produce a lead zirconate titanate-based sintered body, a lead zirconate titanate-based synthetic powder synthesized by a chemical method such as an alkoxide method, an oxalic acid method, a hydrothermal synthesis method, or a calcining synthesis method is used. The body was molded by a known press molding method, a tape molding method, or the like, and fired in an air atmosphere (oxygen concentration is about 20% by volume).
【０００４】しかしながら、ＰｂＯを主成分とした鉛系
複合材料を大気雰囲気中で焼成すると、ＰｂＯが蒸発し
て圧電諸特性が劣化することが知られている。[0004] However, it is known that when a lead-based composite material containing PbO as a main component is fired in an air atmosphere, PbO evaporates and piezoelectric properties deteriorate.
【０００５】その為、大気焼成にて圧電諸特性を劣化さ
せずにチタン酸ジルコン酸鉛系焼結体を得る方法とし
て、特開平１１−１２０３１号公報には、チタン酸ジル
コン酸鉛系合成粉体を得る際に、焼成時に蒸発するＰｂ
Ｏをあらかじめ過剰に加え、圧電諸特性の劣化を防止す
ることが開示されている。Japanese Patent Application Laid-Open No. 11-12031 discloses a method for obtaining a lead zirconate titanate-based sintered body without deteriorating various piezoelectric properties by firing in air. Pb evaporates during firing when obtaining body
It is disclosed that O is added excessively in advance to prevent deterioration of various piezoelectric characteristics.
【０００６】また、チタン酸ジルコン酸鉛系焼結体をア
クチュエータ用圧電部材として用いる場合、圧電定数等
の圧電諸特性が高いことは勿論のこと、高細度、高精度
の加工性が要求され、ダイシングソーやワイヤーソー等
による微細加工においてカケやチッピング等が発生しな
いような機械的特性に優れたアクチュエータ用圧電部材
が望まれていた。そして、ダイシングソーやワイヤーソ
ー等での微細加工によるカケやチッピングの発生を防ぐ
ためには、チタン酸ジルコン酸鉛系焼結体そのものの機
械的強度を向上させるとともに、焼結体内部に存在する
ボイド径やボイド率を小さくすることが必要であった。When a lead zirconate titanate-based sintered body is used as a piezoelectric member for an actuator, not only high piezoelectric properties such as a piezoelectric constant but also high fineness and high precision workability are required. In addition, there has been a demand for a piezoelectric member for an actuator having excellent mechanical properties such that chipping, chipping, and the like do not occur in fine processing using a dicing saw, a wire saw, or the like. In order to prevent the occurrence of chipping and chipping due to fine processing with a dicing saw or wire saw, etc., the mechanical strength of the lead zirconate titanate-based sintered body itself should be improved, and voids existing inside the sintered body should be improved. It was necessary to reduce the diameter and void ratio.
【０００７】その為、緻密化されたチタン酸ジルコン酸
鉛系焼結体を得る方法として、熱間静水圧プレス法（Ｈ
ＩＰ法）にて、ボイドを押しつぶすか、あるいは特許第
２６５２４２５号に開示されているように、昇温時の酸
素濃度を５０体積％以上とし、かつ焼成温度時の酸素濃
度を昇温時の１／２乃至１０体積％にして焼成すること
が提案されていた。Therefore, as a method of obtaining a densified lead zirconate titanate-based sintered body, a hot isostatic pressing method (H
In the IP method), the voids are crushed or, as disclosed in Japanese Patent No. 2652425, the oxygen concentration at the time of temperature increase is 50% by volume or more, and the oxygen concentration at the firing temperature is 1% at the time of temperature increase. It has been proposed to bake at a volume ratio of / 2 to 10% by volume.
【０００８】[0008]
【発明が解決しようとする課題】ところが、特開平１１
−１２０３１号公報に開示されているように、チタン酸
ジルコン酸鉛系合成粉体の秤量時にあらかじめ過剰のＰ
ｂＯを加えるようにしても、大気雰囲気での焼成では、
ＰｂＯの蒸発を防ぐことが難しく、ＰｂＯが焼結体表面
から蒸発するため、焼結体表層部と焼結体内部との組成
差並びにボイド径やボイド率の差が大きく、内外の構造
が均質なチタン酸ジルコン酸鉛系焼結体を得ることがで
きなかった。SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
As disclosed in Japanese Unexamined Patent Publication No. 12031, an excess amount of lead zirconate titanate-based synthetic powder is weighed beforehand.
Even if bO is added, firing in air atmosphere
It is difficult to prevent PbO from evaporating, and PbO evaporates from the surface of the sintered body. Therefore, the composition difference between the surface layer of the sintered body and the inside of the sintered body, and the difference in void diameter and void ratio are large, and the inner and outer structures are homogeneous. A lead zirconate titanate-based sintered body could not be obtained.
【０００９】その為、得られたチタン酸ジルコン酸鉛系
焼結体をアクチュエータ用圧電部材に用いる場合、焼結
体表層部を研削加工にて除去する必要があり、高価な原
料の無駄が多く、また研削時間が長くなるといった不都
合があった。Therefore, when the obtained lead zirconate titanate-based sintered body is used for a piezoelectric member for an actuator, it is necessary to remove the surface layer portion of the sintered body by grinding, which wastes expensive raw materials. In addition, there is a disadvantage that the grinding time is long.
【００１０】また、焼結体表層部を研削加工にて除去し
たとしても、焼結体内部は充分に緻密化されていないた
め、所定の形状に研削するために、ダイシングソーやワ
イヤーソー等にて加工を施すと、カケやチッピング等が
発生し易く、例えば電極や微細な電極引出線を形成する
場合、断線を招く要因となっていた。Even if the surface layer of the sintered body is removed by grinding, the inside of the sintered body is not sufficiently densified. When processing is performed, chipping, chipping, and the like are likely to occur. For example, when an electrode or a fine electrode lead wire is formed, it has been a factor that causes disconnection.
【００１１】しかも、大気雰囲気中での焼成では、大気
圧の変化に伴ってＰｂＯの蒸発量が変化し易いため、チ
タン酸ジルコン酸鉛系焼結体の組成にばらつきが生じ易
く、安定した圧電諸特性を持ったアクチュエータ用圧電
部材を得ることが難しかった。In addition, in firing in an air atmosphere, the amount of evaporation of PbO tends to change with a change in atmospheric pressure, so that the composition of the lead zirconate titanate-based sintered body is apt to vary, and a stable piezoelectric material is obtained. It was difficult to obtain a piezoelectric member for an actuator having various characteristics.
【００１２】一方、熱間静水圧プレス法（ＨＩＰ法）に
て緻密化した場合、全体的に緻密なチタン酸ジルコン酸
鉛系焼結体を得ることができるものの、焼結体表層部と
焼結体内部とでボイドの分布状態に差があり、焼結体内
外において均質な構造を有するチタン酸ジルコン酸鉛系
焼結体を得ることは難しいものであった。On the other hand, when densification is performed by hot isostatic pressing (HIP method), although a dense lead zirconate titanate-based sintered body can be obtained as a whole, the surface layer of the sintered body and the sintered body can be obtained. There is a difference in the distribution of voids inside and inside the sintered body, and it has been difficult to obtain a lead zirconate titanate-based sintered body having a homogeneous structure inside and outside the sintered body.
