JP3362473B2 - Piezoelectric ceramic composition - Google Patents
Piezoelectric ceramic compositionInfo
- Publication number
- JP3362473B2 JP3362473B2 JP24872893A JP24872893A JP3362473B2 JP 3362473 B2 JP3362473 B2 JP 3362473B2 JP 24872893 A JP24872893 A JP 24872893A JP 24872893 A JP24872893 A JP 24872893A JP 3362473 B2 JP3362473 B2 JP 3362473B2
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric ceramic
- ceramic composition
- composition
- added
- piezoelectricity
- 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 - Lifetime
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- Compositions Of Oxide Ceramics (AREA)
Description
【0001】[0001]
【産業上の利用分野】本願発明は、圧電セラミック素
子、特に、圧電セラミックフィルタ、圧電セラミック発
振子などの材料として有用な圧電磁器組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition useful as a material for piezoelectric ceramic elements, particularly piezoelectric ceramic filters and piezoelectric ceramic oscillators.
【0002】[0002]
【従来の技術】圧電セラミックフィルタや圧電セラミッ
ク発振子などの圧電セラミック素子に用いられる材料
(圧電磁器組成物)として、従来より、チタン酸ジルコ
ン酸鉛(Pb(Zr,Ti)O3)を主成分とする圧電
磁器組成物が広く用いられており、さらに、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磁
器組成物が提案されている。2. Description of the Related Art Lead zirconate titanate (Pb (Zr, Ti) O 3 ) has been mainly used as a material (piezoelectric ceramic composition) used for piezoelectric ceramic elements such as piezoelectric ceramic filters and piezoelectric ceramic oscillators. A piezoelectric ceramic composition as a component is widely used, and further, a piezoelectric ceramic composition to which various trace additives are added in order to improve its piezoelectric characteristics has been proposed.
【0003】そして、これらの圧電磁器組成物として、
例えば、Pb(Zr,Ti)O3のPbの一部をBa,
Sr,Caなどの二価の元素で置換したもの、あるいは
Pb(Zr,Ti)O3に第三成分として、Pb(Mn
1/3Sb2/3)O3やPb(Mn1/3Nb2/3)O3を固溶さ
せたものなどが提案されている。And, as these piezoelectric ceramic compositions,
For example, a part of Pb of Pb (Zr, Ti) O 3 is Ba,
What is substituted with a divalent element such as Sr or Ca, or Pb (Zr, Ti) O 3 as Pb (Mn
It has been proposed to use 1/3 Sb 2/3 ) O 3 or Pb (Mn 1/3 Nb 2/3 ) O 3 as a solid solution.
【0004】[0004]
【発明が解決しようとする課題】しかし、Pb(Zr,
Ti)O3を主組成とする上記従来の圧電磁器組成物に
おいては、圧電性と誘電率との間に相関関係があり、一
般に圧電性を大きくすると誘電率も大きくなる傾向があ
る。したがって、誘電損失が大きくなるような高周波用
デバイスに用いるには適当でないという問題点がある。However, Pb (Zr,
In the conventional piezoelectric ceramic composition having Ti) O 3 as a main composition, there is a correlation between the piezoelectricity and the dielectric constant, and generally, when the piezoelectricity is increased, the dielectric constant tends to increase. Therefore, there is a problem that it is not suitable for use in a high frequency device that causes a large dielectric loss.
【0005】また、チタン酸ジルコン酸鉛では、その周
波数定数は2000Hz・m程度であり、例えば、10
MHzの共振周波数を持つ素子を得ようとすると、厚み
振動を利用する場合、その厚みを0.2mm程度にまで薄
くする必要があり、加工が困難になるという問題点があ
る。The frequency constant of lead zirconate titanate is about 2000 Hz · m, and for example, 10
In order to obtain an element having a resonance frequency of MHz, when utilizing thickness vibration, it is necessary to reduce the thickness to about 0.2 mm, which causes a problem that processing becomes difficult.
【0006】さらに、組成中に重金属であるPbを60
%程度含有しているため、Pbが外部に排出されて環境
問題が発生しないように管理する必要があり、製造工程
が複雑になるという問題点がある。Furthermore, Pb, which is a heavy metal, is included in the composition.
