JPH0826826A - Piezoelectric porcelain - Google Patents
Piezoelectric porcelainInfo
- Publication number
- JPH0826826A JPH0826826A JP6166880A JP16688094A JPH0826826A JP H0826826 A JPH0826826 A JP H0826826A JP 6166880 A JP6166880 A JP 6166880A JP 16688094 A JP16688094 A JP 16688094A JP H0826826 A JPH0826826 A JP H0826826A
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- piezoelectric porcelain
- electromechanical coupling
- coupling coefficient
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、セラミックフィル
タ、スピーカー、マイクロホン、ブザー、センサなどの
圧電素子に使用される圧電性磁器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric porcelain used for piezoelectric elements such as ceramic filters, speakers, microphones, buzzers and sensors.
【０００２】[0002]
【従来の技術】セラミックフィルタなどに用いられる圧
電性磁器として、従来より、チタン酸ジルコン酸鉛（Ｐ
ｂ（ＴｉxＺｒ1-x）Ｏ3）を主成分とする圧電性磁器が
広く用いられており、その圧電特性を改善するために種
々の微量添加物を添加した圧電性磁器が用いられてい
る。2. Description of the Related Art Conventionally, lead zirconate titanate (P
Piezoelectric porcelain containing b (Ti x Zr 1-x ) O 3 ) as a main component is widely used, and piezoelectric porcelain containing various trace additives is used to improve its piezoelectric characteristics. There is.
【０００３】チタン酸ジルコン酸鉛系の一つとして知ら
れているＰｂ（Ｎｉ1/3Ｎｂ2/3）Ｏ3−ＰｂＴｉＯ3−Ｐ
ｂＺｒＯ3を基本組成とする圧電性磁器は、通常、酸化
鉛、酸化ジルコニウム、酸化チタン、酸化ニッケル、五
酸化ニオブなどの酸化物原料を所定の化学量論組成とな
るように調合し、ボールミルなどを用いて混合分散させ
た後、所定の温度で仮焼し、さらに、粉砕およびバイン
ダ混合を行った後、所定の形状に成形し、これを１２０
０℃以上の高温で焼成して焼結反応を行わせ、分極処理
を行うことにより製造されている。Pb (Ni 1/3 Nb 2/3 ) O 3 -PbTiO 3 -P, which is known as one of the lead zirconate titanate systems.
Piezoelectric porcelain having a basic composition of bZrO 3 is usually prepared by mixing oxide raw materials such as lead oxide, zirconium oxide, titanium oxide, nickel oxide, and niobium pentoxide so as to have a predetermined stoichiometric composition, and then using a ball mill or the like. After being mixed and dispersed by using, the mixture was calcined at a predetermined temperature, further pulverized and mixed with a binder, and then molded into a predetermined shape.
It is manufactured by firing at a high temperature of 0 ° C. or higher to cause a sintering reaction and a polarization treatment.
【０００４】この圧電性磁器を電気機械変換素子として
応用する場合、スピーカー、マイクロホンのように、大
きい出力電圧とその周波数特性の平坦性を望む応用にお
いては、電気機械結合係数を大きくし、静電容量を大き
くするために材料自体の誘電率が高いものがよい。When the piezoelectric porcelain is applied as an electromechanical conversion element, the electromechanical coupling coefficient is increased and the electrostatic capacitance is increased in applications where a large output voltage and flatness of its frequency characteristic are desired, such as a speaker or a microphone. It is preferable that the material itself has a high dielectric constant in order to increase the capacitance.
【０００５】[0005]
【発明が解決しようとする課題】上記の目的を達成する
圧電性磁器として、Ｐｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ3−Ｐｂ
ＴｉＯ3−ＰｂＺｒＯ3系磁器が、特公昭４４−１７１０
３号公報に記載されているが、電気機械結合係数および
誘電率の高さの点では問題を解決するに至っていない。As a piezoelectric porcelain that achieves the above object, Pb (Mg 1/3 Nb 2/3 ) O 3 -Pb is used.
