JPH09183652A - Ferroelectric ceramic composition - Google Patents
Ferroelectric ceramic compositionInfo
- Publication number
- JPH09183652A JPH09183652A JP8292947A JP29294796A JPH09183652A JP H09183652 A JPH09183652 A JP H09183652A JP 8292947 A JP8292947 A JP 8292947A JP 29294796 A JP29294796 A JP 29294796A JP H09183652 A JPH09183652 A JP H09183652A
- Authority
- JP
- Japan
- Prior art keywords
- pyroelectric
- titanate
- mol
- composition
- porcelain
- 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.)
- Granted
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、チタン酸鉛,チタ
ン酸カルシウム及びチタン酸アンチモンを基本成分とす
る強誘電体磁器組成物に関する。TECHNICAL FIELD The present invention relates to a ferroelectric ceramic composition containing lead titanate, calcium titanate and antimony titanate as basic components.
【0002】[0002]
【従来の技術】強誘電体磁器組成物は、焦電素子,セラ
ミックフィルタ,セラミック共振子などに用いられ、そ
の組成物としては、例えば、硫酸グリシン,ニオブ酸リ
チウム,タンタル酸リチウムなどの単結晶や、チタン酸
ジルコン酸鉛,チタン酸鉛系磁器材料が知られている。2. Description of the Related Art Ferroelectric porcelain compositions are used for pyroelectric elements, ceramic filters, ceramic resonators, etc., and examples of such compositions include single crystals of glycine sulfate, lithium niobate, lithium tantalate, etc. Also known are lead zirconate titanate and lead titanate porcelain materials.
【0003】焦電素子としては、温度変化に対応する自
発分極の変化が大きい程、焦電係数(dPs/dT)が
大きく、比誘電率が小さいほど優れたものであって、キ
ュリー点Tcの高い安定なものが安価に提供されること
が、実用上望ましい。As the pyroelectric element, the pyroelectric coefficient (dPs / dT) is larger as the change in spontaneous polarization corresponding to the temperature change is larger, and the smaller the relative dielectric constant is, the more excellent the pyroelectric element is. It is practically desirable that inexpensive and highly stable products are provided.
【0004】高周波数フィルタ用電圧素子としては、誘
電率,tanδが小さく、共振周波数の温度係数の小さ
い材料が望ましい。As the voltage element for the high frequency filter, a material having a small dielectric constant and tan δ and a small temperature coefficient of resonance frequency is desirable.
【0005】[0005]
【発明が解決しようとする課題】ところが、上記各材料
の有効性について検討した結果によれば、硫酸グリシン
は水溶性の結晶であるため、温度に弱くもろく加工が難
しいうえ、キュリー点が49℃と著しく低いため、焦電
焦電素子としても高周波フィルタ用圧電素子としても使
用温度範囲が著しく限定されて好ましくないことがわか
った。However, according to the results of studying the effectiveness of each of the above materials, glycine sulfate is a water-soluble crystal, so it is weak in temperature and difficult to process, and the Curie point is 49 ° C. Since it is extremely low, it was found that the operating temperature range is extremely limited as a pyroelectric pyroelectric element and a piezoelectric element for a high frequency filter, which is not preferable.
【0006】ニオブ酸リチウムは、加工性は良好である
が焦電係数が小さく高価であり、タンタル酸リチウムは
加工性は良く焦電係数も比較的大きく、切断方位により
零温度係数を持ち、圧電素子としても優れているが、何
分単結晶のため高価で工業上の利用に不利である。Lithium niobate has good workability, but has a low pyroelectric coefficient and is expensive. Lithium tantalate has good workability and a relatively large pyroelectric coefficient, has a zero temperature coefficient depending on the cutting direction, and has a piezoelectric property. Although it is excellent as an element, it is expensive for a few minutes because it is a single crystal, which is disadvantageous for industrial use.
【0007】チタン酸ジルコン酸鉛系磁器は加工性が良
く、焦電係数も組成により大きいものを選ぶことがで
き、圧電材料としてその特性を組成により制御できるこ
とから、この材料系の開発が積極的に行われてきた。Lead zirconate titanate-based porcelain has good workability, and it is possible to choose one having a larger pyroelectric coefficient in composition, and its characteristics can be controlled by composition as a piezoelectric material. Therefore, development of this material system is actively conducted. Has been done to.