%, It is necessary to control so that Pb will not be discharged to the outside and environmental problems will occur, and there is a problem that the manufacturing process becomes complicated.
【0007】本願発明は、上記問題点を解決するもので
あり、低い誘電率と高い周波数定数を有するとともに良
好な電気機械結合係数を有しており、素子加工上の困難
性が少なく、しかもPbを含有せず、環境上の問題を生
じるおそれのない圧電磁器組成物を提供することを目的
とする。The present invention solves the above-mentioned problems and has a low dielectric constant and a high frequency constant as well as a good electromechanical coupling coefficient, so that there is little difficulty in processing the element and Pb is used. It is an object of the present invention to provide a piezoelectric ceramic composition which does not contain any of the above and does not cause environmental problems.
【0008】[0008]
【課題を解決するための手段】上記目的を達成するため
に、本願第1の発明の圧電磁器組成物は、
一般式:(NaXK1-X)(Nb1-YTaY)O3
で表され、かつ、前記一般式中のX及びYが、
0.2≦X≦0.8
0.0≦Y≦0.5
の範囲にあることを特徴とする。In order to achieve the above object, the piezoelectric ceramic composition of the first invention of the present application has the general formula: (Na X K 1-X ) (Nb 1-Y Ta Y ) O 3 And X and Y in the general formula are in the range of 0.2 ≦ X ≦ 0.8 0.0 ≦ Y ≦ 0.5.
【0009】また、本願第2の発明の圧電磁器組成物
は、上記圧電磁器組成物に対して、第一遷移金属を含む
化合物の少なくとも1種を、その含有率が0.01〜
2.0重量%になるような割合で添加したことを特徴と
する。The piezoelectric ceramic composition of the second invention of the present application has a content of 0.01 to 10 of at least one compound containing a first transition metal in the piezoelectric ceramic composition.
It is characterized in that it was added at a ratio of 2.0% by weight.
【0010】本願第1の発明の圧電磁器組成物におい
て、X(すなわちNaのモル分率)を0.2〜0.8と
したのは、Xがこの範囲を外れると完全な焼結体を得る
ことができないことによる。In the piezoelectric ceramic composition of the first invention of the present application, X (that is, the mole fraction of Na) is set to 0.2 to 0.8, because when X is out of this range, a perfect sintered body is obtained. Because you can't get.
【0011】また、Y(すなわちTaのモル分率)を
0.0〜0.5としたのは、Yが0.5を越えると室温
における圧電性が失われ、圧電材料としての用途に供す
ることができなくなることによる。Further, the reason why Y (that is, the mole fraction of Ta) is 0.0 to 0.5 is that when Y exceeds 0.5, the piezoelectricity at room temperature is lost, and it is used as a piezoelectric material. Due to being unable to.
【0012】さらに、本願第2の発明の圧電磁器組成物
において、第一遷移金属を含む化合物の少なくとも1種
を添加するようにしたのは、TiO2,Mn2O3などの
第一遷移金属を含む化合物を添加した場合に圧電性が向
上することによる。Further, in the piezoelectric ceramic composition of the second invention of the present application, at least one compound containing a first transition metal is added so that the first transition metal such as TiO 2 or Mn 2 O 3 is added. This is because the piezoelectricity is improved when a compound containing is added.
【0013】そして、その添加割合を0.01〜2.0
重量%の範囲としたのは、添加量が0.01重量%未満
の場合には、圧電性がほとんど改善されず、また、2.
0重量%を越えて添加した場合には、圧電性向上の効果
が顕著でなくなること、及び完全に焼結することが困難
になることによる。The addition ratio is 0.01 to 2.0.
The range of weight% is that the piezoelectricity is hardly improved when the addition amount is less than 0.01% by weight, and
This is because when the content exceeds 0% by weight, the effect of improving the piezoelectricity becomes insignificant and it becomes difficult to completely sinter.
【0014】[0014]
【実施例】以下、本願発明の実施例を示して、その特徴
とするところをさらに具体的に説明する。EXAMPLES Examples of the present invention will be shown below to describe the features of the present invention more specifically.