TiO 3 -PbZrO 3 based porcelain is disclosed in Japanese Patent Publication No.44-1710
Although it is described in Japanese Patent Publication No. 3, the problem has not been solved in terms of high electromechanical coupling coefficient and high dielectric constant.
【０００６】また、圧電性磁器を電気機械変換素子とし
て応用する濾波器（フィルタ）素子のように、減衰極間
の巾が電気機械結合係数に依存する場合、濾波器（フィ
ルタ）の広帯域化を計るためには、電気機械結合係数が
大きいものがよいが、特公昭４４−１７１０３号公報記
載の圧電性磁器では、解決するに至っていない。When the width between the attenuation poles depends on the electromechanical coupling coefficient, as in the case of a filter element applying a piezoelectric porcelain as an electromechanical conversion element, it is necessary to widen the band of the filter. In order to measure, it is preferable that the electromechanical coupling coefficient is large, but the piezoelectric porcelain disclosed in JP-B-44-17103 has not been able to solve the problem.
【０００７】この発明の目的は、電気機械結合係数が大
きく、共振周波数の温度特性に優れた、広帯域に対応で
きるフィルタ用の圧電性磁器を提供することである。An object of the present invention is to provide a piezoelectric porcelain for a filter which has a large electromechanical coupling coefficient and is excellent in temperature characteristics of resonance frequency and which can be applied to a wide band.
【０００８】[0008]
【課題を解決するための手段】請求項１に係る発明は、
一般式ａＰｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ3−ｂＰｂＴｉＯ3−
ｃＰｂＺｒＯ3（ａ、ｂ、ｃがそれぞれ１≦ａ≦１０、
４２≦ｂ≦６０、３０≦ｃ≦５７、ただし、ａ、ｂ、ｃ
はモル％であり、ａ＋ｂ＋ｃ＝１００）で表されるチタ
ン酸ジルコン酸鉛のＰｂ原子の０．５モル％以上〜５モ
ル％以下をＭｇで置換し、さらに、ＣｒをＣｒ2Ｏ3に換
算して０．１重量％以上〜１重量％以下添加含有させた
圧電性磁器である。The invention according to claim 1 is
Formula aPb (Mg 1/3 Nb 2/3) O 3 -bPbTiO 3 -
cPbZrO 3 (a, b, and c are 1 ≦ a ≦ 10,
42 ≦ b ≦ 60, 30 ≦ c ≦ 57, where a, b, c
Is mol%, and 0.5 mol% to 5 mol% of Pb atoms of lead zirconate titanate represented by a + b + c = 100) is replaced with Mg, and Cr is converted to Cr 2 O 3 . Then, the piezoelectric porcelain containing 0.1 wt% to 1 wt% is added.
【０００９】請求項２に係る発明は、一般式ａＰｂ（Ｍ
ｇ1/3Ｎｂ2/3）Ｏ3−ｂＰｂＴｉＯ3−ｃＰｂＺｒＯ
3（ａ、ｂ、ｃがそれぞれ１≦ａ≦１０、４２≦ｂ≦６
０、３０≦ｃ≦５７、ただし、ａ、ｂ、ｃはモル％であ
り、ａ＋ｂ＋ｃ＝１００）で表されるチタン酸ジルコン
酸鉛のＰｂ原子の１０モル％以下（ただし、０モル％を
含まず）を、Ｍｇ０．５モル％以上〜５モル％以下と少
なくとも１種のＣａ、Ｓｒ、Ｂａ９．５モル％以下（た
だし、０モル％を含まず）で置換し、さらに、ＣｒをＣ
ｒ2Ｏ3に換算して０．１重量％以上〜１重量％以下添加
含有させた圧電性磁器である。The invention according to claim 2 is the general formula aPb (M
g 1/3 Nb 2/3 ) O 3 -bPbTiO 3 -cPbZrO
3 (a, b and c are 1 ≦ a ≦ 10 and 42 ≦ b ≦ 6 respectively
0, 30 ≦ c ≦ 57, where a, b, and c are mol%, and 10 mol% or less (including 0 mol% of Pb atoms of lead zirconate titanate represented by a + b + c = 100) Substituting 0.5 to 5 mol% of Mg with at least one Ca, Sr, and 9.5 mol% or less of Ba (not including 0 mol%), and further Cr is C.
