JPH11209176A - Piezoelectric porcelain composition and its production - Google Patents
Piezoelectric porcelain composition and its productionInfo
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- JPH11209176A JPH11209176A JP10013720A JP1372098A JPH11209176A JP H11209176 A JPH11209176 A JP H11209176A JP 10013720 A JP10013720 A JP 10013720A JP 1372098 A JP1372098 A JP 1372098A JP H11209176 A JPH11209176 A JP H11209176A
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- mol
- polarization
- temperature
- piezoelectric ceramic
- resonance frequency
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は圧電磁器組成物およ
びその製造方法に関するものであり、特に厚みすべりモ
ード共振を利用したフィルタ用圧電磁器で電気機械結合
係数が比較的大きく、耐熱性が良好で温度サイクル前後
での共振周波数および圧電特性の変化が少ない圧電磁器
組成物およびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition and a method for producing the same. More particularly, the present invention relates to a piezoelectric ceramic for filters utilizing thickness-shear mode resonance, which has a relatively large electromechanical coupling coefficient and good heat resistance. TECHNICAL FIELD The present invention relates to a piezoelectric ceramic composition in which changes in resonance frequency and piezoelectric characteristics before and after a temperature cycle are small, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来より圧電磁器組成物としてはチタン
酸バリウム磁器、チタン酸ジルコン酸鉛磁器、マグネシ
ウムニオブ酸チタン酸ジルコン酸鉛磁器、および亜鉛ニ
オブ酸チタン酸ジルコン酸鉛磁器などがあり、使用目的
に応じて種々の改良がなされてきた。2. Description of the Related Art Conventionally, piezoelectric ceramic compositions include barium titanate porcelain, lead zirconate titanate porcelain, magnesium niobate lead zirconate titanate porcelain, and zinc niobate lead zirconate porcelain. Various improvements have been made depending on the purpose.
【０００３】[0003]
【発明が解決しようとする課題】フィルタ、発振子など
に用いる圧電磁器組成物は、エネルギー、環境問題およ
び電気特性のばらつき低減の観点からできるだけ低温で
の焼成が可能でかつ表面実装タイプのチップ部品に対応
するため半田付け実装温度に耐えうる耐熱性（特に耐熱
前後での圧電特性変化ができるだけ小さいもの）が要求
されている。A piezoelectric ceramic composition used for a filter, an oscillator and the like can be fired at a temperature as low as possible from the viewpoint of energy, environmental problems and reduction of variations in electrical characteristics, and is a chip component of a surface mount type. In order to cope with this, heat resistance (particularly, a change in piezoelectric characteristics before and after heat resistance as small as possible) that can withstand the soldering mounting temperature is required.
【０００４】さらに従来の圧電磁器組成物は実用上に重
要な信頼性の一つである温度サイクル前後で共振周波数
が変化するという問題があり、電子機器の安定動作のた
め共振周波数の変化をできるだけ低く押さえる必要があ
った。Further, the conventional piezoelectric ceramic composition has a problem that the resonance frequency changes before and after a temperature cycle, which is one of reliability which is important for practical use. I needed to keep it low.
【０００５】そこで本発明は厚みすべりモード共振を利
用したフィルタに適した比較的低温での焼成が可能で電
気機械結合係数が大きく、２８０℃近傍の半田付け実装
温度でも電気特性劣化が少なく、かつ温度サイクルによ
る共振周波数変化の少ない圧電磁器組成物を提供するこ
とを目的とするものである。Accordingly, the present invention can be fired at a relatively low temperature suitable for a filter utilizing thickness-shear mode resonance, has a large electromechanical coupling coefficient, and has little deterioration in electrical characteristics even at a soldering mounting temperature near 280 ° C. It is an object of the present invention to provide a piezoelectric ceramic composition having a small change in resonance frequency due to a temperature cycle.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に本発明の圧電磁器組成物は、一般式（化３）で表され
る組成物中のＰｂの１モル％以上１０モル％以下をＣ
ａ，Ｓｒ，Ｂａのうち少なくとも一種で置換したものを
主成分とし、副成分としてＣｒ2Ｏ3およびＭｎ3Ｏ4のう
ち少なくとも一種を０．０５〜１．２０重量％含有させ
たことを特徴とするものである。In order to achieve this object, the piezoelectric ceramic composition of the present invention comprises 1 to 10 mol% of Pb in the composition represented by the general formula (Formula 3). C
wherein a, Sr, as a main component obtained by substituting at least one of Ba, that at least one of is contained 0.05 to 1.20 wt% of Cr 2 O 3 and Mn 3 O 4 as a sub-component It is assumed that.
