JP2627480B2 - Oxide piezoelectric material - Google Patents
Oxide piezoelectric materialInfo
- Publication number
- JP2627480B2 JP2627480B2 JP6032414A JP3241494A JP2627480B2 JP 2627480 B2 JP2627480 B2 JP 2627480B2 JP 6032414 A JP6032414 A JP 6032414A JP 3241494 A JP3241494 A JP 3241494A JP 2627480 B2 JP2627480 B2 JP 2627480B2
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric
- oxide
- piezoelectric material
- composition
- pbtio
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 description 11
- 238000010168 coupling process Methods 0.000 description 11
- 238000005859 coupling reaction Methods 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 5
- 229910002056 binary alloy Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｐｂ（Ｙ2/3 Ｗ1/3 ）
Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 系を基本組成とし、
高い電気機械結合係数及び大きい圧電定数を有し、低い
機械的品質係数を有するような酸化物圧電材料に関する
ものである。The present invention relates to Pb (Y 2/3 W 1/3 )
O 3 -PbZrO 3 -PbTiO 3 system as a basic composition,
The present invention relates to an oxide piezoelectric material having a high electromechanical coupling coefficient and a large piezoelectric constant, and having a low mechanical quality factor.
【０００２】[0002]
【従来の技術】一般的に、酸化物圧電材料は、正方晶系
と菱面晶系の間の相境界（ＭＰＢ：Morphotropic Phase
Boundary)で最も優秀な圧電特性を表すと言うＪａｆｆ
ｅの報告が発表されて以来、不純物添加が第３成分であ
るＡＢＯ3 形態のペロブスカイト構造物を変化させるこ
とで、焼結性を始めとする圧電特性及び誘電特性の改善
を試図した種々の研究が持続的に行われている。2. Description of the Related Art In general, an oxide piezoelectric material has a phase boundary between a tetragonal system and a rhombohedral system (MPB: Morphotropic Phase).
Boundary) Jaff says to show the best piezoelectric properties
Since the publication of report e, various attempts have been made to improve the piezoelectric properties and dielectric properties including sintering properties by changing the perovskite structure in the form of ABO 3 , which is the third component, by adding impurities. Research is ongoing.
【０００３】例えば、ＰｂＺｒＯ3 −ＰｂＴｉＯ3 系酸
化物圧電材料は、超音波振動子、音響フィルタ等の振動
素子として従来から利用されており、現在、その用途
は、医療機器、ロボット、工場自動化、非破壊検査及び
精密位置決定等のアクチュエータとして利用するまでに
至るようになった。For example, a PbZrO 3 -PbTiO 3 -based oxide piezoelectric material has been conventionally used as a vibrating element such as an ultrasonic vibrator, an acoustic filter, and the like. It has come to be used as an actuator for nondestructive inspection and precise position determination.
【０００４】[0004]
【発明が解決しようとする課題】ところで、従来、この
様な各種の装置に使用する素材として、ＰｂＺｒＯ3 −
ＰｂＴｉＯ3 にＮｂ2 Ｏ5 やＷＯ3 等種々の不純物を添
加したもの（F.Kulcsar:J.Am.Ceram.Soc,42(1959)343,
H.Banno:Jan.J.Appl.Phy.6(1976)954）や、Ｐｂ（Ｍｇ
1/3 Ｎｂ2/3 ）Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 等の
諸３元系組成のものが開発されて来たが（田中哲郎等：
圧電セラミック材料，学献社,(1943)110−130)、これら
の素材は、電気機械結合係数（Ｋｐ）、機械的品質係数
（Ｑｍ）、又は誘電定数の値が低いだけでなく、圧電定
数（ｄ33）値が低いことから、水中聴音機（Hydro-phon
e)、フォノピックアップ（Phonopickup)、音響探知機
（Sounddetector) 、加速度計（Accelerometer)、遅延
線（Delay line) 等、信号受電用素子としては勿論、超
音波モータ、ディフォーマブルミラー（Deformable mir
ror)等のアクチュエータとして応用するにも適合でない
実情である。By the way, conventionally, PbZrO 3-
PbTiO 3 to which various impurities such as Nb 2 O 5 and WO 3 are added (F. Kulcsar: J. Am. Ceram. Soc, 42 (1959) 343,
H. Banno: Jan. J. Appl. Phy. 6 (1976) 954) and Pb (Mg
Various ternary compositions such as 1/3 Nb 2/3 ) O 3 -PbZrO 3 -PbTiO 3 have been developed (Tetsuro Tanaka et al .:
Piezoceramic materials, Gakusensha, (1943) 110-130), these materials have low values of electromechanical coupling coefficient (Kp), mechanical quality factor (Qm), or dielectric constant, as well as piezoelectric constant. (d 33) from the low value, hydrophones machine (Hydro-phon
e), phono pickup (Phonopickup), sound detector (Sounddetector), accelerometer (Accelerometer), delay line (Delay line), etc., as well as ultrasonic wave motor, deformable mirror (Deformable mirror)
It is not suitable for application as an actuator such as ror).