This is a piezoelectric porcelain containing 0.1% by weight or more and 1% by weight or less in terms of r 2 O 3 .
【００１０】請求項の組成範囲に限定したのは次の理由
による。つまり、ａＰｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ3成分の
ａの値が、１モル％未満、あるいは１０モル％を越える
と、電気機械結合係数が低くなる。また、ｂＰｂxＴｉ
Ｏ3成分のｂの値が、４２モル％未満、あるいは６０モ
ル％を越えると、電気機械結合係数が低くなり、fr-TC
の絶対値が大きくなる。さらに、ｃＰｂxＺｒＯ3成分の
ｃの値が、３０モル％未満、あるいは５７モル％を越え
ると、電気機械結合係数が低くなる。The reason for limiting the composition range of the claims is as follows. That is, when the value of a of the aPb (Mg 1/3 Nb 2/3 ) O 3 component is less than 1 mol% or exceeds 10 mol%, the electromechanical coupling coefficient becomes low. Also, bPb x Ti
When the b value of the O 3 component is less than 42 mol% or more than 60 mol%, the electromechanical coupling coefficient becomes low, and fr-TC
The absolute value of increases. Further, when the value of c of the cPb x ZrO 3 component is less than 30 mol% or exceeds 57 mol%, the electromechanical coupling coefficient becomes low.
【００１１】次に、置換されるＰｂ成分が、１０モル％
越えると、電気機械結合係数が低くなる。また、置換さ
れるＰｂ成分のうちＭｇが、０．５モル％未満、５モル
％越え、Ｃａ、Ｓｒ、Ｂａが９．５モル％を越えると電
気機械結合係数が低くなる。さらに、添加されるＣｒ2
Ｏ3が０．１重量％未満、１重量％を越えると電気機械
結合係数が低くなる。Next, the Pb component to be replaced is 10 mol%
When it exceeds, the electromechanical coupling coefficient becomes low. In addition, if Mg of less than 0.5 mol% and more than 5 mol% and Ca, Sr, and Ba of more than 9.5 mol% among Pb components to be replaced exceed the electromechanical coupling coefficient. In addition, Cr 2 added
If O 3 is less than 0.1% by weight and exceeds 1% by weight, the electromechanical coupling coefficient becomes low.
【００１２】[0012]
【作用】この発明の圧電性磁器によれば、鉛含有複合酸
化物の３成分が請求項の範囲内で、鉛の一部をマグネシ
ウムと少なくとも１種類のストロンチウム、バリウム、
カルシウムで置換することにより、電気機械結合係数が
大きく、比誘電率が大きく、温度特性の良好な圧電性磁
器が得られる。According to the piezoelectric porcelain of the present invention, the three components of the lead-containing composite oxide are within the scope of the claims, and a part of lead is magnesium and at least one strontium, barium,
By substituting with calcium, a piezoelectric porcelain having a large electromechanical coupling coefficient, a large relative dielectric constant, and good temperature characteristics can be obtained.