【０００７】[0007]
【化３】 Embedded image
【０００８】この構成によると、Ｐｂを特定比率のＣ
ａ，Ｓｒ，Ｂａのうち少なくとも一種で置換することに
より比誘電率の値を調整し、デバイスに応じた適切なも
のとすることができ、かつ温度サイクルによる共振周波
数変化を低減できる。According to this configuration, Pb is converted into C at a specific ratio.
By substituting at least one of a, Sr, and Ba, the value of the relative dielectric constant can be adjusted to be appropriate for the device, and the change in resonance frequency due to a temperature cycle can be reduced.
【０００９】またＰｂ量を化学量論比より若干多くする
ことにより、焼成時のＰｂＯ飛散の影響を低減し、ＰＺ
Ｔ組成系でＰｂ（Ｉｎ1/2Ｎｂ1/2）Ｏ3およびＰｂ（Ｍ
ｇ1/3Ｎｂ2/3）Ｏ3を第３成分、第４成分として固溶さ
せることにより焼成温度低減（焼結性向上）と、電気機
械結合係数増加、耐熱性向上を図った。Further, by making the Pb amount slightly larger than the stoichiometric ratio, the influence of PbO scattering at the time of firing can be reduced,
Pb (In 1/2 Nb 1/2 ) O 3 and Pb (M
g 1/3 Nb 2/3 ) O 3 was dissolved as a third component and a fourth component to reduce the firing temperature (improve sinterability), increase the electromechanical coupling coefficient, and improve heat resistance.
【００１０】さらに副成分としてＣｒ2Ｏ3およびＭｎ3
Ｏ4を添加することにより、圧電性を低下させることな
く耐熱性と温度サイクルでの電気特性変化低減を実現し
た。Further, Cr 2 O 3 and Mn 3
By adding O 4 , the heat resistance and the reduction in changes in electrical characteristics in a temperature cycle were realized without lowering the piezoelectricity.
【００１１】これにより発振子、フィルタなどに適した
２８０℃近傍の半田付け実装温度でも電気特性変化が少
なく、かつ温度サイクルによる共振周波数変化も少ない
圧電磁器組成物が得られる。As a result, it is possible to obtain a piezoelectric ceramic composition which is suitable for an oscillator, a filter, and the like even at a soldering mounting temperature of around 280 ° C. and has little change in electric characteristics and little change in resonance frequency due to a temperature cycle.
【００１２】[0012]
【発明の実施の形態】本発明の請求項１に記載の発明
は、一般式（化４）で表される組成物中のＰｂの１モル
％以上１０モル％以下をＣａ，Ｓｒ，Ｂａのうち少なく
とも一種で置換したものを主成分に、副成分としてＣｒ
2Ｏ3およびＭｎ3Ｏ4のうち少なくとも一種を０．０５〜
１．２０重量％含有させたことを特徴とする圧電磁器組
成物であり、厚みすべりモード共振を利用した発振子、
フィルタに適した比較的低温での焼成が可能で電気機械
結合係数が比較的大きく、２８０℃近傍の半田付け実装
温度でも電気特性劣化の少ない、温度サイクルによる共
振周波数変化の少ないものである。BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention relates to a composition represented by the general formula (Chem. 4), wherein 1 mol% or more and 10 mol% or less of Pb are contained in Ca, Sr, and Ba. Of which at least one is substituted as the main component,
At least one of 2 O 3 and Mn 3 O 4
1. A piezoelectric ceramic composition characterized by containing 20% by weight, comprising: an oscillator utilizing thickness-shear mode resonance;
It can be fired at a relatively low temperature suitable for a filter, has a relatively large electromechanical coupling coefficient, has little deterioration in electrical characteristics even at a soldering mounting temperature near 280 ° C., and has little change in resonance frequency due to temperature cycles.