【０００５】特に、アクチュエータとして応用する場
合、電気機械結合係数と圧電定数が大きくなくてはなら
ない。万一、電気機械結合係数が低ければ、素子が電気
的入力を機械的振動に変化させる時に内部熱が発生しエ
ネルギ損失は勿論、酸化物圧電材料の特性劣化が起こ
る。又、印加された電気的入力に対する機械的変位を大
きく発生させるためにも圧電定数が大であらねばならな
い。In particular, when applied as an actuator, the electromechanical coupling coefficient and the piezoelectric constant must be large. If the electromechanical coupling coefficient is low, internal heat is generated when the element changes electrical input into mechanical vibration, resulting in energy loss as well as deterioration of the characteristics of the oxide piezoelectric material. In addition, the piezoelectric constant must be large in order to generate a large mechanical displacement with respect to the applied electric input.
【０００６】従って、本発明は、電気機械結合係数が高
く機械的品質係数の低い信号受電用素子は勿論、アクチ
ュエータとしても十分に適合可能な高い電気機械結合係
数及び大きい圧電定数を持つ酸化物圧電材料を提供する
にその目的がある。Accordingly, the present invention provides an oxide piezoelectric element having a high electromechanical coupling coefficient and a large piezoelectric constant that can be sufficiently adapted as an actuator as well as a signal receiving element having a high electromechanical coupling coefficient and a low mechanical quality coefficient. Providing the material has its purpose.
【０００７】[0007]
【課題を解決するための手段及び作用】このため、本発
明の酸化物圧電材料は、ｘＰｂ（Ｙ2/3 Ｗ1/3 ）Ｏ3 −
ｙＰｂＺｒＯ3 −ｚＰｂＴｉＯ3 系を基本組成とし、 0.01≦ｘ≦0.20 0.215 ≦ｙ，ｚ≦0.764 （但し、ｘ＋ｙ＋ｚ＝１） の組成範囲を有することを特徴とする。Accordingly, the oxide piezoelectric material according to the present invention has a composition of xPb (Y 2/3 W 1/3 ) O 3 −
It has a basic composition of yPbZrO 3 -zPbTiO 3 and has a composition range of 0.01 ≦ x ≦ 0.20 0.215 ≦ y, z ≦ 0.764 (where x + y + z = 1).
【０００８】また、添加物として、Ｌａ2 Ｏ3 、ＭｎＯ
2 、Ｎｂ2 Ｏ5 、Ｃｒ2 Ｏ3 及びＴａ 2 Ｏ 5 のうちのい
ずれか一つを0.1 〜1.0 重量％含有させるとよい。この
様な本発明の酸化物圧電材料は次のような一般的に広く
用いられる酸化物混合方法で容易に製作が可能である。
即ち、先ずＰｂＯ、ＴｉＯ2 、ＺｒＯ2 、Ｙ2 Ｏ3 、Ｗ
Ｏ3 等の酸化物を適正比率で正確に計量しジルコニアボ
ールミルを利用し混合, 粉砕する。一方、この時使用す
る原料として、加熱すれば酸化物に容易に転換する化合
物、即ち、水酸化物及び炭酸塩等の包含した原料化合物
を使用することも出来る。混合の完了した試料は８００
−９００℃で仮焼きした後、更に、ボールミルにより再
粉砕させ合成粉末を造り、以後、この粉末に水又はＰＶ
Ａ水溶液等の結合剤を微量添加し１ ton／cm2 の圧力で
加圧、成型した後、１１５０−１２２５℃の温度で焼結
する。このような焼結時には、低い揮発温度（約８８０
℃）を持つＰｂＯの揮発に伴う圧電特性の低下を防止す
るために密閉容器内で焼結を遂行する。Further, La 2 O 3 and MnO are used as additives.