【００１３】[0013]
【実施例】以下、この発明を実施例により説明する。原
料として、酸化鉛、酸化ジルコン、酸化チタン、炭酸ス
トロンチウム、炭酸カルシウム、炭酸バリウム、水酸化
マグネシウム、酸化クロムおよび酸化ニオブを準備し、
これを表１に示す組成比率で調合し、この調合原料をボ
ールミルを用いて湿式混合した後、脱水、乾燥し、８５
０〜９５０℃で２時間仮焼し、この仮焼粉をボールミル
を用いて再度湿式粉砕することにより調整粉末を得た。EXAMPLES The present invention will be described below with reference to examples. As raw materials, lead oxide, zirconium oxide, titanium oxide, strontium carbonate, calcium carbonate, barium carbonate, magnesium hydroxide, chromium oxide and niobium oxide are prepared,
This was blended in the composition ratio shown in Table 1, and the blended raw materials were wet mixed using a ball mill, dehydrated and dried.
The powder was calcined at 0 to 950 ° C. for 2 hours, and the calcined powder was wet-milled again using a ball mill to obtain a conditioned powder.
【００１４】[0014]
【表１】 [Table 1]
【００１５】そして、この調整粉末に水またはポリビニ
ルアルコールなどの粘結剤を添加し、プレス成形を行っ
た後、１２００〜１３００℃で２時間焼成し、焼結体を
得た。次に、得られた焼結体を直径２０mm、厚さ１mmの
円板状に研磨し、両端面に銀電極を焼き付けた後、６０
℃の絶縁オイル中で６０分間、３〜４kV／mmの直流電圧
を印加することにより分極処理を行って圧電性磁器を得
た。Then, a binder such as water or polyvinyl alcohol was added to the adjusted powder, and press molding was performed, followed by firing at 1200 to 1300 ° C. for 2 hours to obtain a sintered body. Next, the obtained sintered body was polished into a disk shape having a diameter of 20 mm and a thickness of 1 mm, and silver electrodes were baked on both end faces, and then 60
A polarization treatment was performed by applying a DC voltage of 3 to 4 kV / mm in insulating oil at 60 ° C. for 60 minutes to obtain a piezoelectric porcelain.
【００１６】この圧電性磁器を用いて、比誘電率（ε33
T／ε0）、拡がり方向振動の電気機械結合係数（Kp）、
拡がり振動の共振周波数（fr）の温度変化率（fr-TC）
について調べた。拡がり振動の共振周波数の温度変化率
（fr-TC）は−２０℃〜＋８０℃の温度範囲での共振周
波数の最大値と最小値との差を、２０℃での共振周波数
値で除した商をあらわしている。測定は、インピーダン
ス測定器を用い、比誘電率の測定周波数は１kHzであ
り、拡がり方向振動の電気機械結合係数の測定には、共
振、***振法を用いた。測定結果を表２に示した。Using this piezoelectric porcelain, the relative permittivity (ε 33
T / ε 0 ), electromechanical coupling coefficient (Kp) of vibration in the spreading direction,
Temperature change rate (fr-TC) of resonance frequency (fr) of spreading vibration
Was examined. The temperature change rate (fr-TC) of the resonance frequency of the spreading vibration is the quotient of the difference between the maximum and minimum values of the resonance frequency in the temperature range of -20 ℃ to + 80 ℃ divided by the resonance frequency value at 20 ℃. Is represented. The measurement was performed using an impedance measuring instrument, the measurement frequency of the relative permittivity was 1 kHz, and the resonance and anti-resonance method was used to measure the electromechanical coupling coefficient of the vibration in the spreading direction. The measurement results are shown in Table 2.
【００１７】[0017]
【表２】 [Table 2]
【００１８】表１、表２において、試料番号に＊印を付
したものは、この発明の範囲外のものであり、その他の
ものはこの発明の範囲内のものである。In Tables 1 and 2, the sample numbers marked with * are outside the scope of the present invention, and the others are within the scope of the present invention.