【００１３】[0013]
【化４】 Embedded image
【００１４】請求項２に記載の発明は、一般式（化５）
で表される組成物中のＰｂの１モル％以上１０モル％以
下をＣａ，Ｓｒ，Ｂａのうち少なくとも一種で置換した
ものを主成分とし、副成分としてＣｒ2Ｏ3およびＭｎ3
Ｏ4のうち少なくとも一種を０．０５〜１．２重量％添
加、混合して成形体を得る第１の工程と、この成形体を
焼成して焼結体を得る第２の工程と、この焼結体に分極
電極を形成後、１３０〜１８０℃の温度範囲で、３．５
ｋＶ／mm以上の直流電界を印加して分極する第３の工程
と、この分極済み焼結体の前記分極電極間を短絡させた
状態で２２０〜２８０℃で熱処理する第４の工程とを備
えたことを特徴とする圧電磁器組成物の製造方法であ
り、厚みすべりモード共振を利用した発振子、フィルタ
に適した比較的低温での焼成が可能で電気機械結合係数
が比較的大きく、２８０℃近傍の半田付け実装温度でも
電気特性劣化の少ない、温度サイクルによる共振周波数
変化の少ない圧電磁器組成物を得ることができる。The invention according to claim 2 is a compound of the general formula (5)
A composition in which 1 mol% or more and 10 mol% or less of Pb in the composition represented by the formula is replaced with at least one of Ca, Sr, and Ba as main components, and Cr 2 O 3 and Mn 3 as subcomponents.
A first step of adding and mixing 0.05 to 1.2% by weight of O 4 to obtain a molded body, a second step of firing this molded body to obtain a sintered body, After forming the polarized electrode on the sintered body, the temperature was set to 3.5 in a temperature range of 130 to 180 ° C.
a third step of applying a DC electric field of kV / mm or more to polarize, and a fourth step of performing a heat treatment at 220 to 280 ° C. with the polarized electrodes of the polarized sintered body short-circuited. A method for producing a piezoelectric ceramic composition characterized by the fact that it can be fired at a relatively low temperature suitable for an oscillator using thickness-shear mode resonance and a filter, and has a relatively large electromechanical coupling coefficient of 280 ° C. It is possible to obtain a piezoelectric ceramic composition in which electrical characteristics are less deteriorated even at a soldering mounting temperature in the vicinity and a change in resonance frequency due to a temperature cycle is small.
【００１５】[0015]
【化５】 Embedded image
【００１６】以下本発明の一実施の形態について図面を
参照しながら説明する。 （実施の形態１）図１は本実施の形態における厚みすべ
りモード共振子の斜視図であり、圧電磁器１の上、下両
面に共振電極２を形成したものである。図２（ａ）〜
（ｃ）は、一般的な焦電効果による分極済み圧電磁器に
おける熱処理時の脱分極機構を説明するための断面図で
あり、３は圧電磁器１の上、下面に形成した分極用電
極、４は分極ベクトル、５は浮遊電荷、６は表面電荷、
７は熱処理で生成した残余の浮遊電荷により生成した反
電界を示す。An embodiment of the present invention will be described below with reference to the drawings. (Embodiment 1) FIG. 1 is a perspective view of a thickness-shear mode resonator according to the present embodiment, in which resonance electrodes 2 are formed on both upper and lower surfaces of a piezoelectric ceramic 1. FIG.
(C) is a cross-sectional view for explaining a depolarization mechanism during heat treatment in a polarized piezoelectric ceramic by a general pyroelectric effect, and 3 is a polarizing electrode formed on the upper and lower surfaces of the piezoelectric ceramic 1 and 4. Is the polarization vector, 5 is the floating charge, 6 is the surface charge,
Numeral 7 indicates a reversal electric field generated by the residual floating charges generated by the heat treatment.