【００１３】その為、熱間静水圧プレス法（ＨＩＰ法）
にて緻密化した焼結体もまたアクチュエータ用圧電部材
として用いる場合、研削加工にて焼結体表層部を除去し
なければならなかった。[0013] Therefore, hot isostatic pressing (HIP method)
When the sintered body densified in the above is also used as a piezoelectric member for an actuator, the surface layer portion of the sintered body must be removed by grinding.
【００１４】 しかも、熱間静水圧プレス法（ＨＩＰ法）
は、外圧を加えながら焼成する方法であるため、焼結体
中に残留応力が残り、ダイシングソーやワイヤーソーで
の研削加工時に応力が開放され、カケやチッピングが発
生する恐れもあった。[0014] Moreover, hot isostatic pressing (HIP method)
Is a method in which firing is performed while applying external pressure.
Residual stress remains inside, using a dicing saw or wire saw
Stress is released during grinding of chips, causing chipping and chipping.
There was also a fear of living.
【００１５】 その上、熱間静水圧プレス法（ＨＩＰ法）
は、高価な加圧設備を必要とするためにコストがかか
り、アクチュエータ用圧電部材が高額なものになってし
まうとともに、量産化に適さないといった課題もあっ
た。[0015] In addition, hot isostatic pressing (HIP method)
Is expensive due to the need for expensive pressurized equipment
And the piezoelectric member for the actuator becomes expensive.
There are also issues that are not suitable for mass production
Was.
【００１６】これに対し、特許第２６５２４２５号に開
示された方法では、焼成時における炉内雰囲気の変化を
少なくでき、かつＰｂＯの蒸発を制御することができる
ため、チタン酸ジルコン酸鉛系焼結体を全体的に緻密化
できるものの、この方法においても大きなボイドが焼結
体中に残ることがあった。On the other hand, in the method disclosed in Japanese Patent No. 2652425, a change in the furnace atmosphere during firing can be reduced, and the evaporation of PbO can be controlled. Although the body can be densified as a whole, large voids sometimes remain in the sintered body in this method.
【００１７】この理由としては、チタン酸ジルコン酸鉛
系粒子間に形成される空孔内の酸素濃度と外気の酸素濃
度の勾配が大きくなると、酸素が拡散することにより、
チタン酸ジルコン酸鉛系粒子間の隙間を埋めてボイドを
追い出すとともに、粒成長を助長し、焼結を促進させ、
ボイド径を小さくする傾向があり、ある程度の大きさの
ボイドは消失し、ボイド率を小さくできるのであるが、
粒成長とともに、粒子界面に孤立したボイドがチタン酸
ジルコン酸鉛系粒子中に取り込まれてしまうためである
と思われる。そして、チタン酸ジルコン酸鉛系粒子中に
取り込まれたボイドを取り除くことは、粒子界面に孤立
したボイドを取り除くより困難であった。The reason for this is that when the gradient between the oxygen concentration in the pores formed between the lead zirconate titanate-based particles and the oxygen concentration in the outside air increases, oxygen diffuses,
Fill gaps between lead zirconate titanate-based particles to expel voids, promote grain growth, promote sintering,
There is a tendency to reduce the void diameter, voids of a certain size disappear, and the void ratio can be reduced,
It is considered that voids isolated at the particle interface are taken into the lead zirconate titanate-based particles along with the grain growth. Then, it was more difficult to remove the voids incorporated in the lead zirconate titanate-based particles than to remove the voids isolated at the particle interface.
【００１８】その為、大きなボイドが存在するチタン酸
ジルコン酸鉛系焼結体に研削加工を施すと、欠けやチッ
ピングの原因となるとともに、電極や微細な電極引出線
を形成する場合、断線を招く要因となっていた。Therefore, grinding a lead zirconate titanate-based sintered body having large voids causes chipping and chipping, and when an electrode or a fine electrode lead wire is formed, disconnection may occur. It was an inviting factor.
【００１９】[0019]
【課題を解決するための手段】そこで、本発明は上記課
題に鑑み、基本組成式がＰｂＺｒＴｉＯ3 で表されるペ
ロブスカイト組成を有し、前記基本組成式のＰｂがＢ
ａ、Ｓｒ、Ｌａのうち少なくとも１種以上の元素で一部
置換され、且つＺｒ及びＴｉがＮｂ、Ｚｎ、Ｓｂ、Ｎ
ｉ、Ｍｇのうち少なくとも１種以上の元素で一部置換さ
れているチタン酸ジルコン酸鉛系焼結体からなるアクチ
ュエータ用圧電部材において、前記焼結体の密度が理論
密度の９８％以上、最大結晶粒子径が１０μｍ以下、最
大ボイド径が１０μｍ以下であるとともに、無研磨状態
での前記焼結体表面における表面粗度が中心線平均粗さ
（Ｒａ）で０．３μｍ以下であり、前記焼結体表面から
１００μｍまでの深さを焼結体表層部、それ以外を焼結
体内部とした時、該焼結体内部におけるボイド率が１．
０％以下でかつ焼結体表層部と焼結体内部におけるボイ
ド率の差が１．０％以下であることを特徴とする。In view of the above problems, the present invention has a basic composition formula having a perovskite composition represented by PbZrTiO 3 , wherein Pb of the basic composition formula is Bb
a, Sr, and La are partially substituted with at least one or more elements, and Zr and Ti are replaced with Nb, Zn, Sb, N
In a piezoelectric member for an actuator made of a lead zirconate titanate-based sintered body partially substituted with at least one or more of i and Mg, the density of the sintered body is 98% or more of the theoretical density, The crystal grain diameter is 10 μm or less, the maximum void diameter is 10 μm or less, and the surface roughness of the surface of the sintered body in a non-polished state is 0.3 μm or less in center line average roughness (Ra). When the depth from the surface of the sintered body to 100 μm is defined as the surface layer portion of the sintered body and the other portion is defined as the inside of the sintered body, the void ratio inside the sintered body is 1.
0% or less and a difference in void ratio between the surface layer portion of the sintered body and the inside of the sintered body is 1.0% or less.
【００２０】また、本発明は前記アクチュエータ用圧電
部材を製造するにあたり、平均粒径が０．４〜０．７μ
ｍ、粒度分布の標準偏差が０．２μｍ以下、ＢＥＴ比表
面積が５〜１３ｍ2 ／ｇであるチタン酸ジルコン酸鉛系
合成粉体を所定の形状に成形した成形体を、マグネシア
系セラミックス又はジルコニア系セラミックスからなる
半密閉容器に入れ、炉内雰囲気の酸素濃度を２５体積％
以上に保ちながら焼成することを特徴とする。Further, according to the present invention, when manufacturing the piezoelectric member for an actuator, the average particle diameter is 0.4 to 0.7 μm.
m, a standard deviation of particle size distribution of 0.2 μm or less, and a BET specific surface area of 5 to 13 m 2 / g. A molded body obtained by molding a lead zirconate titanate-based synthetic powder into a predetermined shape is formed of magnesia ceramic or zirconia. In a semi-hermetic container made of ceramics, and set the oxygen concentration in the furnace atmosphere to 25% by volume
It is characterized by firing while keeping the above.