2 , Nb 2 O 5 , Cr 2 O 3 and Ta 2 O 5 are preferably contained in an amount of 0.1 to 1.0% by weight. Such an oxide piezoelectric material of the present invention can be easily manufactured by the following widely used oxide mixing method.
That is, first, PbO, TiO 2 , ZrO 2 , Y 2 O 3 , W
Oxides such as O 3 are accurately measured at an appropriate ratio, mixed and pulverized using a zirconia ball mill. On the other hand, as a raw material to be used at this time, a compound which can be easily converted to an oxide when heated, that is, a raw material compound including a hydroxide and a carbonate can also be used. 800 samples after mixing
After calcination at −900 ° C., the powder was further re-ground by a ball mill to produce a synthetic powder.
A small amount of a binder such as an aqueous solution A is added, pressurized and molded at a pressure of 1 ton / cm 2 , and then sintered at a temperature of 1150 to 1225 ° C. During such sintering, low volatilization temperatures (about 880)
C), sintering is performed in a closed container in order to prevent the deterioration of the piezoelectric properties due to the volatilization of PbO.
【０００９】この様にして製造した焼結体は一般的な方
法により両面に電極が形成されるが、９０−１１０℃程
度のシリコン油内でその電極に直流電界３５ＫＶ／ｃｍ
を３０分間印加することで分極が行われる。この様な製
造工程を通じ従来のＰｂＺｒＯ3 −ＰｂＴｉＯ3 ２元系
又はＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −ＰｂＺｒＯ3 −Ｐ
ｂＴｉＯ3 ３元系の圧電材料とは相違した組成を持つ材
料で優秀な圧電特性を具備した酸化物圧電材料が容易に
得られる。Electrodes are formed on both sides of the sintered body manufactured in this manner by a general method, and a DC electric field of 35 KV / cm is applied to the electrodes in a silicon oil at about 90 to 110 ° C.
Is polarized for 30 minutes. Through such a manufacturing process, a conventional PbZrO 3 -PbTiO 3 binary system or Pb (Mg 1/3 Nb 2/3 ) O 3 -PbZrO 3 -P
An oxide piezoelectric material having excellent piezoelectric properties can be easily obtained from a material having a composition different from that of the bTiO 3 ternary piezoelectric material.
【００１０】また、添加物としてＣｒ2 Ｏ3 、Ｌａ2 Ｏ
3 、Ｔａ2 Ｏ5 、ＭｎＯ2 及びＮｂ 2 Ｏ5 のいずれか１
つを添加する場合は、添加する酸化物を、上記のＰｂ
Ｏ、ＴｉＯ2 、ＺｒＯ2 、Ｙ2 Ｏ3 、ＷＯ3 等の酸化物
に加えて適正比率で正確に計量しジルコニアボールミル
を利用し混合, 粉砕し、上述した方法で製造すればよ
い。そして、このような添加物を添加することにより、
圧電特性の改善が図れるようになる。Further, Cr is used as an additive.TwoOThree, LaTwoO
Three, TaTwoOFive, MnOTwoAnd Nb TwoOFiveAny one of
When one is added, the oxide to be added is
O, TiOTwo, ZrOTwo, YTwoOThree, WOThreeOxides such as
Zirconia ball mill
Mixing using,Crushed and manufactured by the method described above
No. And by adding such additives,
The piezoelectric characteristics can be improved.