【００１７】まず原料としてＰｂＯ，ＴｉＯ2，Ｚｒ
Ｏ2，Ｉｎ2Ｏ3，Ｎｂ2Ｏ5，ＭｇＯ，Ｃｒ2Ｏ3，Ｍｎ3Ｏ
4，ＣａＣＯ3，ＳｒＣＯ3，ＢａＣＯ3を（表１），（表
２）の組成となるように正確に秤量し、ボールミルによ
りよく混合した。First, as raw materials PbO, TiO 2 , Zr
O 2 , In 2 O 3 , Nb 2 O 5 , MgO, Cr 2 O 3 , Mn 3 O
4 , CaCO 3 , SrCO 3 , and BaCO 3 were accurately weighed to have the compositions shown in (Table 1) and (Table 2) and mixed well by a ball mill.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】なお原料は上記酸化物に限られるものでな
く化学反応により上記の酸化物を生成するものであれば
他の化合物を使用しても良い。次に前記混合物を８５０
℃の温度で仮焼し、さらにボールミルにより粉砕した。
これを乾燥した後、結合剤としてのポリビニールアルコ
ール水溶液を加え、造粒した後１ton／cm2の圧力で加圧
成形し、縦５０mm、横４５mm、厚み７mmの成形体を得
た。ここで得られた成形体を閉炉中で１１５０〜１２８
０℃の温度で１時間焼成し、得られた圧電磁器１より厚
みすべり振動共振子を以下のようにして作製した。The raw material is not limited to the above oxides, and other compounds may be used as long as they produce the above oxides by a chemical reaction. The mixture is then placed at 850
It was calcined at a temperature of ° C. and further pulverized by a ball mill.
After drying, an aqueous polyvinyl alcohol solution as a binder was added, and the mixture was granulated and pressed under a pressure of 1 ton / cm 2 to obtain a formed body having a length of 50 mm, a width of 45 mm and a thickness of 7 mm. The molded body obtained here was placed in a closed furnace at 1150 to 128
It was fired at a temperature of 0 ° C. for 1 hour, and a thickness-shear vibration resonator was produced from the obtained piezoelectric ceramic 1 as follows.
【００２１】まず矩形板状の圧電磁器を研磨して厚み５
mmの圧電磁器１とした後、両面に銀電極を焼き付け分極
用電極３とし、１２５〜１８５℃のシリコンオイル中で
３．４〜４．０ｋＶ／mmの直流電界を３０分間印加して
分極処理し、ついで分極用電極３間を短絡させた状態で
熱処理を行った。次に厚み方向に０．５mm間隔でスライ
スし０．０５μｍＣｒ−１μｍＡｕの二層蒸着膜よりな
る共振電極２をスライス面に形成し、分極方向にダイシ
ングすることにより図１に示した矩形板状の厚みすべり
モード共振子を得た。これらの試料につき密度ρ、比誘
電率ε11 T／ε0、電気機械結合係数ｋ15を測定した。耐
熱性は共振子を２８０℃のホットプレート上で１分間保
持した後、３０分経過時点でのｋ15および共振周波数の
変化率を測定した。ｋ15≧０．４、｜ｋ15変化率｜≦５
％、｜共振周波数変化率｜≦０．３％を耐熱性良好と判
定した。測定結果の内で本発明の範囲内の分極および分
極後熱処理を施したものを磁器焼成温度（密度最大）と
ともに（表３），（表４）にまとめた。First, a rectangular plate-shaped piezoelectric ceramic is polished to a thickness of 5 mm.
After forming a piezoelectric ceramic 1 mm in thickness, silver electrodes are baked on both surfaces to form a polarizing electrode 3, and a DC electric field of 3.4 to 4.0 kV / mm is applied in silicon oil at 125 to 185 ° C. for 30 minutes to perform polarization treatment. Then, heat treatment was performed in a state where the electrodes for polarization 3 were short-circuited. Next, by slicing in the thickness direction at intervals of 0.5 mm, a resonance electrode 2 made of a two-layer deposited film of 0.05 μm Cr-1 μm Au was formed on the slice surface, and diced in the polarization direction to form a rectangular plate-like shape shown in FIG. A thickness-shear mode resonator was obtained. These samples were measured for density ρ, relative dielectric constant ε 11 T / ε 0 , and electromechanical coupling coefficient k 15 . The heat resistance was measured by measuring the change rate of k 15 and the resonance frequency after 30 minutes, after holding the resonator on a hot plate at 280 ° C. for 1 minute. k 15 ≧ 0.4, | k 15 change rate | ≦ 5
%, | Resonance frequency change rate | ≦ 0.3%, it was determined that the heat resistance was good. Among the measurement results, those subjected to polarization and post-polarization heat treatment within the scope of the present invention are summarized in Tables 3 and 4 together with the porcelain firing temperature (maximum density).