【００２１】[0021]
【発明の実施の形態】本発明に係るアクチュエータ用圧
電部材は、基本組成式がＰｂＺｒＴｉＯ3 で表されるペ
ロブスカイト組成を有し、前記基本組成式のＰｂがＢ
ａ、Ｓｒ、Ｌａのうち少なくとも１種以上の元素で一部
置換され、且つＺｒ及びＴｉがＮｂ、Ｚｎ、Ｓｂ、Ｎ
ｉ、Ｍｇのうち少なくとも１種以上の元素で一部置換さ
れたチタン酸ジルコン酸鉛系焼結体からなり、緻密で均
質な構造を有し、かつ無研磨状態での焼結体表面が滑ら
かであることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The piezoelectric member for an actuator according to the present invention has a perovskite composition whose basic composition formula is represented by PbZrTiO 3 , and Pb of the basic composition formula is B
a, Sr, and La are partially substituted with at least one or more elements, and Zr and Ti are replaced with Nb, Zn, Sb, N
It is made of a lead zirconate titanate-based sintered body partially substituted with at least one or more elements of i and Mg, has a dense and homogeneous structure, and has a smooth surface in a non-polished state. It is characterized by being.
【００２２】基本組成式のＰｂを前記元素で一部置換す
るとともに、Ｚｒ及びＴｉを前記元素で一部置換するの
は、圧電諸特性、特に圧電定数を高めるのに有効である
からで、変位特性の優れたアクチュエータ用圧電部材と
することができる。The partial replacement of Pb in the basic composition formula with the above-mentioned elements and the partial replacement of Zr and Ti with the above-mentioned elements is effective for increasing the piezoelectric characteristics, especially the piezoelectric constant. A piezoelectric member for an actuator having excellent characteristics can be obtained.
【００２３】また、本発明において緻密とは、焼結体の
密度が理論密度の９８％以上を有することを言い、緻密
化することで圧電定数等の圧電諸特性をさらに向上させ
ることができるからであり、また、本発明において無研
磨状態での焼結体表面が滑らかであるとは、中心線平均
粗さ（Ｒａ）で０．３μｍ以下であることを言い、研削
加工などを施さなくても断線を生じることなく電極や電
極引出線を直接焼結体表面に形成することができる。In the present invention, the term "density" means that the density of the sintered body is 98% or more of the theoretical density. Since densification can further improve various piezoelectric characteristics such as a piezoelectric constant. Further, in the present invention, that the surface of the sintered body in a non-polished state is smooth means that the center line average roughness (Ra) is 0.3 μm or less, and the surface is not subjected to grinding or the like. Also, electrodes and electrode leads can be directly formed on the surface of the sintered body without causing disconnection.
【００２４】さらに、本発明において均質な構造を有す
るとは、焼結体中におけるチタン酸ジルコン酸鉛系粒子
の最大結晶粒子径が１０μｍ以下でかつ最大ボイド径が
１０μｍ以下であるとともに、焼結体表面から１００μ
ｍまでの深さを焼結体表層部、それ以外を焼結体内部と
した時、焼結体内部におけるボイド率が１．０％以下で
かつ焼結体表層部と焼結体内部におけるボイド率の差が
１．０％以下であることを言う。In the present invention, having a homogeneous structure means that the maximum crystal particle diameter of the lead zirconate titanate-based particles in the sintered body is 10 μm or less and the maximum void diameter is 10 μm or less, 100μ from body surface
When the depth up to m is defined as the surface layer of the sintered body and the other portion is defined as the inside of the sintered body, the void ratio in the sintered body is 1.0% or less and the void in the surface layer of the sintered body and the inside of the sintered body are reduced. It means that the difference between the rates is 1.0% or less.
【００２５】ここで、チタン酸ジルコン酸鉛系粒子の最
大結晶粒径を１０μｍ以下としたのは、最大結晶粒径が
１０μｍを越えると、無研磨状態での焼結体表面を中心
線平均粗さ（Ｒａ）で０．３μｍ以下とすることができ
ず、また、焼結体の４点曲げ強度が大幅に低下して破損
し易く、研削加工を施すとカケやチッピングが発生する
からである。Here, the reason why the maximum crystal grain size of the lead zirconate titanate-based particles is set to 10 μm or less is that when the maximum crystal grain size exceeds 10 μm, the surface of the sintered body in the non-polished state has a center line average roughness. In addition, the sintered body cannot be reduced to 0.3 μm or less, and the four-point bending strength of the sintered body is greatly reduced, so that the sintered body is easily broken, and chipping or chipping occurs when the grinding processing is performed. .
【００２６】また、焼結体中の最大ボイド径を１０μｍ
以下としたのは、最大ボイド径が１０μｍを越えると、
研削加工を施した時にこのボイドを起点としてカケやチ
ッピングが発生するからであり、また、このボイドが焼
結体表面に存在する時には、電極や微細な電極引出線を
形成する際に断線を引き起こす原因となるからである。The maximum void diameter in the sintered body is 10 μm.
The reason is that if the maximum void diameter exceeds 10 μm,
This is because chipping and chipping occur from this void as a starting point when grinding is performed, and when this void is present on the surface of the sintered body, disconnection occurs when an electrode or a fine electrode lead line is formed. It is because it causes.
【００２７】さらに、焼結体内部のボイド率を１．０％
以下としたのは、ボイド率が１．０％を越えると、焼結
体の密度を理論密度の９８％以上とすることができず、
研削加工を施した時にカケやチッピングの起点となるボ
イドが占める比率が多くなってしまうからである。Further, the void ratio inside the sintered body is set to 1.0%
The reason is that if the void ratio exceeds 1.0%, the density of the sintered body cannot be made 98% or more of the theoretical density,
This is because the ratio of voids, which are the starting points of chipping and chipping when grinding is performed, increases.
【００２８】そして、焼結体表層部と焼結体内部におけ
るボイド率の差を１．０％以下としたのは、１．０％を
越えると、焼結体表層部と焼結体内部での圧電諸特性や
研削加工時の研削性が大きくことなるために、均質な構
造を有するものとは言い難く、アクチュエータ用圧電部
材として用いるには、焼結体表層部を研削加工にて除去
する必要があるからである。The difference between the void ratio between the surface layer of the sintered body and the inside of the sintered body is set to 1.0% or less. It is difficult to say that it has a homogeneous structure because the piezoelectric properties of the material and the grindability during grinding are large. To use it as a piezoelectric member for an actuator, the surface layer of the sintered body is removed by grinding. It is necessary.
【００２９】その為、前記組成及び構造を満足する本発
明のチタン酸ジルコン酸鉛系焼結体からなるアクチュエ
ータ用圧電部材を用いれば、優れた圧電諸特性を有する
ことから、超音波モーターやインクジェットプリンタヘ
ッド等の圧電型アクチュエータとしても好適に用いるこ
とができるとともに、所定の形状に形成するにあたり研
削加工を施しても欠けやチッピングを生じることがな
く、さらには焼結した焼き放し面のままでも滑らかで大
きなボイドが存在しないため、直接電極や電極引出線を
形成することができ、研磨工程を不要あるいは研磨時間
を短くでき、かつ高価な原料無駄を無くすことができ
る。Therefore, if the piezoelectric member for an actuator made of the lead zirconate titanate-based sintered body of the present invention which satisfies the above-mentioned composition and structure is used, since it has excellent piezoelectric characteristics, it can be used for an ultrasonic motor or an ink jet. It can be suitably used as a piezoelectric actuator such as a printer head, and does not cause chipping or chipping even when subjected to grinding in forming a predetermined shape, and even as it is as a sintered annealed surface Since smooth and large voids do not exist, electrodes and electrode leads can be directly formed, so that a polishing step is not required or the polishing time can be shortened, and expensive raw material waste can be eliminated.