【００１１】ここで、上記のｘ、ｙ及びｚが、上記の範
囲（0.01≦ｘ≦0.20、0.215 ≦ｙ，ｚ≦0.764 ）より多
過ぎても少な過ぎても、良好な圧電特性及び誘電特性を
得ることができない。また、Ｃｒ2 Ｏ3 、Ｌａ2 Ｏ3 、
Ｔａ2 Ｏ5 、ＭｎＯ2 及びＮｂ2 Ｏ5 の各添加物の添加
範囲についても、同様で、0.1 〜1.0 重量％の範囲より
多過ぎても少な過ぎても、良好な圧電特性及び誘電特性
を得ることができない。Here, if the above-mentioned x, y and z are too large or too small to be in the above range (0.01 ≦ x ≦ 0.20, 0.215 ≦ y, z ≦ 0.764), good piezoelectric and dielectric properties are obtained. Can not get. Further, Cr 2 O 3 , La 2 O 3 ,
The same applies to the range of addition of each additive of Ta 2 O 5 , MnO 2 and Nb 2 O 5 , and good piezoelectric properties and dielectric properties are obtained when the content is too large or too small in the range of 0.1 to 1.0% by weight. I can't get it.
【００１２】[0012]
【実施例】以下、本発明の実施例について説明する。ま
ず、添加物のない実施例について説明する。ｘＰｂ（Ｙ
2/3 Ｗ1/3 ）Ｏ3 −ｙＰｂＺｒＯ3 −ｚＰｂＴｉＯ3 の
３元系において、 0.01≦ｘ≦0.20 0.215 ≦ｙ，ｚ≦0.764 （但し、ｘ＋ｙ＋ｚ＝１） の組成範囲となるようＰｂＯ、ＴｉＯ2 、ＺｒＯ2 、Ｙ
2 Ｏ3 及びＷＯ3 等の酸化物を各モル比に従い１０-4ｇ
まで正確に計量し、ジルコニアボールミル中で混合, 粉
砕した。次に、混合の完了した試料は８００−９００℃
で仮焼きした後、ボールミルで再粉砕し、その粉砕され
たものに水又はＰＶＡ水溶液等の結合剤を微量添加し１
ton／cm2 の圧力で加圧、成型した後、１１５０−１２
２５℃の温度で焼結した。焼結時、組成成分中の１つで
あるＰｂＯの揮発温度（約８８０℃）が低いため、正確
な化学的等量を成し遂げられず圧電特性の低下を招来す
る虞れがあるので、実施組成と同一な組成の粉末をＰｂ
Ｏの揮発抑制用雰囲気粉末にし密閉した容器内で焼結を
行い、この時、最高温度での維持時間は１時間とした。Embodiments of the present invention will be described below. First, examples without additives will be described. xPb (Y
In a ternary system of 2/3 W 1/3 ) O 3 -yPbZrO 3 -zPbTiO 3 , PbO and TiO are adjusted to have a composition range of 0.01 ≦ x ≦ 0.20 0.215 ≦ y, z ≦ 0.764 (where x + y + z = 1). 2 , ZrO 2 , Y
Oxides such as 2 O 3 and WO 3 are added in an amount of 10 −4 g according to the molar ratio.
The mixture was accurately weighed and mixed and pulverized in a zirconia ball mill. Next, the mixed sample is 800-900 ° C.
After calcining in a ball mill, the mixture is reground by a ball mill, and a small amount of a binder such as water or an aqueous PVA solution is added to the ground material.
After pressurizing and molding at a pressure of ton / cm 2 , 1150-12
Sintered at a temperature of 25 ° C. Sintering, because the volatilization temperature of PbO, which is one in the composition components (about 880 ° C.) is low, because there is a possibility to lead to deterioration of the piezoelectric characteristics not be achieved form a precise chemical equivalent amount, A powder having the same composition as the working composition was Pb
Sintering was carried out in a sealed container with an atmosphere powder for suppressing volatilization of O, and the maintenance time at the maximum temperature was 1 hour.
【００１３】焼結の完了した成形焼結体は、直径１５ｍ
ｍ、厚さ１ｍｍの円板状に加工した後、両面に電極を形
成し、この電極に直流電界３５ＫＶ／cmを約９０−１１
０℃のシリコン油内で３０分間印加し分極をした。分極
の完了した試片に対し、ＩＲＥ，ＳＴＤ（Proc.IRE,137
(1949)1378）に従い、電気機械結合係数（Ｋｐ）、機械
的品質係数（Ｑｍ）及び周波数定数（Frequency Consta
nt) 等を測定した所、組成比の異なる各焼結体の測定結
果は下の表１の通りである。[0013] The sintered compact having been sintered has a diameter of 15 m.