【0008】このチタン酸ジルコン酸鉛系材料は、Pb
(Zr−Ti)O3を主体としたものであって、さらに
Mn,Cr,Nb,Co,Feなどの金属酸化物を添加
するか、Pb(Mg1/3Nb2/3)O3などの複合酸化物
を固溶させるなどの改良が圧電材料分野において広く行
われている。This lead zirconate titanate-based material is Pb
(Zr-Ti) be one of O 3 as a main component, further Mn, Cr, Nb, Co, or the addition of metal oxides such as Fe, Pb (Mg 1/3 Nb 2/3 ) O 3 , etc. Improvements such as solid solution of the complex oxide are widely made in the field of piezoelectric materials.
【0009】しかしながら、このようなチタン酸ジルコ
ン酸鉛系磁器では一般に温度特性の良い組成では、誘電
率は500〜1200程度と高く、焦電材料や高周波圧
電材料としては適していない。そのため、誘電率の小さ
い材料が検討されているが、実効的誘電率を350より
小さくすることは困難である。However, in such a lead zirconate titanate porcelain, a composition having a good temperature characteristic generally has a high dielectric constant of about 500 to 1200 and is not suitable as a pyroelectric material or a high frequency piezoelectric material. Therefore, a material having a small dielectric constant has been studied, but it is difficult to make the effective dielectric constant smaller than 350.
【0010】さらにチタン酸鉛系磁器は、焦電係数が大
きく比誘電率も比較的小さいが、これは焼結しにくく、
鉛が焼成中蒸発して均一な組成で安定した圧電特性を持
つ磁器を得ることは難しいという欠点がある。しかもこ
の磁器は、分極にかなり高電圧が必要である。一方これ
らの欠点を改善するために、希土類,その他金属酸化物
を同時添加又は置換したチタン酸鉛系磁器が知られてい
る。この材料は誘電率が150〜300程度とジルコン
チタン酸鉛に比べて低く、圧電特性も良好であるが、焼
結性にやや難点があり、大型磁器が得られにくいこと
や、分極条件が厳しいため、工業化における歩留りを高
めにくいなどの欠点があり、また、高価な希土類の添加
物を用いるため、その商品化には難点があった。Further, the lead titanate porcelain has a large pyroelectric coefficient and a relatively small dielectric constant, but it is difficult to sinter,
There is a drawback that it is difficult to obtain a porcelain having a uniform composition and stable piezoelectric characteristics because lead evaporates during firing. Moreover, this porcelain requires a fairly high voltage for polarization. On the other hand, in order to improve these drawbacks, lead titanate-based porcelain to which rare earths and other metal oxides are simultaneously added or substituted is known. This material has a dielectric constant of about 150 to 300, which is lower than that of lead zircon titanate and has good piezoelectric characteristics, but has a slight difficulty in sinterability, making it difficult to obtain a large porcelain and strict polarization conditions. Therefore, there are drawbacks such that it is difficult to increase the yield in industrialization, and since an expensive rare earth additive is used, there is a problem in commercialization thereof.
【0011】この問題を解決する先行例として、特開昭
63−144165号公報には、(Pb1-x・Cax)
〔(Mn1/2・Sb1/2)y・Ti1-y〕O3で表わ
される基本組成において、x,yを次に示される範囲、 x=0.10〜0.40 y=0.01〜0.20 にあることを特徴とする焦電素子用酸化物磁器材料が記
載されている。この先行例は、焦電素子用の材料として
知られる純粋なPbTiO3磁器については、従来より
焦電素子の材料として性能的に期待されながら、製造上
の厳しさから未だ十分な性能を有する物が生産されてい
ないことから、PbTiO3に特定の変性化を行い、M
n1/2・Sb1/2の条件の下で大量生産に適した安
価で高性能な焦電素子用材料を提供しようとするもので
ある。この試みにおいては、試料についての比誘電率
と、焦電係数と、焦電効果出力指数とのデータを収集し
て従来の材料に比較して特性的に優れているという効果
が強調されている。As a prior art example for solving this problem, Japanese Patent Application Laid-Open No. 63-144165 discloses (Pb 1- x.Cax).
In the basic composition represented by [(Mn1 / 2 · Sb1 / 2 ) y · Ti 1-y ] O 3, x, ranges shown below the y, x = 0.10~0.40 y = 0.01 The oxide porcelain material for a pyroelectric element is characterized by being about 0.20. In this prior art example, pure PbTiO 3 porcelain, which is known as a material for a pyroelectric element, is expected to be a material for a pyroelectric element from the prior art, but it still has sufficient performance due to the strictness in manufacturing. Since PbTiO 3 is not produced, PbTiO 3 is subjected to a specific modification,
It aims to provide an inexpensive and high-performance pyroelectric element material suitable for mass production under the condition of n1 / 2 · Sb1 / 2. In this attempt, the effect of being excellent in characteristics as compared with the conventional material by collecting data of the relative permittivity, the pyroelectric coefficient, and the pyroelectric effect output index of the sample is emphasized. .