【００３０】ところで、このアクチュエータ用圧電部材
を製造するには、チタン酸ジルコン酸鉛系焼結体を構成
する各元素の化合物を秤量し、アルコキシド法、蓚酸
法、水熱合成法等の化学的方法や仮焼合成法等で合成し
て基本組成式がＰｂＺｒＴｉＯ3 で表されるペロブスカ
イト組成を有し、前記基本組成式のＰｂがＢａ、Ｓｒ、
Ｌａのうち少なくとも１種以上の元素で一部置換され、
且つＺｒとＴｉがＮｂ、Ｚｎ、Ｓｂ、Ｎｉ、Ｍｇのうち
少なくとも１種以上で一部置換されたチタン酸ジルコン
酸鉛系合成粉末を作製する。ここで、チタン酸ジルコン
酸鉛系焼結体を構成する各元素の化合物としては、基本
成分であるＰｂ3 Ｏ4 、ＺｒＯ2 、ＴｉＯ2 に対し、Ｐ
ｂと一部置換する成分として、ＢａＣＯ3 、ＳｒＣ
Ｏ3 、Ｌａ2 Ｏ3 の少なくとも一種以上を、Ｚｒ及び
Ｔｉと一部置換する成分として、Ｎｂ2 Ｏ5 、ＺｎＯ、
Ｓｂ2 Ｏ3 、ＮｉＯ、ＭｇＣＯ3 の少なくとも１種以上
をそれぞれ添加する。In order to manufacture the piezoelectric member for an actuator, the compounds of the respective elements constituting the lead zirconate titanate-based sintered body are weighed and subjected to a chemical method such as an alkoxide method, an oxalic acid method, or a hydrothermal synthesis method. A perovskite composition represented by PbZrTiO 3 synthesized by a method or a calcining synthesis method, wherein Pb of the basic composition formula is Ba, Sr,
La is partially substituted with at least one or more elements of La;
In addition, a lead zirconate titanate-based synthetic powder in which Zr and Ti are partially substituted with at least one of Nb, Zn, Sb, Ni, and Mg is produced. Here, as a compound of each element constituting the lead zirconate titanate-based sintered body, Pb 3 O 4 , ZrO 2 , and TiO 2 which are basic components
BaCO 3 , SrC
As a component that partially replaces at least one of O 3 and La 2 O 3 with Zr and Ti, Nb 2 O 5 , ZnO,
At least one of Sb 2 O 3 , NiO and MgCO 3 is added.
【００３１】そして、チタン酸ジルコン酸鉛系合成粉末
を回転ミル等にて平均粒径が０．４〜０．７μｍ、粒度
分布の標準偏差が０．２μｍ以下、ＢＥＴ比表面積が５
〜１３ｍ2 ／ｇになるまで粉砕する。Then, the lead zirconate titanate-based synthetic powder is prepared by a rotary mill or the like to have an average particle size of 0.4 to 0.7 μm, a standard deviation of the particle size distribution of 0.2 μm or less, and a BET specific surface area of 5 μm or less.
Ground to a ~13m 2 / g.
【００３２】チタン酸ジルコン酸鉛系合成粉末の平均粒
径が０．７μｍを越えると、ＢＥＴ比表面積が５ｍ2 ／
ｇ未満となり、全エネルギーにしめる表面エネルギーの
割合が小さくなるために焼成温度を下げる効果がなく、
粒成長を促進されて焼結体中におけるチタン酸ジルコン
酸鉛系粒子の最大結晶粒径が１０μｍを越え、粒成長に
よってボイドがチタン酸ジルコン酸鉛系粒子中に取り込
まれて最大ボイド径１０μｍ以下、焼結体内部のボイド
率１％以下を達成することができず、逆に平均粒径が
０．４μｍ未満では、ＢＥＴ比表面積が１３ｍ2 ／ｇ以
下となるように粉砕することが難しくなるとともに、メ
ディアの摩耗粉が混入して組成が変わってしまうからで
ある また、粒度分布の標準偏差が０．２μｍを超えると、粒
径のバラツキが大きく、粒径の小さなチタン酸ジルコン
酸鉛系粒子は、粒径の大きなチタン酸ジルコン酸鉛系粒
子に取り込まれて粒成長し易くなり、焼結後におけるチ
タン酸ジルコン酸鉛系粒子の最大結晶粒径を１０μｍ以
下とすることが難しく、また、ボイドが取り込まれて焼
結体中の最大ボイド径１０μｍ以下、焼結体内部のボイ
ド率１％以下を達成することができないからである。When the average particle diameter of the lead zirconate titanate-based synthetic powder exceeds 0.7 μm, the BET specific surface area is 5 m 2 /
g, there is no effect of lowering the firing temperature because the ratio of surface energy to the total energy is reduced,
Grain growth is promoted and the maximum crystal grain size of the lead zirconate titanate-based particles in the sintered body exceeds 10 μm, and voids are taken into the lead zirconate titanate-based particles by the grain growth and the maximum void diameter is 10 μm or less. On the other hand, when the void ratio inside the sintered body is not more than 1%, if the average particle diameter is less than 0.4 μm, it is difficult to pulverize the sintered body so that the BET specific surface area becomes 13 m 2 / g or less. When the standard deviation of the particle size distribution exceeds 0.2 μm, the dispersion of the particle size is large and the particle size is small, and the lead zirconate titanate having a small particle size is used. The particles are easily incorporated into the lead zirconate titanate-based particles having a large particle diameter, so that the particles can easily grow, and it is difficult to reduce the maximum crystal grain size of the lead zirconate titanate-based particles after sintering to 10 μm or less. Ku, also below the maximum void diameter 10μm sintered body in voids is captured, it is not possible to achieve less than 1% void of the sintered body portion.
【００３３】なお、チタン酸ジルコン酸鉛系合成粉末の
粉砕にあたっては、回転ミル以外に、振動ミルや他粉砕
手法を用いれば良い。そして、合成粉末の粒径を調整す
るには、ボールやビーズ等のメディア径を適宜選択し、
湿式で１０〜６０Ｈｒ時間粉砕すれば良い。In grinding the lead zirconate titanate-based synthetic powder, a vibration mill or another grinding method may be used in addition to the rotary mill. And, in order to adjust the particle diameter of the synthetic powder, the media diameter of balls, beads, etc. is appropriately selected,
What is necessary is just to grind for 10 to 60 hours by wet type.
【００３４】次に、得られたチタン酸ジルコン酸鉛系合
成粉末を有機バインダーと混合し、プレス成形法やテー
プ成形法等周知のセラミック成形手段にて、所定の形状
に成形したあと、２００℃〜９００℃の大気雰囲気中に
て有機バインダーを脱脂し、次いで鉛雰囲気調整用の粉
体と共にマグネシア系セラミックス又はジルコニア系セ
ラミックスからなる半密閉容器中に入れる。Next, the obtained lead zirconate titanate-based synthetic powder is mixed with an organic binder and molded into a predetermined shape by a known ceramic molding means such as a press molding method or a tape molding method. The organic binder is degreased in an air atmosphere at about 900 ° C., and then placed in a semi-closed container made of magnesia-based ceramics or zirconia-based ceramics together with a powder for adjusting lead atmosphere.