After processing into a disk having a thickness of 1 mm and a thickness of 1 mm, electrodes are formed on both sides, and a DC electric field of 35 KV / cm is applied to the electrodes for about 90-11.
Polarization was performed by applying a voltage of 30 ° C. in silicone oil for 30 minutes. IRE, STD (Proc. IRE, 137)
(1949) 1378), the electromechanical coupling coefficient (Kp), the mechanical quality factor (Qm) and the frequency constant (Frequency Consta
nt) and the like, the measurement results of the respective sintered bodies having different composition ratios are as shown in Table 1 below.
【００１４】[0014]
【表１】 [Table 1]
【００１５】上記の表１で、Ｆ．Ｔは焼結温度（℃）、
Ｋｐは電気機械結合係数（％）、Ｋ 33 T は１ＫＨｚの周
波数で２５℃で測定した試片の誘電率、ｄ33は圧電定数
(×10-2C/N)、Ｑｍは機械的品質係数をそれぞれ表す。
表１から明らかのように、Ｐｂ（Ｙ2/3 Ｗ1/3 ）Ｏ3 が
１−３モル％で固溶される時、電気機械結合係数が高く
圧電定数が非常に大で優秀な圧電特性を表した。In Table 1 above, F.I. T is the sintering temperature (° C),
Kp is the electromechanical coupling coefficient (%), K 33 TIs the frequency of 1 kHz
Dielectric constant of the specimen, measured at 25 ° C. at wavenumber, d33Is the piezoelectric constant
(× 10-2C / N) and Qm represent mechanical quality factors, respectively.
As is clear from Table 1, Pb (Y2/3W1/3) OThreeBut
High electromechanical coupling coefficient when solid solution at 1-3 mol%
The piezoelectric constant was very large and exhibited excellent piezoelectric properties.
【００１６】本発明のＰｂ（Ｙ2/3 Ｗ1/3 ）Ｏ3 −Ｐｂ
ＺｒＯ3 −ＰｂＴｉＯ3 ３元系圧電材料は、従来のＰｂ
ＺｒＯ3 −ＰｂＴｉＯ3 ２元系に比べ相当に広い範囲に
わたり優秀な圧電特性を保有しており、２元系であるＰ
ｂＺｒＯ3 −ＰｂＴｉＯ3 系と本発明の３元系Ｐｂ（Ｙ
2/3 Ｗ1/3 ）Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 ３元系
との圧電特性を比較すれば次の表２の通りである。The Pb (Y 2/3 W 1/3 ) O 3 -Pb of the present invention
ZrO 3 -PbTiO 3 3-element piezoelectric material, conventional Pb
ZrO 3 -PbTiO 3 has excellent piezoelectric properties over a considerably wide range as compared with the binary system, and the binary system P
bZrO 3 -PbTiO 3 system and the ternary system Pb (Y
2/3 W 1/3 ) O 3 —PbZrO 3 —PbTiO 3 A comparison of the piezoelectric characteristics with the ternary system is shown in Table 2 below.
【００１７】[0017]
【表２】 [Table 2]
【００１８】上記の表２において、２元系であるＰｂＺ
ｒＯ3 −ＰｂＴｉＯ3 系の場合、優秀な圧電特性を表す
範囲がＭＰＢ領域に局限するのに対し、本発明組成の場
合は相当広い組成範囲で優秀な特性を持つ素材が容易に
得られることを表している。更に詳述すれば、参考例１
及び参考例２に見るように２元系組成の場合、一点に局
限して比較的優秀な特性を表すが、本発明の実施例によ
れば、実施例５−実施例７そして実施例１３−実施例１
５まで等、広い領域にわたり圧電定数（ｄ33）特性が改
善されるのを観察することができる。In Table 2 above, the binary system PbZ
In the case of the rO 3 -PbTiO 3 system, the range exhibiting excellent piezoelectric properties is limited to the MPB region, whereas the composition of the present invention can easily obtain a material having excellent properties in a considerably wide composition range. Represents. More specifically, Reference Example 1
In addition, as shown in Reference Example 2, in the case of the binary composition, relatively excellent characteristics are exhibited at one point. However, according to the embodiment of the present invention, Examples 5 to 7 and 13 to 13 Example 1
It can be observed that the piezoelectric constant (d 33 ) characteristics are improved over a wide area such as up to 5.