【0012】上記目的に使用される強誘電体磁器組成物
は、近年用途が増々拡大しつつあり、用途拡大に伴って
組成物に要求される特性は多岐にわたり、しかも要求さ
れる特性のレベルはますます厳しくなり、従来の特性の
レベルでは満足できず、さらに優れた特性でしかも安定
した強磁性体磁器組成物の開発が強く望まれている。Ferroelectric porcelain compositions used for the above purposes have been expanding their applications in recent years, and the properties required for the compositions are wide-ranging with the expansion of their applications. There is a strong demand for the development of a ferromagnetic porcelain composition which has become more and more strict, is not satisfactory at the level of conventional characteristics, and has even more excellent characteristics and is stable.
【0013】本発明の目的は、上記要求に応じて誘電
率,結合係数が高く、圧電特性,誘電特性,焦電特性を
維持しながら広い組成範囲にわたって焼結性に優れた強
誘電体磁器組成物を提供することにある。An object of the present invention is to satisfy the above requirements, a ferroelectric ceramic composition having a high dielectric constant and a high coupling coefficient, and excellent sinterability over a wide composition range while maintaining piezoelectric characteristics, dielectric characteristics and pyroelectric characteristics. To provide things.
【0014】[0014]
【課題を解決するための手段】上記目的を達成するた
め、本発明による強誘電体磁器組成物においては、チタ
ン酸鉛,チタン酸カルシウム及びチタン酸アンチモンを
基本成分とする強誘電体磁器組成物であって、基本組成
が化学式、 (1−x−y)PbTiO3−xCaTiO3−ySb
2/3TiO3 但しxは1.0〜35mol%,yは1.0〜30mo
l%で表わされ、上記化学式のTiは、Mnで0.5〜
5mol%置換されているものである。To achieve the above object, in a ferroelectric ceramic composition according to the present invention, a ferroelectric ceramic composition containing lead titanate, calcium titanate and antimony titanate as basic components. Where the basic composition is represented by the chemical formula: (1-x-y) PbTiO 3 -xCaTiO 3 -ySb
2/3 TiO 3 where x is 1.0 to 35 mol% and y is 1.0 to 30 mo
It is represented by 1% and Ti in the above chemical formula is 0.5 to Mn.
5 mol% is substituted.
【0015】[0015]
【発明の実施の形態】発明者らは焦電素子として優れた
素子を提供すべく鋭意研究を重ねた結果、チタン酸鉛,
チタン酸カルシウム,チタン酸アンチモンを基本構成成
分とする特定の組成物について、TiがMnにより特定
の割合で置換されたものが、誘電特性,圧電特性,焦電
特性及びその温度特性に優れており、その上良好な焼結
性を有し、かつ分極条件が穏かであることを見出し、こ
の知見に基づいて本発明を完成するに至った。BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies conducted by the inventors to provide an excellent element as a pyroelectric element, lead titanate,
A specific composition containing calcium titanate and antimony titanate as a basic constituent, in which Ti is replaced by Mn in a specific ratio, is excellent in dielectric properties, piezoelectric properties, pyroelectric properties and its temperature properties. Moreover, they have found that they have good sinterability and have mild polarization conditions, and have completed the present invention based on this finding.
【0016】本発明の強誘電体磁器組成物は、基本組成
が、化学式:(1−x−y)PbTiO3−xCaTi
O3−ySb2/3TiO3で表わされるチタン酸鉛,チタ
ン酸カルシウム,チタン酸アンチモンを基本構成成分と
する組成物からなるもので、この組成物のチタン酸カル
シウムの含有割合については上記化学式のxが1.0〜
35mol%の範囲であることが必要である。このxの
値が1.0mol%未満であると圧電特性とその温度特
性とがともに劣化し、焦電係数も小さく、焦電素子とし
ても不適合である。また35mol%を超えると誘電率
が300を超え、焦電用としても高周波用としても適さ
なくなる。The ferroelectric ceramic composition of the present invention has a basic composition of the chemical formula: (1-x-y) PbTiO 3 -xCaTi.
The composition is composed of lead titanate, calcium titanate, and antimony titanate represented by O 3 -ySb 2/3 TiO 3 as basic constituent components. The content ratio of calcium titanate in this composition is represented by the above chemical formula. X is 1.0 to
It should be in the range of 35 mol%. When the value of x is less than 1.0 mol%, both the piezoelectric characteristics and the temperature characteristics are deteriorated, the pyroelectric coefficient is small, and the pyroelectric element is not suitable. Further, when it exceeds 35 mol%, the dielectric constant exceeds 300, which makes it unsuitable for pyroelectric use and high frequency use.