【００３５】ここで、半密閉容器を用いる理由として
は、焼成炉内の雰囲気置換段階において、容器内へ酸素
が容易に置換され、さらにチタン酸ジルコン酸鉛系粒子
間に形成されるボイド内に十分な酸素を供給する必要が
あるからである。また、半密閉容器をマグネシア系セラ
ミックス又はジルコニア系セラミックスにより形成する
ことで、チタン酸ジルコン酸鉛系焼結体との相互拡散反
応を防ぐことができる。そして、焼成炉内に酸素を流入
させた状態で、１０００℃〜１３００℃で焼成すれば良
い。Here, the reason for using a semi-closed container is that oxygen is easily replaced in the container during the atmosphere replacement step in the firing furnace, and furthermore, the inside of the void formed between the lead zirconate titanate-based particles is reduced. This is because it is necessary to supply sufficient oxygen. Further, by forming the semi-hermetic container with magnesia-based ceramics or zirconia-based ceramics, it is possible to prevent a mutual diffusion reaction with the lead zirconate titanate-based sintered body. Then, firing may be performed at 1000 ° C. to 1300 ° C. with oxygen flowing into the firing furnace.
【００３６】ただし、焼成炉内の容積１リットル当たり
に供給する酸素流入量が０．１リットル／分より少なく
と、焼結体中におけるチタン酸ジルコン酸鉛系粒子間に
形成されるボイド内に十分な酸素を供給することができ
ず、ボイド内の酸素濃度と外気の酸素濃度の勾配が小さ
くなって酸素拡散が抑制されるため、ボイドを追い出す
効果が小さく、逆に、焼成炉内の容積１リットル当たり
に供給する酸素流入量が２．０リットル／分より多くな
ると、炉内の温度が安定しなかったり、炉内の温度が低
下するために、焼成ムラを生じることがある。その為、
焼成時における酸素流入量は、焼成炉内の容積１リット
ル当たり０．１〜２．０リットル／分とする。However, if the flow rate of oxygen supplied per liter of volume in the firing furnace is less than 0.1 liter / min, the voids formed between the lead zirconate titanate-based particles in the sintered body will be reduced. Sufficient oxygen cannot be supplied, and the gradient between the oxygen concentration in the void and the oxygen concentration in the outside air is reduced, thereby suppressing oxygen diffusion. If the flow rate of oxygen supplied per liter is more than 2.0 liters / minute, the temperature in the furnace may not be stable or the temperature in the furnace may be reduced, resulting in uneven firing. For that reason,
The flow rate of oxygen during firing is 0.1 to 2.0 liters / minute per liter of volume in the firing furnace.
【００３７】また、炉内雰囲気の酸素濃度が２５体積％
未満では、酸素濃度が低すぎるため、ＰｂＯの蒸発、分
解が著しく、またボイド中の酸素濃度が低いことから、
焼結時においてボイド内の酸素拡散が起り難く、ボイド
を収縮させることができないために緻密化することがで
きない。その為、ボイドの収縮速度を速めるためには、
炉内雰囲気の酸素濃度を、２５体積％以上、好ましくは
５０体積％以上、さらに望ましくは８０体積％以上とす
ることが良い。The oxygen concentration in the furnace atmosphere is 25% by volume.
If the oxygen concentration is less than 0, the oxygen concentration is too low, so that the evaporation and decomposition of PbO are remarkable, and the oxygen concentration in the void is low.
At the time of sintering, diffusion of oxygen in the void hardly occurs, and the void cannot be shrunk, so that the void cannot be densified. Therefore, in order to increase the contraction speed of the void,
The oxygen concentration in the furnace atmosphere is preferably at least 25% by volume, preferably at least 50% by volume, and more preferably at least 80% by volume.
【００３８】以上のように、チタン酸ジルコン酸鉛系合
成粉体の平均粒径、粒度分布の標準偏差、ＢＥＴ比表面
積を前述したように制御するとともに、焼成過程で生成
されたボイド中に酸素を供給して拡散させることで、ボ
イドを小さくしたり、消失させることができるため、チ
タン酸ジルコン酸鉛系焼結体中における最大ボイド径を
１０μｍ以下、焼結体内部におけるボイド率を１．０％
以下、さらに焼結体表層部と焼結体内部におけるボイド
率の差を１．０％以下とすることができるとともに、焼
結体の密度を理論密度の９８％以上に緻密化することが
できるため、アクチュエータとして重要な圧電定数等の
圧電諸特性を向上させることができるとともに、所望の
形状とするために研削加工を施しても欠けやチッピング
を生じることがない。しかも、無研磨状態ので焼結体表
面の表面粗度を中心線平均粗さ（Ｒａ）で０．３μｍ以
下の滑らかな面とすることができるため、直接電極や電
極引出線を形成することができ、製作工程を減らせると
ともに、高価が原料無駄を防ぐことができるといった効
果を有するアクチュエータ用圧電部材を形成することが
できる。As described above, the average particle size, the standard deviation of the particle size distribution, and the BET specific surface area of the lead zirconate titanate-based synthetic powder are controlled as described above, and oxygen is contained in the voids generated during the firing process. By supplying and diffusing, the voids can be reduced or eliminated, so that the maximum void diameter in the lead zirconate titanate-based sintered body is 10 μm or less and the void ratio inside the sintered body is 1. 0%
Hereinafter, the difference in void ratio between the surface layer portion of the sintered body and the inside of the sintered body can be reduced to 1.0% or less, and the density of the sintered body can be reduced to 98% or more of the theoretical density. Therefore, various piezoelectric characteristics such as a piezoelectric constant, which are important as an actuator, can be improved, and chipping or chipping does not occur even if grinding is performed to obtain a desired shape. In addition, since the surface roughness of the surface of the sintered body can be made a smooth surface having a center line average roughness (Ra) of 0.3 μm or less in an unpolished state, it is possible to directly form an electrode or an electrode lead wire. Accordingly, a piezoelectric member for an actuator can be formed which has an effect of reducing the number of manufacturing steps and preventing waste of raw materials although expensive.
【００３９】[0039]
【実施例】以下、本発明に係るアクチュエータ用圧電部
材の一例について説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an example of a piezoelectric member for an actuator according to the present invention will be described.
【００４０】出発原料に、Ｐｂ3 Ｏ4 、ＳｒＣＯ3 、Ｚ
ｒＯ2 、ＴｉＯ2 、Ｎｂ2 Ｏ5 、ＺｎＯの粉末を用い、
各粉末を所定量秤量し、ボールミルにて２０時間湿式混
合したあと、脱水乾燥し、しかるのち９００℃で３時間
仮焼してチタン酸ジルコン酸鉛系合成粉体を得た。そし
て、得られた合成粉体、直径０．５〜１０ｍｍのジルコ
ニアボール、イオン交換水を１：５：２の割合で容器に
投入し、回転ミルにて２０〜６０時間粉砕することで、
平均粒径、粒径の標準偏差、ＢＥＴ比表面積を表１に示
すように異ならせた。As starting materials, Pb 3 O 4 , SrCO 3 , Z
Using powders of rO 2 , TiO 2 , Nb 2 O 5 and ZnO,
A predetermined amount of each powder was weighed, wet-mixed in a ball mill for 20 hours, dehydrated and dried, and then calcined at 900 ° C. for 3 hours to obtain a lead zirconate titanate-based synthetic powder. Then, the obtained synthetic powder, zirconia balls having a diameter of 0.5 to 10 mm, and ion-exchanged water are charged into a container at a ratio of 1: 5: 2, and pulverized by a rotary mill for 20 to 60 hours.