【００１９】次に、上述のＰｂ（Ｙ2/3 Ｗ1/3 ）Ｏ3 −
ＰｂＺｒＯ3 −ＰｂＴｉＯ3 ３元系の圧電材料の圧電特
性を更に向上させることを目的として、Ｐｂ（Ｙ2/3 Ｗ
1/3）Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 ３元系に添加
物を添加した実施例について説明する。本発明のＰｂ
（Ｙ2/3 Ｗ1/3 ）Ｏ3 −ＰｂＺｒＯ3 −ＰｂＴｉＯ3 ３
元系では、添加物としてＬａ2 Ｏ3 、ＭｎＯ2 ，Ｔａ2
Ｏ5 、Ｎｂ2 Ｏ5 及びＣｒ2 Ｏ3酸化物中のいずれか１
つを添加することで圧電特性を改善できる。Next, the above-mentioned Pb (Y 2/3 W 1/3 ) O 3 −
In order to further improve the piezoelectric characteristics of the ternary piezoelectric material of PbZrO 3 -PbTiO 3 , Pb (Y 2/3 W
1/3 ) Examples in which additives are added to the ternary system of O 3 —PbZrO 3 —PbTiO 3 will be described. Pb of the present invention
(Y 2/3 W 1/3) O 3 -PbZrO 3 -PbTiO 3 3
In the original system, La 2 O 3 , MnO 2 , Ta 2
Any one of O 5 , Nb 2 O 5 and Cr 2 O 3 oxide
The addition of one can improve the piezoelectric characteristics.
【００２０】この場合の製造方法は、ＰｂＯ、Ｔｉ
Ｏ2 、ＺｒＯ2 、Ｙ2 Ｏ3 及びＷＯ3 等の酸化物に加え
て、Ｌａ2 Ｏ3 、ＭｎＯ2 ，Ｔａ2 Ｏ5 、Ｎｂ2 Ｏ5 及
びＣｒ2Ｏ3 のいずれか１を、それぞれ添加物として加
えて各モル比に従い１０-4ｇまで正確に計量した後、前
述した添加物のない場合と同じようにして製造すればよ
い。In this case, the manufacturing method includes PbO, Ti
In addition to oxides such as O 2 , ZrO 2 , Y 2 O 3 and WO 3 , any one of La 2 O 3 , MnO 2 , Ta 2 O 5 , Nb 2 O 5 and Cr 2 O 3 is added, respectively. After adding as an additive and weighing accurately up to 10 -4 g according to each molar ratio, it may be produced in the same manner as in the case where the additive is not used.
【００２１】本実施例では、表１に示した実施例１４の
組成（ｘ＝0.02、ｙ＝0.51、ｚ＝0.47）に各々の添加物
を添加した場合における、添加物の添加に伴う圧電特性
の変化を次の表３に表した。In this embodiment, when each additive is added to the composition of Example 14 (x = 0.02, y = 0.51, z = 0.47) shown in Table 1, the piezoelectric characteristics accompanying the addition of the additive are shown. Are shown in Table 3 below.
【００２２】[0022]
【表３】 [Table 3]
【００２３】上記の表３で明らかなように、Ｌａ
2 Ｏ3 、ＭｎＯ2 、Ｔａ2 Ｏ5 、Ｎｂ2 Ｏ 5 及びＣｒ2
Ｏ3 のいずれか１つを微量添加することで、電気機械結
合係数、圧電定数等の圧電特性が向上するのは勿論、Ｍ
ｎＯ2 添加の場合には、圧電特性の大きな低下なく機械
的品質係数が増大し、機械的品質係数の要求される用途
に適合する素子を得ることができる。As is apparent from Table 3 above, La
TwoOThree, MnOTwo, TaTwoOFive, NbTwoO FiveAnd CrTwo
OThreeBy adding a small amount of either one of
In addition to the improvement of the piezoelectric characteristics such as the integration coefficient and the piezoelectric constant,
nOTwoIn the case of addition, there is no significant decrease in piezoelectric characteristics
Applications where mechanical quality factor is increased and mechanical quality factor is required
Can be obtained.