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【表４】 [Table 4]
【００２４】温度サイクル（外１）前後での共振周波数
の変化率（（ｆr−ｆr0）／ｆr0の値；％）も上記共振
子により測定し（表３），（表４）に示した。The temperature cycle (out 1) the rate of change of resonant frequency before and after ((value of f r -f r0) / f r0 ;%) was also measured by the resonator (Table 3), in (Table 4) Indicated.
【００２５】[0025]
【外１】 [Outside 1]
【００２６】温度サイクルによる共振周波数変動につい
ては０．３％以下のものを良品と判定した。With respect to the variation of the resonance frequency due to the temperature cycle, those having a resonance frequency of 0.3% or less were judged to be good.
【００２７】（表５）は（表１），（表２）の共振子を
分極条件、分極後熱処理条件を種々に変えた場合の共振
子特性を示したものである。それぞれの分極以降の加工
条件で本発明の請求項１に記載の圧電磁器組成物の内で
最も共振子特性的に不利なものを選んで分極後熱処理
（６０分）を施して３０分経過後の電気機械結合係数ｋ
15と熱処理前後での共振周波数変化率および温度サイク
ル（外１）前後での共振周波数の変化率を記載した。こ
こで例えば加工条件（ア）ではＭＰＢ組成近傍の磁器組
成物である試料No.２であればもともとｋ15は大きいた
め熱処理後のｋ15も本発明の範囲外の低めの分極温度で
ｋ15＞０．４となるが、ＰｂＴｉＯ3もしくはＰｂＺｒ
Ｏ3の含有量の多い磁器組成物である試料No.２５，２
６，２９，３０を選び本発明の範囲外の例とした。これ
により本発明の請求項１に記載する磁器組成物は、請求
項２に記載する製造方法を用いることによって所望の共
振子特性を得ることができることを示した。Table 5 shows the resonators of Tables 1 and 2.
Resonance when polarization conditions and post-polarization heat treatment conditions are variously changed
This shows the child characteristics. Processing after each polarization
Under the conditions, the piezoelectric ceramic composition according to claim 1 of the present invention
Post-polarization heat treatment with the most disadvantageous resonator characteristics
(60 minutes) and 30 minutes after the electromechanical coupling coefficient k
FifteenFrequency change rate and temperature cycle before and after heat treatment
The rate of change of the resonance frequency before and after (1) is described. This
Here, for example, under the processing condition (a), the porcelain set near the MPB composition
If it is sample No. 2 which is a product,FifteenIs big
K after heat treatmentFifteenAlso at lower polarization temperatures outside the scope of the invention
kFifteen> 0.4, but PbTiOThreeOr PbZr
OThreeNo. 25, 2 which is a porcelain composition having a high content of
6, 29 and 30 were selected as examples outside the scope of the present invention. this
Thus, the porcelain composition according to claim 1 of the present invention
By using the production method described in Item 2,
It was shown that pendulum characteristics could be obtained.
【００２８】[0028]
【表５】 [Table 5]
【００２９】以下本実施の形態について表を参照しなが
ら説明する。（表１）〜（表４）によるとα＜１．０の
試料No.９，１０は焼成温度が１２５０℃以上と上昇す
ると同時に、焼結性が低下し分極時に貫通破壊しやすく
なっている。α＞１．０４の試料No.１３，１４は電気
機械結合係数ｋ15が０．４以下まで低下しているが、こ
れは過剰のＰｂＯがガラス成分となって焼結体中に残留
したためである。従ってαは１．０≦α≦１．０４の範
囲に限定した。The present embodiment will be described below with reference to a table. According to Tables 1 to 4, Sample Nos. 9 and 10 with α <1.0 have the firing temperature increased to 1250 ° C. or higher, and at the same time, the sinterability is reduced and the fracture is likely to occur during polarization. . Samples Nos. 13 and 14 with α> 1.04 have the electromechanical coupling coefficient k 15 reduced to 0.4 or less, because excess PbO becomes a glass component and remains in the sintered body. is there. Therefore, α is limited to the range of 1.0 ≦ α ≦ 1.04.