The average particle size, the standard deviation of the particle size, and the BET specific surface area were varied as shown in Table 1.
【００４１】次に、得られた合成粉体に有機バインダー
を添加混練し、乾燥、造粒して顆粒を作製したあと、得
られた顆粒を１．２ｔ／ｃｍ2 の圧力で一軸加圧成型し
て成形体を形成したあと、３００℃の大気雰囲気中にて
有機バインダーを脱脂し、しかるのち鉛雰囲気調整用の
粉体と共にジルコニアセラミックス、マグネシアセラミ
ックス、アルミナセラミックスからなる半密閉容器中に
入れ、焼成炉内に供給する酸素流入量及び酸素濃度を表
１のように調整して１１００℃で焼成することにより、
表２に示す試料Ａ〜Ｏのチタン酸ジルコン酸鉛系焼結体
からなるアクチュエータ用圧電部材を得た。Next, an organic binder is added to the obtained synthetic powder, kneaded, dried and granulated to produce granules, and the obtained granules are uniaxially pressed under a pressure of 1.2 t / cm 2. After forming a molded body, the organic binder is degreased in an air atmosphere at 300 ° C., and then placed in a semi-closed container made of zirconia ceramics, magnesia ceramics, and alumina ceramics together with a lead atmosphere adjusting powder. By adjusting the inflow amount of oxygen and the oxygen concentration to be supplied into the firing furnace as shown in Table 1, and firing at 1100 ° C.,
A piezoelectric member for an actuator comprising a lead zirconate titanate-based sintered body of Samples A to O shown in Table 2 was obtained.
【００４２】また、従来例として、表１の試料Ｐに示す
平均粒径、粒径の標準偏差、ＢＥＴ比表面積を有するチ
タン酸ジルコン酸鉛系合成粉体を用い、脱脂処理した成
形体を大気雰囲気下、１０００℃で焼成し、得られたチ
タン酸ジルコン酸鉛系焼結体を、鉛雰囲気調整用の粉体
と共にマグネシアセラミックスからなる半密閉容器中に
入れたまま加圧・加熱室に入れ、２０体積％の酸素を含
んだアルゴンガスを充填し、２０００ｋｇｆ／ｃｍ2 の
圧力で、１１００℃で焼結することにより、表２に示す
試料Ｐのチタン酸ジルコン酸鉛系焼結体からなるアクチ
ュエータ用圧電部材を得た。Further, as a conventional example, a degreasing-processed molded body using a lead zirconate titanate-based synthetic powder having an average particle diameter, a standard deviation of the particle diameter, and a BET specific surface area shown in Sample P in Table 1 was air-conditioned. It is fired at 1000 ° C under an atmosphere, and the obtained lead zirconate titanate-based sintered body is put in a pressurized / heated chamber while being placed in a semi-closed container made of magnesia ceramics together with a powder for adjusting lead atmosphere. , Sintered at 1100 ° C. under a pressure of 2,000 kgf / cm 2 , thereby obtaining a sample P lead zirconate titanate-based sintered body shown in Table 2. A piezoelectric member for an actuator was obtained.
【００４３】そして、得られたチタン酸ジルコン酸鉛系
焼結体について、焼結体の相対密度、最大結晶粒子径、
最大ボイド径、無研磨状態での焼結体表面における表面
粗度、焼結体内部におけるボイド率、焼結体表層部と焼
結体内部におけるボイド率の差、焼結体の４点曲げ強度
及び圧電定数（ｄ15）、並びに研削加工を施した時の欠
け等の有無について調べた。Then, with respect to the obtained lead zirconate titanate-based sintered body, the relative density of the sintered body, the maximum crystal particle diameter,
Maximum void diameter, surface roughness of sintered body surface in non-polished state, void fraction inside sintered body, difference in void fraction between surface layer of sintered body and inside sintered body, 4-point bending strength of sintered body Then, the piezoelectric constant (d 15 ) and the presence or absence of chipping or the like during the grinding were examined.
【００４４】 なお、焼結体の最大ボイド径、焼結体内部
のボイド率、焼結体内外におけるボイド率の差の測定に
ついては、焼結体に鏡面加工（ダイヤモンド砥粒０〜１
μｍ仕上げ）を施し、ニレコ製ＬＵＺＥＸーＦＳ画像解
析装置を用いて、顕微鏡倍率２００倍、測定ポイント１
０ヶ所、測定面積１０．０×１０3 μｍ2 条件にて画像
解析して測定した。[0044] The maximum void diameter of the sintered body,
Measurement of the void fraction of porcelain, and the void fraction inside and outside the sintered body
The mirror surface processing (diamond abrasive grains 0 to 1)
μm finish) and Nireco's LUZEX-FS image solution
Using a analyzer, microscope magnification 200 times, measurement point 1
0 places, measurement area 10.0 × 10ThreeμmTwoImage by condition
Analyzed and measured.
【００４５】チタン酸ジルコン酸鉛系粒子の最大結晶粒
径については、塩酸にてケミカルエッチングを行ない、
金属顕微鏡にて２００倍の視野で３００μｍ×３００μ
ｍの範囲を１０ヶ所測定し、その最大径を最大結晶粒子
径とした。The maximum crystal grain size of the lead zirconate titanate-based particles was subjected to chemical etching with hydrochloric acid,
300μm × 300μ with a 200 × field of view with a metallographic microscope
The range of m was measured at 10 points, and the maximum diameter was defined as the maximum crystal particle diameter.
【００４６】無研磨状態での焼結体表面の表面粗度は、
ＪＩＳ Ｂ ０６０１に準拠して測定し、次に電極を形
成した時の断線の有無を確認するために、スパッタリン
グによって、３０μｍの線幅、０．１μｍ厚みを有する
金属膜を形成し、この金属膜に通電して断線がなかった
ものを○、断線していたものを×として評価した。The surface roughness of the sintered body surface in a non-polished state is as follows:
A metal film having a line width of 30 μm and a thickness of 0.1 μm was formed by sputtering in order to confirm whether or not there was a disconnection when an electrode was formed, by measuring according to JIS B 0601. Were evaluated as ○ when no current was applied and no disconnection was observed, and x was evaluated when disconnected.
【００４７】４点曲げ強度については、ＪＩＳ Ｒ１６
０１−１９９５に準拠し、圧電定数（ｄ15）について
は、ＥＭＡＳ−６００５に準じて行った。Regarding the four-point bending strength, JIS R16
The piezoelectric constant (d 15 ) was measured in accordance with EMAS-6005 in accordance with the method described in JP-A-01-1995.
【００４８】さらに、研削加工による欠けやチッピング
の有無を確認するため、厚み１００μm のダイヤモンド
ブレードを用いて、２００μｍピッチでダイシングを行
い、幅１００μｍ、深さ３５０μｍの溝を３００本形成
し、カケやチッピングの発生が見られないものを○、カ
ケやチッピングが発生したものを×として評価した。そ
れぞれの条件及び結果は表１及び表２に示す通りであ
る。Further, in order to confirm the presence or absence of chipping or chipping due to grinding, dicing was performed at a pitch of 200 μm using a diamond blade having a thickness of 100 μm, and 300 grooves having a width of 100 μm and a depth of 350 μm were formed. When no chipping was observed, it was evaluated as ○, and when chipping or chipping occurred, it was evaluated as x. The respective conditions and results are as shown in Tables 1 and 2.