【００２４】図１には、本発明の酸化物圧電材料の組成
比範囲を示したＰｂ（Ｙ2/3 Ｗ1/3）Ｏ3 −ＰｂＺｒＯ
3 −ＰｂＴｉＯ3 の３元系図で、Ａ、Ｂ、Ｃ、Ｄで囲ま
れた多角形内の斜線の部分が、本発明の酸化物成分の組
成範囲を示す。ここで、図１の３元系図に表示された本
発明の組成範囲を示す多角形のＡ点は実施例４７、Ｂ点
は実施例３８、Ｃ点は実施例１、Ｄ点は実施例４を各々
示すものである。FIG. 1 shows Pb (Y 2/3 W 1/3 ) O 3 -PbZrO showing the composition ratio range of the oxide piezoelectric material of the present invention.
In the ternary diagram of 3- PbTiO 3 , the hatched portion in the polygon surrounded by A, B, C, and D indicates the composition range of the oxide component of the present invention. Here, the point A of the polygon indicating the composition range of the present invention displayed in the ternary diagram of FIG. 1 is Example 47, the point B is Example 38, the point C is Example 1, and the point D is Example 4. Are respectively shown.
【００２５】図２は、表１に示した実施例１３から１８
について、Ｐｂ（Ｙ2/3 Ｗ1/3 ）Ｏ 3 の固溶量に伴う電
気機械結合係数、機械的品質係数、誘電率及び圧電定数
の各変化を示したものである。また、実施例５から実施
例１１、実施例２０から実施例２６についても略同じ傾
向を示した。これは、Ｐｂ（Ｙ2/3 Ｗ1/3 ）Ｏ3 の固溶
量を適切に選択することで諸般の圧電特性を向上させる
ことができるのは勿論、表３に示した様に、添加物の量
を調節することで用途に適合した特性の素子を得ること
ができることを示している。FIG. 2 shows Embodiments 13 to 18 shown in Table 1.
For Pb (Y2/3W1/3) O ThreeWith the solid solution amount of
Coupling coefficient, mechanical quality coefficient, dielectric constant and piezoelectric constant
Are shown. Also, the operation is performed from the fifth embodiment.
Example 11, Example 20 to Example 26 have substantially the same inclination.
The direction was shown. This is because Pb (Y2/3W1/3) OThreeSolid solution
Improve various piezoelectric properties by selecting the appropriate amount
Of course, as shown in Table 3,
To obtain an element with characteristics suitable for the application by adjusting
Indicates that it can be done.
【００２６】[0026]
【発明の効果】以上説明したように本発明によれば、従
来に比べて高い電気機械結合係数と大きい圧電定数とを
有する圧電特性に優れた新規な酸化物圧電材料を得るこ
とができる。従って、酸化物圧電材料の用途範囲の拡大
を図ることができる。また、Ｌａ2 Ｏ3 、ＭｎＯ2 、Ｎ
ｂ2 Ｏ5 、Ｃｒ2 Ｏ3 及びＴａ2 Ｏ5 の各添加物のいず
れか１つを添加すれば、圧電材料の圧電特性をより向上
させることが可能である。特に、ＭｎＯ2 を添加した場
合には、圧電特性を低下させずに機械的品質係数を高め
ことができ、信号帯域の巾が広い信号受電素子に適合し
たものを得ることができるという効果を有する。As described above, according to the present invention, it is possible to obtain a novel oxide piezoelectric material having a high electromechanical coupling coefficient and a large piezoelectric constant as compared with the prior art and having excellent piezoelectric characteristics. Therefore, the range of use of the oxide piezoelectric material can be expanded. La 2 O 3 , MnO 2 , N
If any one of the additives b 2 O 5 , Cr 2 O 3 and Ta 2 O 5 is added, the piezoelectric properties of the piezoelectric material can be further improved. In particular, when MnO 2 is added, the mechanical quality factor can be increased without lowering the piezoelectric characteristics, and an effect that a signal receiving element having a wide signal band can be obtained can be obtained. .