【００１９】表１、表２の結果から、ＰｂをＭｇで置換
し、さらにＣｒを添加することにより、電気機械結合係
数を大きくし、共振周波数の温度変化率の絶対値を小さ
くできる。また、Ｍｇの置換量が０．５モル％未満では
電気機械結合係数を増加させる効果がなく、また、５モ
ル％を越えると電気機械結合係数が低下する。しかも、
ＰｂをＭｇで置換することにより、圧電性磁器の焼結が
均一に進み、焼成後の磁器の変形、ソリが小さく、外観
状安定した圧電性磁器が得られる。さらに、Ｃｒの添加
量が０．１重量％未満では、電気機械結合係数が小さ
く、共振周波数の温度変化率の改善に対する効果が乏し
く、１重量％を越えると電気機械結合係数が低下すると
ともに、磁器の固有抵抗が下がり分極が困難になる。From the results of Tables 1 and 2, by substituting Mg for Pb and adding Cr, the electromechanical coupling coefficient can be increased and the absolute value of the temperature change rate of the resonance frequency can be reduced. Further, if the substitution amount of Mg is less than 0.5 mol%, there is no effect of increasing the electromechanical coupling coefficient, and if it exceeds 5 mol%, the electromechanical coupling coefficient decreases. Moreover,
By substituting Pb with Mg, sintering of the piezoelectric porcelain proceeds uniformly, deformation and warpage of the porcelain after firing are small, and a piezoelectric porcelain having a stable appearance can be obtained. Further, when the amount of Cr added is less than 0.1% by weight, the electromechanical coupling coefficient is small, and the effect of improving the temperature change rate of the resonance frequency is poor, and when it exceeds 1% by weight, the electromechanical coupling coefficient decreases. The specific resistance of the porcelain decreases, making polarization difficult.
【００２０】次に、ＰｂをＳｒ、Ｃａ、Ｂａの少なくと
も１種類で置換する場合、置換量を増加させると比誘電
率が増加し、電気機械結合係数が低くなる。さらに、Ｍ
ｇを含めた置換量が１０モル％を越えると電気機械結合
係数が低下し、キュリー温度が低下し、材料の圧電特性
が経時的に劣化する。Next, when Pb is replaced with at least one of Sr, Ca and Ba, if the amount of substitution is increased, the relative dielectric constant increases and the electromechanical coupling coefficient decreases. Further, M
If the substitution amount including g exceeds 10 mol%, the electromechanical coupling coefficient decreases, the Curie temperature decreases, and the piezoelectric characteristics of the material deteriorate with time.
【００２１】[0021]
【発明の効果】この発明の圧電性磁器において、各成分
を請求範囲内にすることにより、電気機械結合係数が大
きく、共振周波数の温度変化が小さい圧電性磁器が得ら
れ、フィルターの広帯域化が計れる。また、スピーカ
ー、マイクロホン、ブザー、センサ等への応用にも充分
可能な圧電性磁器が得られる。EFFECTS OF THE INVENTION In the piezoelectric porcelain of the present invention, by setting each component within the scope of claims, a piezoelectric porcelain having a large electromechanical coupling coefficient and a small change in resonance frequency with temperature can be obtained, and the band of the filter can be broadened. Can be measured. Further, a piezoelectric porcelain sufficiently applicable to a speaker, a microphone, a buzzer, a sensor, etc. can be obtained.
Claims (2)
ｂＰｂＴｉＯ3−ｃＰｂＺｒＯ3（ａ、ｂ、ｃがそれぞれ
１≦ａ≦１０、４２≦ｂ≦６０、３０≦ｃ≦５７、ただ
し、ａ、ｂ、ｃはモル％であり、ａ＋ｂ＋ｃ＝１００）
で表されるチタン酸ジルコン酸鉛のＰｂ原子の０．５モ
ル％以上〜５モル％以下をＭｇで置換し、さらに、Ｃｒ
をＣｒ2Ｏ3に換算して０．１重量％以上〜１重量％以下
添加含有させたことを特徴とする圧電性磁器。1. A general formula aPb (Mg 1/3 Nb 2/3 ) O 3 −
bPbTiO 3 —cPbZrO 3 (a, b and c are 1 ≦ a ≦ 10, 42 ≦ b ≦ 60, 30 ≦ c ≦ 57, respectively, where a, b and c are mol% and a + b + c = 100)
Substituting 0.5 to 5 mol% of Pb atoms of lead zirconate titanate represented by
Piezoelectric ceramics, wherein a was contained added terms to 0.1% by weight or more to 1% by weight or less Cr 2 O 3.