【0017】一方、チタン酸アンチモンの含有割合は、
yが1.0〜30mol%の範囲であることが必要であ
る。On the other hand, the content ratio of antimony titanate is
It is necessary that y is in the range of 1.0 to 30 mol%.
【0018】このyの値が1.0mol%未満では該磁
器の焼結性が劣り、素体の変形が著しいし、また30m
ol%を超えると粒界に異相が析出し、圧電特性が劣化
し、焦電材料として使用できない。When the value of y is less than 1.0 mol%, the sinterability of the porcelain is poor, the deformation of the element body is remarkable, and the length is 30 m.
If it exceeds ol%, a heterogeneous phase precipitates at the grain boundaries and the piezoelectric characteristics deteriorate, so that it cannot be used as a pyroelectric material.
【0019】また本発明の磁器組成物においては、上記
化学式におけるTiがMnで0.5〜5mol%置換さ
れることが必要である。この割合が、0.5mol%未
満では分極中絶縁破壊を起こしやすく、製造上好ましく
ない傾向を示し、また5mol%を超えると焼結性が悪
くなり、かつ電気的特性が著しく減少して分極不能とな
り、焦電素子として、あるいは圧電素子としては使用で
きない。Further, in the porcelain composition of the present invention, Ti in the above chemical formula needs to be replaced by Mn by 0.5 to 5 mol%. If this ratio is less than 0.5 mol%, dielectric breakdown tends to occur during polarization, which is not preferable in manufacturing. If it exceeds 5 mol%, the sinterability deteriorates, and the electrical characteristics significantly decrease, making polarization impossible. Therefore, it cannot be used as a pyroelectric element or a piezoelectric element.
【0020】本発明の磁器は次に示すような通常の窯業
的手法によって容易に製造することができる。The porcelain of the present invention can be easily manufactured by a usual ceramic method as described below.
【0021】例えばPbO,TiO2,CaCO3,Sb
2O3MnO2又は焼成により酸化物に変換し得る、それ
ぞれに対応する水酸化物,炭酸塩,蓚酸塩,硝酸塩など
を出発原料として、これら原料粉末を所定の割合で配合
し、ボールミルなどを用いて十分混合し、この混合物を
700〜900℃の温度範囲で仮焼し、さらにボールミ
ルなどにより粉砕する。次いで、このようにして得られ
た仮焼粉末に水又はポリビニールアルコールなどのバイ
ンダーを少量添加して0.5〜2ton/cm2の圧力
で加圧成形した後、この成形体を1150℃〜1250
℃の温度範囲で2〜4時間焼成することにより本発明の
磁器が得られる。For example, PbO, TiO 2 , CaCO 3 , Sb
2 O 3 MnO 2 or corresponding hydroxides, carbonates, oxalates, nitrates, etc. that can be converted into oxides by firing are used as starting materials, and these raw material powders are blended at a predetermined ratio, and a ball mill or the like is used. The resulting mixture is thoroughly mixed, calcined in the temperature range of 700 to 900 ° C., and further pulverized by a ball mill or the like. Then, a small amount of water or a binder such as polyvinyl alcohol is added to the calcined powder thus obtained, and pressure molding is performed at a pressure of 0.5 to 2 ton / cm 2 , and then the molded body is heated to 1150 ° C. 1250
The porcelain of the present invention can be obtained by firing in the temperature range of ° C for 2 to 4 hours.
【0022】本発明による磁器は、通常の空気中の焼成
においても緻密なものが得られるが、酸素雰囲気焼成や
ホットプレス法,熱間静水圧プレス法などを用いること
により一層緻密なものが得られる。The porcelain according to the present invention can be dense even when it is fired in normal air, but a more dense one can be obtained by using oxygen atmosphere firing, hot pressing, hot isostatic pressing or the like. To be
【0023】本発明の磁器における組成図を図1に示
す。図1は、Pb(Ti1-mMnm)O3,Ca(Ti1-m
Mnm)O3,Sb2/3(Ti1-mMnm)O3を頂点とする三
角座標で示されたものであり、MnはMnO2で0.5
〜5mol%である。図中、本発明に適合する最大の範
囲を斜線の領域で示している。A composition diagram of the porcelain of the present invention is shown in FIG. FIG. 1 shows Pb (Ti 1-m M nm ) O 3 , Ca (Ti 1-m
M nm ) O 3 and Sb 2/3 (Ti 1-m M nm ) O 3 are shown in triangular coordinates with apexes, and Mn is MnO 2 of 0.5.