【図１】本発明の組成範囲を表したｘＰｂ（Ｙ2/3 Ｗ
1/3 ）Ｏ3 −ｙＰｂＺｒＯ3 −ｚＰｂＴｉＯ3 ３元系図FIG. 1 shows xPb (Y 2/3 W) representing the composition range of the present invention.
1/3) O 3 -yPbZrO 3 -zPbTiO 3 3 yuan genealogy
【図２】本発明の実施例試片のＰｂ（Ｙ2/3 Ｗ1/3 ）Ｏ
3 固溶量に伴う種々の圧電特性の変化を示しグラフFIG. 2 shows a sample of Pb (Y 2/3 W 1/3 ) O according to an embodiment of the present invention.
3 Graph showing changes in various piezoelectric properties with the amount of solid solution
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−169780（ＪＰ，Ａ) 特開 平２−172825（ＪＰ，Ａ) 特公 平４−38710（ＪＰ，Ｂ２) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-169780 (JP, A) JP-A-2-172825 (JP, A) JP 4-38710 (JP, B2)
Claims (2)
Ｏ3 −ｚＰｂＴｉＯ 3 系を基本組成とし、 0.01≦ｘ≦0.20 0.215 ≦ｙ，ｚ≦0.764 （但し、ｘ＋ｙ＋ｚ＝１） の組成範囲を持つ酸化物圧電材料。1. The method of claim 1, wherein xPb (Y2/3W1/3) OThree-YPbZr
OThree-ZPbTiO ThreeAn oxide piezoelectric material having a basic composition and a composition range of 0.01 ≦ x ≦ 0.20 0.215 ≦ y, z ≦ 0.764 (where x + y + z = 1).
ｂ2 Ｏ5 、Ｃｒ2 Ｏ 3 及びＴａ2 Ｏ5 のうちのいずれか
一つを0.1 〜1.0 重量％含有した請求項１記載の酸化物
圧電材料。2. An additive comprising LaTwoOThree, MnOTwo, N
bTwoOFive, CrTwoO ThreeAnd TaTwoOFiveAny of
2. The oxide according to claim 1, wherein one of said oxides is contained in an amount of 0.1 to 1.0% by weight.
Piezoelectric material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR3009/1993 | 1993-03-02 | ||
| KR1019930003009A KR950014290B1 (en) | 1993-03-02 | 1993-03-02 | Oxide piezo electric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0710638A JPH0710638A (en) | 1995-01-13 |
| JP2627480B2 true JP2627480B2 (en) | 1997-07-09 |
Family
ID=19351463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6032414A Expired - Fee Related JP2627480B2 (en) | 1993-03-02 | 1994-03-02 | Oxide piezoelectric material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2627480B2 (en) |
| KR (1) | KR950014290B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4671522B2 (en) * | 2001-03-29 | 2011-04-20 | 京セラ株式会社 | Piezoelectric ceramic, multilayer piezoelectric element, and injection device |
| JP4688329B2 (en) * | 2001-03-29 | 2011-05-25 | 京セラ株式会社 | Piezoelectric ceramic for actuator, laminated piezoelectric actuator, and injection device |
| JP4688330B2 (en) * | 2001-03-30 | 2011-05-25 | 京セラ株式会社 | Piezoelectric ceramic, multilayer piezoelectric element, and injection device |
| KR100641338B1 (en) * | 2001-12-22 | 2006-10-31 | 재단법인 포항산업과학연구원 | Piezoelectric ceramic composition for accelerometer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63169780A (en) * | 1987-01-08 | 1988-07-13 | Denki Kagaku Kogyo Kk | Composition for lead titanate zirconate piezoelectric device |
| KR910006708B1 (en) * | 1988-11-24 | 1991-08-31 | 한국과학기술원 | Oxide piezo-electric material |
| JPH0438710A (en) * | 1990-06-01 | 1992-02-07 | Matsushita Electric Ind Co Ltd | Permanent magnet type erasing head and magnetizing device for the same |
-
1993
- 1993-03-02 KR KR1019930003009A patent/KR950014290B1/en not_active IP Right Cessation
-
1994
- 1994-03-02 JP JP6032414A patent/JP2627480B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR950014290B1 (en) | 1995-11-24 |
| KR940022936A (en) | 1994-10-22 |
| JPH0710638A (en) | 1995-01-13 |
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