ｂＰｂＴｉＯ3−ｃＰｂＺｒＯ3（ａ、ｂ、ｃがそれぞれ
１≦ａ≦１０、４２≦ｂ≦６０、３０≦ｃ≦５７、ただ
し、ａ、ｂ、ｃはモル％であり、ａ＋ｂ＋ｃ＝１００）
で表されるチタン酸ジルコン酸鉛のＰｂ原子の１０モル
％以下（ただし、０モル％を含まず）を、Ｍｇ０．５モ
ル％以上〜５モル％以下と少なくとも１種のＣａ、Ｓ
ｒ、Ｂａ９．５モル％以下（ただし、０モル％を含ま
ず）で置換し、さらに、ＣｒをＣｒ2Ｏ3に換算して０．
１重量％以上〜１重量％以下添加含有させたことを特徴
とする請求項１記載の圧電性磁器。2. The general formula aPb (Mg 1/3 Nb 2/3 ) O 3 −
bPbTiO 3 —cPbZrO 3 (a, b and c are 1 ≦ a ≦ 10, 42 ≦ b ≦ 60, 30 ≦ c ≦ 57, respectively, where a, b and c are mol% and a + b + c = 100)
In the lead titanate zirconate represented by the formula, 10 mol% or less (however, not including 0 mol%) of Pb atoms, and 0.5 mol% to 5 mol% of Mg and at least one kind of Ca and S
r, Ba 9.5 mol% or less (however, 0 mol% is not included) is substituted, and Cr is converted to Cr 2 O 3 to be 0.
The piezoelectric porcelain according to claim 1, characterized in that it is added and contained in an amount of 1% by weight or more and 1% by weight or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16688094A JP3221241B2 (en) | 1994-07-19 | 1994-07-19 | Piezoelectric porcelain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16688094A JP3221241B2 (en) | 1994-07-19 | 1994-07-19 | Piezoelectric porcelain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0826826A true JPH0826826A (en) | 1996-01-30 |
| JP3221241B2 JP3221241B2 (en) | 2001-10-22 |
Family
ID=15839335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16688094A Expired - Fee Related JP3221241B2 (en) | 1994-07-19 | 1994-07-19 | Piezoelectric porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3221241B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550096A (en) * | 1983-10-21 | 1996-08-27 | Nippon Shokubai Koguko Kogyo Co., Ltd. | Catalyst for purifying nitrogen oxides from exhaust and waste gases |
| DE102005040317A1 (en) * | 2004-08-27 | 2006-03-23 | Tdk Corp. | Piezoelectric ceramic composition |
| US8142677B2 (en) | 2004-03-26 | 2012-03-27 | Tdk Corporation | Piezoelectric ceramic composition |
-
1994
- 1994-07-19 JP JP16688094A patent/JP3221241B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550096A (en) * | 1983-10-21 | 1996-08-27 | Nippon Shokubai Koguko Kogyo Co., Ltd. | Catalyst for purifying nitrogen oxides from exhaust and waste gases |
| US8142677B2 (en) | 2004-03-26 | 2012-03-27 | Tdk Corporation | Piezoelectric ceramic composition |
| DE102005040317A1 (en) * | 2004-08-27 | 2006-03-23 | Tdk Corp. | Piezoelectric ceramic composition |
| DE102005040317B4 (en) * | 2004-08-27 | 2008-02-07 | Tdk Corp. | Piezoelectric ceramic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3221241B2 (en) | 2001-10-22 |
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