~ 5 mol%. In the figure, the maximum range compatible with the present invention is indicated by a shaded area.
【0024】本発明の強誘電体磁器組成物は広い領域に
わたって、 は100〜260,電気機械結合係数(kt)は35〜
50%と高い値を示し、焦電素子や高周波用フィルタ素
子として圧電特性,誘電特性,焦電特性を維持しながら
広い組成範囲にわたって焼結性が良く、かつ緻密で、大
型の磁器が容易に得られ、分極処理が80〜120℃,
40KV/cm〜60KV/cmと容易であること,希
土類元素は使用しないため比較的安価であることなどの
点から極めて工業的価値の高いものである。The ferroelectric ceramic composition of the present invention covers a wide area, Is 100 to 260, and the electromechanical coupling coefficient (kt) is 35 to
It shows a high value of 50% and has good sinterability over a wide composition range while maintaining piezoelectric characteristics, dielectric characteristics, and pyroelectric characteristics as a pyroelectric element and high-frequency filter element, and it is easy to make large porcelain. Obtained, the polarization treatment is 80 to 120 ° C.,
It is of extremely high industrial value because it is as easy as 40 KV / cm to 60 KV / cm and is relatively inexpensive because it does not use rare earth elements.
【0025】(実施例)次に実施例により本発明をさら
に詳細に説明するが、本発明はこれらの例によって何ら
限定されるものではない。(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【0026】化学式:(1−x−y)Pb(Ti1-mM
nm)O3−xCa(Ti1-mMnm)−ySb2/3(Ti1-m
Mnm)O3におけるx,y,mの値を変化させ、それぞ
れの組成の試料No.1〜No.30における圧電磁器
の諸特性を表1に示す。Chemical formula: (1-xy) Pb (Ti 1-m M
nm) O 3 -xCa (Ti 1 -m M nm) -ySb 2/3 (Ti 1-m
The values of x, y, and m in M nm ) O 3 are changed, and the sample No. of each composition is changed. 1 to No. Table 1 shows various characteristics of the piezoelectric ceramic of No. 30.
【0027】[0027]
【表1】 [Table 1]
【0028】なお、圧電磁器の各特性を次の方法で求め
た。 (1)誘電特性および圧電特性 直径20mm,厚さ1mmの円板磁器を作成し、この円
板磁器の両面にAg電極を焼付け80〜120℃,40
〜60KV/cmの条件で分極処理を行い、24時間放
置後1KHzで誘電率(ε),tanδを測定し、ま
た、IREの標準回路の方法に従って厚み方向の電気機
械結合係数を求めた。また共振周波数の温度計数frT
cも求めた。Each characteristic of the piezoelectric ceramic was determined by the following method. (1) Dielectric and Piezoelectric Properties A disk porcelain having a diameter of 20 mm and a thickness of 1 mm was prepared, and Ag electrodes were baked on both sides of the disk porcelain at 80 to 120 ° C. and 40 ° C.
Polarization treatment was performed under the conditions of -60 KV / cm, and after standing for 24 hours, the dielectric constant (ε) and tan δ were measured at 1 KHz, and the electromechanical coupling coefficient in the thickness direction was determined according to the method of the IRE standard circuit. Also, the temperature coefficient frT of the resonance frequency
I also asked for c.
【0029】(2)焦電特性 直径20mm,厚さ1mmの磁器円板を作成し(1)の
方法で分極処理を施した後、焦電特性の測定を行った。(2) Pyroelectric property A porcelain disk having a diameter of 20 mm and a thickness of 1 mm was prepared, polarized by the method of (1), and then the pyroelectric property was measured.
【0030】(比較例)出発原料としてPbO,TiO
3,Sb2O3,CaCO3,MnO2の各粉末を用い、こ
れらの粉末を所定の割合で配合し、この混合物を900
℃で2時間仮焼して得られた仮焼物を、ボールミルで粉
砕した。次いで、バインダーとポリビニールアルコール
を少量添加し、2ton/cm2の圧力で加圧成形した
後、この成形体を1150℃〜1220℃の温度で3時
間焼成して圧電磁器を作成した。このようにして得られ
た圧電磁器の各性能を組成とともに表2に示す。(Comparative Example) PbO and TiO as starting materials
3 , Sb 2 O 3 , CaCO 3 , and MnO 2 powders were used, and these powders were blended at a predetermined ratio, and the mixture was mixed with 900
The calcined product obtained by calcining at 0 ° C. for 2 hours was crushed with a ball mill. Next, a small amount of a binder and polyvinyl alcohol were added, and the mixture was pressure-molded at a pressure of 2 ton / cm 2 , and the molded body was fired at a temperature of 1150 ° C to 1220 ° C for 3 hours to prepare a piezoelectric ceramic. The performances of the piezoelectric ceramics thus obtained are shown in Table 2 together with their compositions.