【0015】まず、出発原料として、K2CO3,Ta原
料(例えばTa 2 O 5 ),Na2CO3,Nb2O5,TiO
2,Mn2O3を用意し、これらの出発原料を表1に示す
ような組成となるように秤取して、ボールミルを用いて
約5時間湿式混合し、得られた混合物を乾燥した後、7
00〜900℃で仮焼した。それから、この仮焼体を粗
粉砕した後、有機バインダを適量加え、ボールミルを用
いて5〜10時間湿式粉砕し、40メッシュのふるいを
通して粒度調整を行った。次に、これを750〜100
0kg/cm2の圧力で直径12mm、厚さ1.2mmの円板に
成形した後、1000〜1250℃の温度で焼成を行な
い、磁器円板を得た。First, K 2 CO 3 and Ta raw materials are used as starting materials.
Materials (for example, Ta 2 O 5 ) , Na 2 CO 3 , Nb 2 O 5 , TiO
2 , Mn 2 O 3 were prepared, these starting materials were weighed so as to have the composition shown in Table 1, wet-mixed for about 5 hours using a ball mill, and the obtained mixture was dried. , 7
It was calcined at 00 to 900 ° C. Then, after roughly crushing the calcined body, an appropriate amount of an organic binder was added, and wet crushing was performed for 5 to 10 hours using a ball mill, and the particle size was adjusted through a 40 mesh sieve. Next, add this to 750-100
A disk having a diameter of 12 mm and a thickness of 1.2 mm was formed at a pressure of 0 kg / cm 2 , and then baked at a temperature of 1000 to 1250 ° C. to obtain a porcelain disk.
【0016】そして、この磁器円板の表面(両主面)
に、通常の方法により、銀ペーストを塗布焼付けして銀
電極を形成した後、150〜200℃の絶縁オイル中で
3〜5kV/mmの直流電圧を30分間印加して分極処理
を施し、圧電磁器円板(試料)を得た。The surface (both main surfaces) of this porcelain disc
Then, a silver paste is applied and baked by a usual method to form a silver electrode, and a DC voltage of 3 to 5 kV / mm is applied for 30 minutes in an insulating oil of 150 to 200 ° C. to perform polarization treatment. A porcelain disc (sample) was obtained.
【0017】そして、これらの各圧電磁器円板(試料)
について、比誘電率(εr),径方向及び厚み方向の振
動における電気機械結合係数(Kp及びKt)、周波数
定数及び共振周波数の温度変化率f−TCを測定した。
その結果を表1に示す。なお、上記特性は、インピーダ
ンス測定器により共振周波数及び反共振周波数を測定
し、計算により求めた。Each of these piezoelectric ceramic discs (samples)
The relative dielectric constant (εr), the electromechanical coupling coefficient (Kp and Kt) in vibration in the radial direction and the thickness direction, the frequency constant, and the temperature change rate f-TC of the resonance frequency were measured.
The results are shown in Table 1. In addition, the said characteristic was calculated | required by measuring the resonance frequency and anti-resonance frequency with an impedance measuring device.
【0018】[0018]
【表1】 [Table 1]
【0019】表1に示すように、この発明の実施例にか
かる各試料については、εrが150〜400、Kpが
27〜48%、Ktが33〜50%、周波数定数が33
90〜3520、f−TCが−200〜+150の範囲
にあり、従来のチタン酸ジルコン酸鉛系の圧電磁器組成
物では限界があった、低誘電率及び高周波数定数が実現
されており、かつ、比較的良好な電気機械結合係数が得
られていることがわかる。As shown in Table 1, for each sample according to the embodiment of the present invention, εr is 150 to 400, Kp is 27 to 48%, Kt is 33 to 50%, and frequency constant is 33.
90 to 3520, f-TC is in the range of -200 to +150, and low dielectric constant and high frequency constant, which have been limited in the conventional lead zirconate titanate-based piezoelectric ceramic composition, are realized, and It can be seen that a relatively good electromechanical coupling coefficient is obtained.