【００３０】Ａ＜０．０１である試料No.１５は温度サ
イクルによる共振周波数変化率が０．３％以上と大き
く、Ａ＞０．１２である試料No.１８，１９は比抵抗が
低下して分極が困難になるためＡは０．０１≦Ａ≦０．
１２の範囲に限定した。Sample No. 15 where A <0.01 has a large change rate of the resonance frequency due to the temperature cycle of 0.3% or more, and Sample Nos. 18 and 19 where A> 0.12 have a low specific resistance. A becomes 0.01 ≦ A ≦ 0.
The range was limited to 12.
【００３１】Ｂ＜０．０１である試料No.２０は耐熱性
が低いため、Ｂ＞０．１５である試料No.２３は圧電性
が低下（ｋ15＜０．４）するためＢは０．０１≦Ｂ≦
０．１５の範囲に限定した。Sample No. 20 with B <0.01 has low heat resistance, and Sample No. 23 with B> 0.15 has low piezoelectricity (k 15 <0.4), so that B is 0. .01 ≦ B ≦
It was limited to the range of 0.15.
【００３２】Ｃ＜０．３０である試料No.２４は焼結性
および圧電性が低下する（ｋ15＜０．４）ため、Ｃ＞
０．６５である試料No.２７は焼結性が低下するためＣ
は０．３０≦Ｃ≦０．６０の範囲に限定した。In sample No. 24 having C <0.30, the sinterability and piezoelectricity are reduced (k 15 <0.4).
Sample No. 27, which is 0.65, has a low C
Was limited to the range of 0.30 ≦ C ≦ 0.60.
【００３３】Ｄ＜０．２５である試料No.２８は焼結性
が低下するため、Ａ，Ｂ，Ｃを上記範囲に限定したとき
Ｄは必然的にＤ≦０．６８となるため、Ｄは０．２５≦
Ｄ≦０．６８の範囲に限定した。Since the sinterability of Sample No. 28 with D <0.25 is reduced, D is inevitably D ≦ 0.68 when A, B, and C are limited to the above ranges. Is 0.25 ≦
It was limited to the range of D ≦ 0.68.
【００３４】ＰｂのＣａ，Ｓｒ，Ｂａのうち少なくとも
一種での置換量が１モル％以下である試料No.３１，３
２，３３，３４，３５，３６，３７は温度サイクルによ
る共振周波数変化率が０．３％以上と大きいため、置換
量が１０モル％以上ある試料No.４２，４３，４４，４
５，４６は耐熱性が低下しているため本発明の範囲から
除外した。Sample Nos. 31 and 3 in which the substitution amount of at least one of Pb with Ca, Sr, and Ba is 1 mol% or less.
Samples Nos. 42, 43, 44, and 4 having a replacement amount of 10 mol% or more have a large change rate of the resonance frequency due to the temperature cycle of 0.3% or more in 2, 33, 34, 35, 36, and 37.
Nos. 5, 46 were excluded from the scope of the present invention because of their reduced heat resistance.
【００３５】副成分であるＣｒ2Ｏ3およびＭｎ3Ｏ4（少
なくとも一種）の添加量については０．０５重量％以下
の試料No.４７，４８では耐熱性の低下もしくは温度サ
イクルによる共振周波数変化が０．３％以上と大きなも
のがあるため、１．２０重量％以上の試料５１では焼結
性および圧電性が低下するため本発明の範囲から除外し
た。With respect to the addition amounts of Cr 2 O 3 and Mn 3 O 4 (at least one type) as the auxiliary components, in Samples Nos. 47 and 48 in which the content was 0.05% by weight or less, the heat resistance was reduced or the resonance frequency was changed due to the temperature cycle. Is as large as 0.3% or more, and the sample 51 with 1.20% by weight or more has a reduced sinterability and piezoelectricity, and is therefore excluded from the scope of the present invention.
【００３６】分極条件については（表５）に示したよう
に分極温度が１３０℃より低い加工条件（ア）の試料で
は分極未飽和で、分極温度が１８０℃より高い加工条件
（エ）の試料では圧電磁器１の抵抗が低下し３．５ｋＶ
／mm以上の電圧が印加できなくなることから、分極時の
直流印加電圧については本発明の温度範囲で３．５ｋＶ
／mm以下の加工条件（オ）の試料では分極未飽和となる
ため本発明の範囲から除外した。Regarding the polarization conditions, as shown in (Table 5), the sample under the processing condition (a) whose polarization temperature is lower than 130 ° C. is not polarized, and the sample under the processing condition (d) whose polarization temperature is higher than 180 ° C. The resistance of the piezoelectric ceramic 1 is reduced to 3.5 kV
/ Mm or more cannot be applied, and the DC applied voltage during polarization is 3.5 kV within the temperature range of the present invention.