【0031】[0031]
【表2】 [Table 2]
【0032】誘電率(ε)は、小さい方が焦電素子の感
度が向上する。高周波フィルタとしても小さい方がイン
ピーダンスのマッチングがとれ易くフィルタ特性が良く
なる。表1より、本発明によれば100〜260の範囲
の値が得られている。The smaller the dielectric constant (ε), the higher the sensitivity of the pyroelectric element. The smaller the high frequency filter is, the better the impedance matching is, and the better the filter characteristics are. From Table 1, according to the present invention, values in the range of 100 to 260 are obtained.
【0033】誘電損失(tanδ)は、小さい方がよ
い。焦電素子としても小さい方がノイずが少ない。高周
波フィルタとしても、伝送特性が改善される。本発明で
は0.5〜1.9%以下の値が得られている。The smaller the dielectric loss (tan δ), the better. Smaller pyroelectric elements have less noise. The transmission characteristics are also improved as a high frequency filter. In the present invention, a value of 0.5 to 1.9% or less is obtained.
【0034】キュリー点(Tc)は、強誘電特性が消失
する温度で、なるべく高い方が、焦電特性,フィルタ特
性共に安定である。本発明では、200℃以上の値が得
られている。The Curie point (Tc) is the temperature at which the ferroelectric characteristic disappears, and the higher the Curie point, the more stable the pyroelectric characteristic and the filter characteristic. In the present invention, a value of 200 ° C. or higher is obtained.
【0035】結合係数(kt)は、大きい方が良い。焦
電素子では、感度が向上し、フィルタでは帯域幅が大き
くなりフィルタの設計が楽になる。本発明によれば35
%〜50%である。The larger the coupling coefficient (kt), the better. The pyroelectric element improves the sensitivity, and the filter has a large bandwidth, which facilitates the filter design. According to the invention 35
% To 50%.
【0036】焦電係数(dPs/dT)は、大きい程焦
電素子の感度は向上する。本発明によれば、4.0×1
0-8coul/cm3K以上である。The larger the pyroelectric coefficient (dPs / dT), the higher the sensitivity of the pyroelectric element. According to the invention, 4.0 × 1
It is 0 -8 coul / cm 3 K or more.
【0037】共振周波数の温度係数(frTc)は、小
さい程フィルタの伝送特性が安定で温度変化に対して中
心周波数がずれない。本発明によれば±50ppm/℃
以下である。The smaller the temperature coefficient (frTc) of the resonance frequency, the more stable the transmission characteristics of the filter and the more the center frequency does not shift with respect to the temperature change. According to the invention ± 50 ppm / ° C
It is as follows.
【0038】なお、表2における比較例としての試料N
o.31はxが1.0mol%未満のものであり、焦電
係数が小さい。試料No.32はxが35mol%を超
えるものであり、焦電係数が小さく、誘電率も300を
はるかに超え、焦電用,高周波用のいずれにも適さな
い。Sample N as a comparative example in Table 2
o. 31 has x of less than 1.0 mol% and has a small pyroelectric coefficient. Sample No. In the case of 32, x exceeds 35 mol%, the pyroelectric coefficient is small, and the dielectric constant far exceeds 300, which is not suitable for both pyroelectric use and high frequency use.
【0039】試料No.33はyが1.0mol%未満
のものであり、焼結性が劣り素体の変形が著しい。試料
No.34はyが30mol%を超えるものであり、粒
界に異相が析出して圧電特性が著しく劣化している。Sample No. In 33, y was less than 1.0 mol%, the sinterability was poor, and the element body was significantly deformed. Sample No. In No. 34, y exceeds 30 mol%, and a different phase is precipitated at the grain boundary, and the piezoelectric characteristics are significantly deteriorated.