【0020】なお、本願発明の圧電磁器組成物は、上記
実施例に限定されるものではなく、発明の要旨の範囲内
において、その組成を変化させることが可能である。The piezoelectric ceramic composition of the present invention is not limited to the above-mentioned examples, and the composition can be changed within the scope of the gist of the invention.
【0021】[0021]
【発明の効果】上述のように、本願第1の発明の圧電磁
器組成物は、一般式:(NaXK1-X)(Nb1-YTaY)
O3で表され、かつ、前記一般式中のX及びYが、0.
2≦X≦0.8,0.0≦Y≦0.5の範囲にあるよう
な組成を有していることから、従来のチタン酸ジルコン
酸鉛系の圧電磁器組成物では限界があった低誘電率と高
周波数定数を同時に実現するとともに、比較的良好な電
気機械結合係数を得ることができる。As described above, the piezoelectric ceramic composition of the first invention of the present application has the general formula: (Na X K 1-X ) (Nb 1-Y Ta Y ).
Is represented by O 3 , and X and Y in the general formula are 0.
Since the composition is in the range of 2 ≦ X ≦ 0.8 and 0.0 ≦ Y ≦ 0.5, there is a limit in the conventional lead zirconate titanate-based piezoelectric ceramic composition. A low dielectric constant and a high frequency constant can be realized at the same time, and a relatively good electromechanical coupling coefficient can be obtained.
【0022】また、本願第2の発明の圧電磁器組成物
は、本願第1の発明の圧電磁器組成物に、さらに、第一
遷移金属を含む化合物の少なくとも1種を、その含有率
が0.01〜2.0重量%になるような割合で添加して
いるので、上記第1の発明の圧電磁器組成物よりもさら
に圧電性に優れた圧電磁器組成物を得ることが可能にな
る。Further, the piezoelectric ceramic composition of the second invention of the present application is the same as the piezoelectric ceramic composition of the first invention of the present application, in which the content of at least one compound containing the first transition metal is 0. Since it is added in a proportion of 01 to 2.0% by weight, it becomes possible to obtain a piezoelectric ceramic composition having more excellent piezoelectricity than the piezoelectric ceramic composition of the first invention.
【0023】したがって、本願発明の圧電磁器組成物に
よれば、低誘電損失の高周波フィルタに応用するのに適
したセラミック素子を得ることができる。Therefore, according to the piezoelectric ceramic composition of the present invention, it is possible to obtain a ceramic element suitable for application to a high frequency filter having a low dielectric loss.
【0024】また、周波数定数が従来のチタン酸ジルコ
ン酸鉛系の圧電磁器組成物より大きい(約1.5倍)こ
とから、同じ共振周波数を有する素子を得ようとした場
合に、その寸法(厚み)が約1.5倍になり、それだ
け、素子加工上の問題を軽減することが可能になる。Further, since the frequency constant is larger than that of the conventional lead zirconate titanate-based piezoelectric ceramic composition (about 1.5 times), the dimensions ( (Thickness) is about 1.5 times, and it becomes possible to reduce the problem in device processing.
【0025】さらに、組成中にPbを含有しないので、
Pbが排出されることによる環境問題の発生を防止する
ことができる。Furthermore, since Pb is not contained in the composition,
It is possible to prevent the occurrence of environmental problems due to the discharge of Pb.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭49−33907(JP,A) 特開 昭61−106454(JP,A) 特開 昭58−167467(JP,A) 特開 平5−178694(JP,A) 特開 平5−301798(JP,A) (58)調査した分野(Int.Cl.7,DB名) C04B 35/495 CA(STN)─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-49-33907 (JP, A) JP-A-61-106454 (JP, A) JP-A-58-167467 (JP, A) JP-A-5- 178694 (JP, A) JP-A-5-301798 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C04B 35/495 CA (STN)
Claims (2)
aY)O3 で表され、かつ、前記一般式中のX及びYが、 0.2≦X≦0.8 0.0≦Y≦0.5 の範囲にあることを特徴とする圧電磁器組成物。1. The general formula: (Na X K 1-X ) (Nb 1-Y T
a Y ) O 3 and X and Y in the general formula are in the range of 0.2 ≦ X ≦ 0.8 0.0 ≦ Y ≦ 0.5. Composition.