【００４９】[0049]
【表１】 [Table 1]
【００５０】[0050]
【表２】 [Table 2]
【００５１】この結果、従来例である試料Ｐは、緻密化
されているものの、最大ボイド径が１０μｍを超え、ま
た焼結体表層部と焼結体内部におけるポイド率の差が１
％を超えているため、アクチュエータ用圧電部材として
用いるには焼結体表層部を研削する必要があり、さらに
研削加工を施すと欠けやチッピングが発生した。As a result, although the sample P, which is a conventional example, was densified, the maximum void diameter exceeded 10 μm, and the difference in the void ratio between the surface layer portion of the sintered body and the inside of the sintered body was 1%.
%, It was necessary to grind the surface layer of the sintered body in order to use it as a piezoelectric member for an actuator, and further grinding resulted in chipping and chipping.
【００５２】また、焼成時に半密閉容器の材質としてア
ルミナセラミックスを用いた試料Ｇ，Ｌでは、チタン酸
ジルコン酸鉛系焼結体との反応が見られ、この焼結体を
アクチュエータ用圧電部材として用いるには焼結体表層
部を研削加工にて除去する必要があった。In Samples G and L using alumina ceramics as the material of the semi-closed container during firing, a reaction with a lead zirconate titanate-based sintered body was observed, and this sintered body was used as a piezoelectric member for an actuator. For use, it was necessary to remove the surface layer of the sintered body by grinding.
【００５３】一方、試料Ａは、表１に見られるように、
チタン酸ジルコン酸鉛系合成粉体の平均粒径が０．７μ
ｍより大きく、粒子の標準偏差が０．２を超え、さらに
ＢＥＴ比表面積が５ｍ2 ／ｇ未満であるため、焼結体と
した時には焼結体内部のボイド率が１％を超え、焼結体
の密度が理論密度の９８％未満と緻密化が不十分であっ
た。その為、圧電定数（ｄ15）が６００ｐｍ／Ｖ未満と
低く、また、研削加工を施すと欠けやチッピングが発生
した。しかも焼結体表層部と焼結体内部におけるボイド
率の差も１％を超え大きいため、アクチュエータ用圧電
部材として用いるには焼結体表層部を研削する必要があ
った。その上、無研磨状態での焼結体表面が粗いため、
その表面上に微少幅の金属膜を形成すると断線した。On the other hand, as shown in Table 1, sample A
The average particle size of the lead zirconate titanate-based synthetic powder is 0.7μ.
m, the standard deviation of the particles exceeds 0.2, and the BET specific surface area is less than 5 m 2 / g. When the body density was less than 98% of the theoretical density, densification was insufficient. For this reason, the piezoelectric constant (d 15 ) was as low as less than 600 pm / V, and chipping and chipping occurred when grinding was performed. In addition, the difference in void ratio between the surface layer portion of the sintered body and the inside of the sintered body is more than 1%, so that the surface layer portion of the sintered body must be ground in order to use it as a piezoelectric member for an actuator. In addition, because the surface of the sintered body in the unpolished state is rough,
When a minute width metal film was formed on the surface, the wire was broken.
【００５４】また、試料Ｄは、焼成時の酸素濃度が低い
ため、焼結体とした時には焼結体内部のボイド率が１％
を超え、焼結体の密度が理論密度の９８％未満と緻密化
が不十分であった。その為、圧電定数（ｄ15）が６００
ｐｍ／Ｖ未満と低く、また、研削加工を施すと欠けやチ
ッピングが発生した。しかも焼結体表層部と焼結体内部
におけるボイド率の差も１％を超え大きいため、アクチ
ュエータ用圧電部材として用いるには焼結体表層部を研
削する必要があった。Since the sample D had a low oxygen concentration at the time of firing, when it was formed into a sintered body, the void ratio inside the sintered body was 1%.
, And the density of the sintered body was less than 98% of the theoretical density, resulting in insufficient densification. Therefore, the piezoelectric constant (d 15 ) is 600
It was as low as less than pm / V, and chipping and chipping occurred when grinding was performed. In addition, the difference in void ratio between the surface layer portion of the sintered body and the inside of the sintered body is more than 1%, so that the surface layer portion of the sintered body must be ground in order to use it as a piezoelectric member for an actuator.
【００５５】これに対し、試料Ｂ，Ｃ，Ｅ，Ｆ，Ｈ〜
Ｋ，Ｍ〜Ｏは、いずれもチタン酸ジルコン酸鉛系合成粉
体の平均粒径が０．４〜０．７μｍ、粒子の標準偏差が
０．２以下、ＢＥＴ比表面積が５〜１３ｍ2 ／ｇの範囲
にあり、焼成時にはマグネシアセラミックス又はジルコ
ニアセラミックスの半密閉容器を用いて焼成炉内の酸素
濃度を２５体積％以上としてあることから、焼結体とし
た時には、焼結体内部のボイド率を１０％以下、焼結体
の密度を理論密度の９８％以上と充分に緻密化すること
ができ、６００ｐｍ／Ｖ以上の高い圧電定数（ｄ15）を
得ることができるとともに、焼結体中の最大ボイド径を
１０μｍ以下とできるため、研削加工を施しても欠けや
チッピングを生じることがなかった。しかも、最大結晶
粒子径が１０μｍ以下で、無研磨状態での焼結体表面を
中心線平均粗さ（Ｒａ）で０．３μｍ以下とできるた
め、無研磨状態での焼結体表面に直接金属膜を被覆して
も断線は見られないというように優れていた。On the other hand, samples B, C, E, F, H
K and M to O each have an average particle diameter of 0.4 to 0.7 μm, a standard deviation of particles of 0.2 or less, and a BET specific surface area of 5 to 13 m 2 / g, the oxygen concentration in the firing furnace is set to 25% by volume or more using a semi-closed container of magnesia ceramics or zirconia ceramics at the time of firing. 10% or less, and the density of the sintered body to 98% or more of the theoretical density can be sufficiently densified, and a high piezoelectric constant (d 15 ) of 600 pm / V or more can be obtained. Since the maximum void diameter can be set to 10 μm or less, chipping and chipping did not occur even when grinding was performed. Moreover, since the maximum crystal grain diameter is 10 μm or less and the surface of the sintered body in the non-polished state can be 0.3 μm or less in center line average roughness (Ra), the metal is directly applied to the surface of the sintered body in the non-polished state. It was excellent that no disconnection was seen even when the film was coated.