The sample under the processing condition (e) of not more than / mm was polarization-unsaturated and was excluded from the scope of the present invention.
【００３７】分極後の熱処理については本発明による圧
電磁器１は焦電効果が比較的大きく、分極後熱処理した
ときに図２（ａ）〜（ｃ）に示したように分極ベクトル
４と逆方向の反電界７を生ずる余分な浮遊電荷５が残
る。この浮遊電荷５を逃がして分極減少を最低限に押さ
えるため分極用電極３間は短絡した状態で行った。With respect to the heat treatment after polarization, the piezoelectric ceramic 1 according to the present invention has a relatively large pyroelectric effect, and when heat treatment is performed after polarization, the piezoelectric ceramic 1 has a direction opposite to the polarization vector 4 as shown in FIGS. An extra floating charge 5 that produces a reverse electric field 7 remains. In order to release the floating charges 5 and to minimize the decrease in polarization, the polarization electrodes 3 were short-circuited.
【００３８】（表５）で分極後の熱処理時に分極用電極
３間を短絡しない加工条件（キ）の試料では、ｋ15が
０．４以下に低下した。また熱処理温度については（表
５）に示したように２２０℃以下の温度で分極後に熱処
理した加工条件（ク）の試料は耐熱後の共振周波数変化
もしくはｋ15変化が大きいため、また２８０℃以上の温
度で分極後に熱処理した加工条件（サ）の試料は脱分極
が大きく、圧電性低下が顕著（ｋ15＜０．４）であるた
め本発明の範囲から除外した。[0038] In the samples (Table 5) not short between polarizing electrodes 3 during the heat treatment after polarization processing conditions (key), k 15 was reduced to 0.4 or less. As shown in Table 5, the heat treatment temperature of the sample subjected to the heat treatment after polarization at a temperature of 220 ° C. or less (h) has a large change in the resonance frequency or k 15 after heat resistance. The sample of the processing condition (S) which was heat-treated after polarization at the temperature described above was excluded from the scope of the present invention because of large depolarization and significant decrease in piezoelectricity (k 15 <0.4).
【００３９】[0039]
【発明の効果】以上本発明による厚みすべりモード共振
を利用した発振子、フィルタ用圧電磁器で比較的低温で
の焼成が可能で、電気機械結合係数が大きく、２８０℃
近傍の半田付け実装温度でも電気特性劣化の少ない、温
度サイクルによる共振周波数変化の少ない圧電磁器組成
物を提供することができる。As described above, it is possible to sinter at a relatively low temperature with a piezoelectric ceramic for a resonator and a filter utilizing thickness-shear mode resonance according to the present invention, and to have a large electromechanical coupling coefficient of 280 ° C
It is possible to provide a piezoelectric ceramic composition in which electrical characteristics are less deteriorated even at a soldering mounting temperature in the vicinity and a resonance frequency is less changed by a temperature cycle.
【図１】本発明の一実施の形態における厚みすべりモー
ド共振子の斜視図FIG. 1 is a perspective view of a thickness-shear mode resonator according to an embodiment of the present invention.