【0040】試料No.35は、Mnが0.5mol%
未満のものであり、分極中素体が割れ易く絶縁破壊を起
こし易い。試料No.36は、Mnが5mol%を超え
るもので、素体の電気抵抗が低くなり分極中に電流が流
れすぎて分極が困難であった。なお、Sb2/3の添加量
y(%)が、1.0mol%未満のものでは焼結性に劣
り、素体の変形が著しい。Sb2/3の添加量y(%)
は、表1に示したようにMnの添加量の2倍以上添加し
なければ、低レベルの電気特性しか得ることができな
い。Sample No. 35 has Mn of 0.5 mol%
It is less than less than 100%, and the element in polarization is easily cracked and dielectric breakdown is likely to occur. Sample No. In No. 36, Mn was more than 5 mol%, the electric resistance of the element body was low, and an excessive current flowed during polarization, which made polarization difficult. In addition, when the addition amount y (%) of Sb 2/3 is less than 1.0 mol%, the sinterability is inferior and the element body is significantly deformed. Sb 2/3 addition amount y (%)
As shown in Table 1, if the addition amount of Mn is not more than twice the addition amount, only low level electric characteristics can be obtained.
【0041】本発明において、Sb2/3の好ましい添加
量y(%)は、Mnの添加量m(%)の2倍以上であ
る。In the present invention, the preferable addition amount y (%) of Sb 2/3 is twice or more the addition amount m (%) of Mn.
【0042】Mnの添加量mを、m=0.05(5mo
l%)に設定したときの本発明による組成図を図2の領
域Aに示し、m=0.005(0.5mol%)に設定
したときの組成図を図3の領域Cに示す。The addition amount of Mn, m, is set to m = 0.05 (5 mo
The composition diagram according to the present invention when set to 1%) is shown in a region A of FIG. 2, and the composition diagram when set to m = 0.005 (0.5 mol%) is shown in a region C of FIG.
【0043】比較のため、先行例(特開昭63−144
165号公報)に示される(Pb1- x・Cax)〔(M
n1/2・Sb1/2)y・Ti1-y〕O3で表わされる
組成において、Mnの添加量を5mol%に設定したと
きの領域Bを図2に、0.5mol%に設定したときの
領域Dを図3にそれぞれ比較例として示している。図
2,3に明らかなように、本発明によれば菱形の領域と
して特定されるのに対し、比較例では、直線領域で特定
される。すなわち、本発明によれば、広い組成範囲にわ
たって安定した特性が得られる。For comparison, a prior art example (JP-A-63-144)
(Pb 1- x · Cax) [(M
In the composition represented by n1 / 2 · Sb1 / 2) y · Ti 1-y ] O 3, the region B at the time of setting the addition amount of Mn to 5 mol% in FIG. 2, when set to 0.5 mol% Regions D are shown in FIG. 3 as comparative examples. As apparent from FIGS. 2 and 3, according to the present invention, the region is specified as a rhombic region, whereas in the comparative example, it is specified as a linear region. That is, according to the present invention, stable characteristics can be obtained over a wide composition range.
【0044】[0044]
【発明の効果】以上のように本発明によれば、広い領域
にわたって誘電率,電気機械結合係数が高く、圧電特
性,誘電特性,焦電特性を維持しながら広い組成範囲に
わたって焼結性に優れ、誘電率,誘電損失,キュリー
点,結合係数,焦電係数,共振周波数の温度係数は、共
に規格値を満足し、焦電素子,セラミックフィルタ,セ
ラミック共振子などの磁器材料に用いて優れた効果を得
ることができる。As described above, according to the present invention, the dielectric constant and electromechanical coupling coefficient are high over a wide range, and the sinterability is excellent over a wide composition range while maintaining the piezoelectric characteristics, dielectric characteristics, and pyroelectric characteristics. , Dielectric constant, dielectric loss, Curie point, coupling coefficient, pyroelectric coefficient, and temperature coefficient of resonance frequency all satisfy the standard values, and are excellent for use in porcelain materials such as pyroelectric elements, ceramic filters, and ceramic resonators. The effect can be obtained.
【図1】本発明の磁器における組成図である。FIG. 1 is a composition diagram of a porcelain of the present invention.
【図2】Mnの添加量5mol%のときの組成図であ
る。FIG. 2 is a composition diagram when the amount of Mn added is 5 mol%.
【図3】Mnの添加量0.5mol%のときの組成図で
ある。FIG. 3 is a composition diagram when the amount of Mn added is 0.5 mol%.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡部 圭佑 埼玉県狭山市新狭山1丁目11番4号 株式 会社大泉製作所内 (72)発明者 田中 陽一 埼玉県狭山市新狭山1丁目11番4号 株式 会社大泉製作所内 (72)発明者 大沢 準一 富山県上新川郡大沢野町下大久保3158番地 北陸電気工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Keisuke Okabe 1-11-4 Shin-Sayama, Sayama City, Saitama Prefecture Oizumi Manufacturing Co., Ltd. (72) Yoichi Tanaka 1-11-4 Shin-Sayama, Sayama City, Saitama Prefecture Stock company Oizumi Manufacturing (72) Inventor Junichi Osawa 3158 Shimookubo, Osawano-cho, Kamishinkawa-gun, Toyama Prefecture Hokuriku Electric Industry Co., Ltd.
