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
Links
- 239000000919 ceramic Substances 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 title claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 5
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Landscapes
- 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 |
Country Status (1)
| Country | Link |
|---|---|
| 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 |
| DE60323704D1 (en) * | 2002-03-20 | 2008-11-06 | Denso Corp | Piezoelectric ceramic composition, process for its preparation and piezoelectric device |
| JP4212289B2 (en) * | 2002-04-04 | 2009-01-21 | Ｔｄｋ株式会社 | Method of manufacturing a piezoelectric ceramic |
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| CN100386291C (en) * | 2004-07-15 | 2008-05-07 | 清华大学 | Lead free piezoelectric ceramics of potassium sodium niobate and preparation thereof |
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| JP4878133B2 (en) * | 2004-09-13 | 2012-02-15 | 株式会社デンソー | Piezoelectric actuator |
| WO2007119653A1 (en) | 2006-04-13 | 2007-10-25 | Murata Manufacturing Co., Ltd. | Ceramic powder, and method for production of 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
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| Publication number | Publication date |
|---|---|
| JPH0782024A (en) | 1995-03-28 |
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