【図２】（ａ）本発明の一実施の形態における焦電効果
による分極済み圧電磁器における熱処理時の脱分極機構
を説明するための断面図 （ｂ）同断面図 （ｃ）同断面図FIG. 2A is a cross-sectional view for explaining a depolarization mechanism during heat treatment in a polarized piezoelectric ceramic due to a pyroelectric effect according to one embodiment of the present invention; FIG. 2B is a cross-sectional view;
１ 圧電磁器 ２ 共振電極 ３ 分極用電極 ４ 分極ベクトル ５ 浮遊電荷 ６ 表面電荷 ７ 反電界 Reference Signs List 1 piezoelectric ceramic 2 resonant electrode 3 electrode for polarization 4 polarization vector 5 floating charge 6 surface charge 7 demagnetizing field
Claims (2)
ｂの１モル％以上１０モル％以下をＣａ，Ｓｒ，Ｂａの
うち少なくとも一種で置換したものを主成分とし、副成
分としてＣｒ2Ｏ3およびＭｎ3Ｏ4のうち少なくとも一種
を０．０５〜１．２重量％含有させたことを特徴とする
圧電磁器組成物。 【化１】 1. The composition according to claim 1, wherein said compound is represented by the general formula (1):
b is at least 1 mol% and 10 mol% or less of at least one of Ca, Sr, and Ba as a main component, and at least one of Cr 2 O 3 and Mn 3 O 4 as an auxiliary component is 0.05 to 0.05 mol%. A piezoelectric porcelain composition containing 1.2% by weight. Embedded image
ｂの１モル％以上１０モル％以下をＣａ，Ｓｒ，Ｂａの
うち少なくとも一種で置換したものを主成分とし、副成
分としてＣｒ2Ｏ3およびＭｎ3Ｏ4のうち少なくとも一種
を０．０５〜１．２重量％添加、混合して成形体を得る
第１の工程と、この成形体を焼成して焼結体を得る第２
の工程と、この焼結体に分極電極を形成後、１３０〜１
８０℃の温度範囲で、３．５ｋＶ／mm以上の直流電界を
印加して分極する第３の工程と、この分極済み焼結体の
前記分極電極間を短絡させた状態で２２０〜２８０℃で
熱処理する第４の工程とを備えたことを特徴とする圧電
磁器組成物の製造方法。 【化２】 2. P in a composition represented by the general formula (Formula 2)
b is at least 1 mol% and 10 mol% or less of at least one of Ca, Sr, and Ba as a main component, and at least one of Cr 2 O 3 and Mn 3 O 4 as an auxiliary component is 0.05 to 0.05 mol%. A first step of adding and mixing 1.2% by weight to obtain a molded body, and a second step of sintering the molded body to obtain a sintered body.
After forming a polarized electrode on the sintered body,
A third step of applying a DC electric field of 3.5 kV / mm or more in a temperature range of 80 ° C. to polarize, and 220 to 280 ° C. in a state where the polarized electrodes of the polarized sintered body are short-circuited. And a fourth step of heat treatment. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10013720A JPH11209176A (en) | 1998-01-27 | 1998-01-27 | Piezoelectric porcelain composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10013720A JPH11209176A (en) | 1998-01-27 | 1998-01-27 | Piezoelectric porcelain composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11209176A true JPH11209176A (en) | 1999-08-03 |
Family
ID=11841092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10013720A Pending JPH11209176A (en) | 1998-01-27 | 1998-01-27 | Piezoelectric porcelain composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11209176A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005030673A1 (en) * | 2003-09-25 | 2005-04-07 | Tdk Corporation | Piezoelectric ceramic composition and piezoelectric device |
| JP2005219992A (en) * | 2004-02-09 | 2005-08-18 | Murata Mfg Co Ltd | Piezoelectric ceramic composition and piezoelectric element |
| JP2007161516A (en) * | 2005-12-12 | 2007-06-28 | Tdk Corp | Piezoelectric ceramic composition |
| US7608215B2 (en) | 2003-09-24 | 2009-10-27 | Tdk Corporation | Method of manufacturing a piezoelectric ceramic composition |
-
1998
- 1998-01-27 JP JP10013720A patent/JPH11209176A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7608215B2 (en) | 2003-09-24 | 2009-10-27 | Tdk Corporation | Method of manufacturing a piezoelectric ceramic composition |
| WO2005030673A1 (en) * | 2003-09-25 | 2005-04-07 | Tdk Corporation | Piezoelectric ceramic composition and piezoelectric device |
| KR100685327B1 (en) * | 2003-09-25 | 2007-02-22 | 티디케이가부시기가이샤 | Piezoelectric ceramic composition and piezoelectric device |
| CN100408508C (en) * | 2003-09-25 | 2008-08-06 | Tdk株式会社 | Piezoelectric ceramic composition and piezoelectric device |
| JP2005219992A (en) * | 2004-02-09 | 2005-08-18 | Murata Mfg Co Ltd | Piezoelectric ceramic composition and piezoelectric element |
| JP4506187B2 (en) * | 2004-02-09 | 2010-07-21 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric element |
| JP2007161516A (en) * | 2005-12-12 | 2007-06-28 | Tdk Corp | Piezoelectric ceramic composition |
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