Claims (1)
タン酸アンチモンを基本成分とする強誘電体磁器組成物
であって、 基本組成が化学式、 (1−x−y)PbTiO3−xCaTiO3−ySb
2/3TiO3 但しxは1.0〜35mol%,yは1.0〜30mo
l%で表わされ、 上記化学式のTiは、Mnで0.5〜5mol%置換さ
れていることを特徴とする強誘電体磁器組成物。1. A ferroelectric ceramic composition containing lead titanate, calcium titanate and antimony titanate as basic components, wherein the basic composition is represented by the chemical formula: (1-x-y) PbTiO 3 -xCaTiO 3 -ySb.
2/3 TiO 3 where x is 1.0 to 35 mol% and y is 1.0 to 30 mo
A ferroelectric ceramic composition represented by 1%, wherein Ti in the above chemical formula is replaced with Mn in an amount of 0.5 to 5 mol%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8292947A JP2987762B2 (en) | 1996-11-05 | 1996-11-05 | Ferroelectric porcelain composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8292947A JP2987762B2 (en) | 1996-11-05 | 1996-11-05 | Ferroelectric porcelain composition |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2051413A Division JP2932297B2 (en) | 1990-03-02 | 1990-03-02 | Ferroelectric porcelain composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09183652A true JPH09183652A (en) | 1997-07-15 |
JP2987762B2 JP2987762B2 (en) | 1999-12-06 |
Family
ID=17788487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8292947A Expired - Lifetime JP2987762B2 (en) | 1996-11-05 | 1996-11-05 | Ferroelectric porcelain composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2987762B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013035704A (en) * | 2011-08-05 | 2013-02-21 | Nec Tokin Corp | Pyroelectric material, and pyroelectric type infrared sensor using the same |
US10519066B2 (en) | 2015-12-18 | 2019-12-31 | Murata Manufacturing Co., Ltd. | Dielectric porcelain composition, method for producing dielectric porcelain composition, and multilayer ceramic electronic component |
-
1996
- 1996-11-05 JP JP8292947A patent/JP2987762B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013035704A (en) * | 2011-08-05 | 2013-02-21 | Nec Tokin Corp | Pyroelectric material, and pyroelectric type infrared sensor using the same |
US10519066B2 (en) | 2015-12-18 | 2019-12-31 | Murata Manufacturing Co., Ltd. | Dielectric porcelain composition, method for producing dielectric porcelain composition, and multilayer ceramic electronic component |
Also Published As
Publication number | Publication date |
---|---|
JP2987762B2 (en) | 1999-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3482394B2 (en) | Piezoelectric ceramic composition | |
JP2001316182A (en) | Piezoelectric ceramic and piezoelectric resonator | |
KR100305167B1 (en) | Piezoelectric ceramic composition and piezoelectric device using the same | |
JP4493226B2 (en) | Piezoelectric ceramic and piezoelectric element | |
JP4020454B2 (en) | Method for manufacturing piezoelectric ceramics | |
JP3198906B2 (en) | Piezoelectric porcelain composition | |
JP3827915B2 (en) | Piezoelectric material and manufacturing method thereof | |
JP2987762B2 (en) | Ferroelectric porcelain composition | |
US4601841A (en) | Ferroelectric ceramic composition | |
JP3830298B2 (en) | Piezoelectric ceramic composition | |
JP2932297B2 (en) | Ferroelectric porcelain composition | |
JP3114886B2 (en) | Piezoelectric ceramics | |
JP4355115B2 (en) | Piezoelectric ceramic and piezoelectric element | |
JP2737451B2 (en) | Piezoelectric material | |
JP3215013B2 (en) | Piezoelectric ceramic composition | |
JPH04188882A (en) | Piezoelectric porcelain composition | |
JP3006188B2 (en) | High frequency dielectric ceramic composition | |
JPH0283257A (en) | Porcelain composition of high permittivity for temperature compensation and production thereof | |
JPS63182255A (en) | Piezoelectric ceramic composition | |
JPH08268757A (en) | Porcelain composition | |
JP2002137966A (en) | Piezoelectric ceramic and piezoelectric element | |
JPH0660057B2 (en) | Pyroelectric porcelain material | |
JPH09183651A (en) | Dielectric ceramic composition and condenser using the same and production of the dielectric ceramic composition | |
JPH1017364A (en) | Piezoelectric ceramic composition | |
JP2001302333A (en) | Dielectric ceramic composition |