【００５６】 [0056]
【発明の効果】以上のように、本発明によれば、特定の
粒径、粒度分布等を有するチタン酸ジルコン酸鉛系合成
粉体を所定の形状に成形した成形体を、マグネシアセラ
ミックス又はジルコニアセラミックスからなる半密閉容
器中に入れ、炉内雰囲気の酸素濃度を２５体積％以上に
保ちながら焼成することにより、焼結体の密度が理論密
度の９８％以上、最大結晶粒子径が１０μｍ以下、最大
ボイド径が１０μｍ以下であるとともに、無研磨状態で
の前記焼結体表面における表面粗度が中心線平均粗さ
（Ｒａ）で０．３μｍ以下であり、前記焼結体表面から
１００μｍまでの深さを焼結体表層部、それ以外を焼結
体内部とした時、該焼結体内部におけるボイド率が１．
０％以下でかつ焼結体表層部と焼結体内部におけるボイ
ド率の差が１．０％以下であるチタン酸ジルコン酸鉛系
焼結体からなるアクチュエータ用圧電部材を製造するよ
うにしたことから、アクチュエータとして重要な圧電定
数等の圧電諸定数を向上させることができ、超音波モー
タやインクジェットプリンタヘッド等の圧電アクチュエ
ータとして用いた時にはその性能を高めることができる
とともに、均質な構造を有することから、焼結体表層部
を除去する必要がなく、原料の無駄を無くすことができ
る。また、所望の形状とするために研削加工を施しても
欠けやチッピングを生じ難く、無研磨状態での焼結体表
面が滑らかであるため、この焼結体表面に直接電極や電
極引出線を形成することができる。As described above, according to the present invention, a molded body obtained by molding a lead zirconate titanate-based synthetic powder having a specific particle size, a particle size distribution, and the like into a predetermined shape is made of magnesia ceramics or zirconia. By placing in a semi-closed container made of ceramics and firing while maintaining the oxygen concentration in the furnace atmosphere at 25% by volume or more, the density of the sintered body is 98% or more of the theoretical density, the maximum crystal grain size is 10 μm or less, The maximum void diameter is 10 μm or less, and the surface roughness on the surface of the sintered body in a non-polished state is 0.3 μm or less in center line average roughness (Ra), and the surface roughness is 100 μm or less from the surface of the sintered body. When the depth is the surface layer portion of the sintered body and the rest is the inside of the sintered body, the void ratio inside the sintered body is 1.
A piezoelectric member for an actuator made of a lead zirconate titanate-based sintered body having a difference of 0% or less and a void ratio between the surface layer portion of the sintered body and the inside of the sintered body of 1.0% or less is manufactured. Therefore, it is possible to improve various piezoelectric constants such as the piezoelectric constant which is important as an actuator, and to improve the performance when used as a piezoelectric actuator such as an ultrasonic motor or an ink jet printer head, and to have a uniform structure. Therefore, there is no need to remove the surface layer portion of the sintered body, and waste of raw materials can be eliminated. In addition, even if grinding processing is performed to obtain a desired shape, chipping and chipping hardly occur, and the surface of the sintered body in an unpolished state is smooth, so that an electrode or an electrode lead wire is directly formed on the surface of the sintered body. Can be formed.
Claims (2)
ペロブスカイト組成を有し、前記基本組成式のＰｂがＢ
ａ、Ｓｒ、Ｌａのうち少なくとも１種以上の元素で一部
置換され、且つＺｒ及びＴｉがＮｂ、Ｚｎ、Ｓｂ、Ｎ
ｉ、Ｍｇのうち少なくとも１種以上の元素で一部置換さ
れているチタン酸ジルコン酸鉛系焼結体からなるアクチ
ュエータ用圧電部材において、前記焼結体の密度が理論
密度の９８％以上、最大結晶粒子径が１０μｍ以下、最
大ボイド径が１０μｍ以下であるとともに、無研磨状態
での前記焼結体表面における表面粗度が中心線平均粗さ
（Ｒａ）で０．３μｍ以下であり、前記焼結体表面から
１００μｍまでの深さを焼結体表層部、それ以外を焼結
体内部とした時、該焼結体内部におけるボイド率が１．
０％以下でかつ焼結体表層部と焼結体内部におけるボイ
ド率の差が１．０％以下であることを特徴とするアクチ
ュエータ用圧電部材。A basic composition formula has a perovskite composition represented by PbZrTiO 3 , wherein Pb in the basic composition formula is B
a, Sr, and La are partially substituted with at least one or more elements, and Zr and Ti are replaced with Nb, Zn, Sb, N
In a piezoelectric member for an actuator made of a lead zirconate titanate-based sintered body partially substituted with at least one or more of i and Mg, the density of the sintered body is 98% or more of the theoretical density, The crystal grain diameter is 10 μm or less, the maximum void diameter is 10 μm or less, and the surface roughness of the surface of the sintered body in a non-polished state is 0.3 μm or less in center line average roughness (Ra). When the depth from the surface of the sintered body to 100 μm is defined as the surface layer portion of the sintered body and the other portion is defined as the inside of the sintered body, the void ratio inside the sintered body is 1.
A piezoelectric member for an actuator, wherein 0% or less and a difference in void ratio between the surface layer portion of the sintered body and the inside of the sintered body are 1.0% or less.
の標準偏差が０．２μｍ以下、ＢＥＴ比表面積が５〜１
３ｍ2 ／ｇであるチタン酸ジルコン酸鉛系合成粉体を所
定の形状に成形した成形体を、マグネシア系セラミック
ス又はジルコニア系セラミックスからなる半密閉容器に
入れ、炉内雰囲気の酸素濃度を２５体積％以上に保ちな
がら焼成することを特徴とするアクチュエータ用圧電部
材の製造方法。2. An average particle size of 0.4 to 0.7 μm, a standard deviation of particle size distribution of 0.2 μm or less, and a BET specific surface area of 5 to 1 μm.
A molded body obtained by molding a lead zirconate titanate-based synthetic powder of 3 m 2 / g into a predetermined shape is placed in a semi-closed container made of magnesia-based ceramic or zirconia-based ceramic, and the oxygen concentration in the furnace atmosphere is adjusted to 25 vol. %, While firing at a rate of not less than%.
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|---|---|---|---|
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|---|---|---|---|
| JP24264199A JP4582835B2 (en) | 1999-08-30 | 1999-08-30 | Method for manufacturing piezoelectric member for actuator |
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|---|---|---|---|
| JP2010157978A Division JP5132728B2 (en) | 2010-07-12 | 2010-07-12 | Piezoelectric member for actuator |
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| Publication Number | Publication Date |
|---|---|
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Family
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|---|---|---|---|---|
| JP2004158849A (en) * | 2002-10-17 | 2004-06-03 | Kyocera Corp | Actuator and manufacturing method therefor, and printing head |
| WO2006093042A1 (en) * | 2005-03-01 | 2006-09-08 | Ibiden Co., Ltd. | Piezoelectric element |
| WO2006093043A1 (en) * | 2005-03-01 | 2006-09-08 | Ibiden Co., Ltd. | Multilayer piezoelectric element |
| EP1367036A3 (en) * | 2002-05-30 | 2006-09-27 | TDK Corporation | Piezoelectric ceramic production method and piezoelectric element production method |
| JP2007088022A (en) * | 2005-09-20 | 2007-04-05 | Kyocera Corp | Multilayer piezoelectric body |
| WO2008013099A1 (en) * | 2006-07-25 | 2008-01-31 | Tosoh Corporation | Sintered zirconia having high light transmission and high strength, use of the same and process for production thereof |
| JP2008050247A (en) * | 2006-07-25 | 2008-03-06 | Tosoh Corp | Sintered zirconia having high strength and process for production thereof |
| JP2009007197A (en) * | 2007-06-27 | 2009-01-15 | Kyocera Corp | Piezoelectric ceramics, piezoelectric actuator, and liquid discharge head |
| CN114105636A (en) * | 2021-12-30 | 2022-03-01 | 景德镇市鑫惠康电子有限责任公司 | Method for preparing 4M energy-gathering transducer by utilizing indium selenide modified niobium-zinc lead zirconate titanate system |
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