て、第一遷移金属を含む化合物の少なくとも1種を、そ
の含有率が0.01〜2.0重量%になるような割合で
添加したことを特徴とする圧電磁器組成物。2. The piezoelectric ceramic composition according to claim 1, wherein at least one compound containing a first transition metal is contained in a proportion of 0.01 to 2.0% by weight. A piezoelectric ceramic composition characterized by being added.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24872893A JP3362473B2 (en) | 1993-09-08 | 1993-09-08 | Piezoelectric ceramic composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24872893A JP3362473B2 (en) | 1993-09-08 | 1993-09-08 | Piezoelectric ceramic composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0782024A JPH0782024A (en) | 1995-03-28 |
JP3362473B2 true JP3362473B2 (en) | 2003-01-07 |
Family
ID=17182474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24872893A Expired - Lifetime JP3362473B2 (en) | 1993-09-08 | 1993-09-08 | Piezoelectric ceramic composition |
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JP (1) | JP3362473B2 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3531803B2 (en) | 1999-02-24 | 2004-05-31 | 株式会社豊田中央研究所 | Alkali metal containing niobium oxide based piezoelectric material composition |
US6514427B2 (en) | 1999-10-18 | 2003-02-04 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric ceramic composition and piezoelectric element containing the same |
JP2001342065A (en) | 2000-05-30 | 2001-12-11 | Matsushita Electric Ind Co Ltd | Piezoelectric ceramic composition |
JP4929522B2 (en) * | 2000-08-25 | 2012-05-09 | 株式会社豊田中央研究所 | Piezoelectric ceramic composition |
JP3750507B2 (en) * | 2000-08-28 | 2006-03-01 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric ceramic element using the same |
EP1302454A1 (en) | 2001-10-11 | 2003-04-16 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric ceramic composition and piezoelectric element using the same |
JP4616544B2 (en) * | 2002-03-20 | 2011-01-19 | 株式会社豊田中央研究所 | Piezoelectric ceramic composition, production method thereof, and piezoelectric element |
US7150838B2 (en) | 2002-03-20 | 2006-12-19 | Denso Corporation | Piezoelectric ceramic composition, its production method and piezoelectric device |
JP4212289B2 (en) * | 2002-04-04 | 2009-01-21 | Tdk株式会社 | Method of manufacturing a piezoelectric ceramic |
US7101491B2 (en) | 2002-07-16 | 2006-09-05 | Denso Corporation | Piezoelectric ceramic composition and method of production of same, piezoelectric element, and dielectric element |
JP2004155601A (en) * | 2002-11-05 | 2004-06-03 | Nippon Ceramic Co Ltd | Piezoelectric ceramic composition |
EP1457471B1 (en) | 2003-03-14 | 2014-02-26 | Denso Corporation | Crystal oriented ceramics and production method of same |
WO2005021461A1 (en) * | 2003-08-28 | 2005-03-10 | National Institute Of Advanced Industrial Science And Technology | Perovskite solid solution composition and piezoelectric ceramics produced therefrom |
CN100386291C (en) * | 2004-07-15 | 2008-05-07 | 清华大学 | Lead free piezoelectric ceramics of potassium sodium niobate and preparation thereof |
JP4795748B2 (en) * | 2004-09-13 | 2011-10-19 | 株式会社デンソー | Piezoelectric actuator |
JP4878133B2 (en) * | 2004-09-13 | 2012-02-15 | 株式会社デンソー | Piezoelectric actuator |
JP5365986B2 (en) | 2006-04-13 | 2013-12-11 | 株式会社村田製作所 | Ceramic powder and method for producing ceramic powder |
CN100465312C (en) * | 2007-08-24 | 2009-03-04 | 北京科技大学 | Process for producing potassium-sodium niobate/copper piezo-electricity composite material |
-
1993
- 1993-09-08 JP JP24872893A patent/JP3362473B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0782024A (en) | 1995-03-28 |
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