JPH01298063A - Ferroelectric ceramics - Google Patents
Ferroelectric ceramicsInfo
- Publication number
- JPH01298063A JPH01298063A JP63129800A JP12980088A JPH01298063A JP H01298063 A JPH01298063 A JP H01298063A JP 63129800 A JP63129800 A JP 63129800A JP 12980088 A JP12980088 A JP 12980088A JP H01298063 A JPH01298063 A JP H01298063A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ferroelectric
- piezoelectric
- piezoelectric constant
- mno2
- 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
- 239000000919 ceramic Substances 0.000 title claims description 41
- 239000006104 solid solution Substances 0.000 claims description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 24
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- 229910019653 Mg1/3Nb2/3 Inorganic materials 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012255 powdered metal Substances 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- 229910020698 PbZrO3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910008253 Zr2O3 Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
九胛立腹歪±１
本発明は、Ｐｂ（Ｍｇ Ｎｂ ）Ｏ−１／３
２／３ ３
Ｐｂ Ｔｉ ０３−Ｐｂ Ｚｒ Ｏ３系強誘電性セラミ
ックスに関し、さらに詳しくは、圧電定数ｄおよびａ械
的晶質係数Ｑｒｍのともに大きな
Ｐｂ （Ｍｇ Ｎｂ ） ＯＰ ｂ Ｔｉ
０３−１／３ ２／３ ３
Ｐｂ Ｚｒ Ｏ３系強誘電性セラミックスに関する。[Detailed Description of the Invention] The present invention is characterized in that Pb(MgNb)O-1/3
2/3 3 Pb Ti 03-Pb Zr Regarding O3-based ferroelectric ceramics, in more detail, Pb (Mg Nb ) OP b Ti has a large piezoelectric constant d and a mechanical crystallinity coefficient Qrm.
03-1/3 2/3 3 Pb Zr O3-based ferroelectric ceramics.
Ｈの ′０″′景ｆらびに の問題飄
従来、強誘電性セラミックスからなる圧電材料は、圧電
フィルタ、圧電トランス、超音波振動子あるいは圧電ブ
ザーなどの種々の用途に利用されている。これらの用途
に用いられている鱈も代表的な強誘電性セラミックスと
しては、ＰｂＴｉＯ３−ＰｂＺｒＯ３系固溶体が知られ
ている。また、さらに圧電特性を改良したＰｂ （Ｍ
（＋ １７３Ｎｂ ）Ｏ−ＰｂＴｉＯ３−ＰｂＺｒ
Ｏ３系２／３ ３
固溶体（特公昭４２−９７１６号公報など）ならびにこ
れらの固溶体にＢａＴｉ Ｏ，５ｒＴｉ Ｏ３またはＣ
ａ Ｔ ｉ Ｏ３を含有させた強誘電性セラミックスな
ども知られている。Piezoelectric materials made of ferroelectric ceramics have been used in various applications such as piezoelectric filters, piezoelectric transformers, ultrasonic vibrators, and piezoelectric buzzers. A PbTiO3-PbZrO3 solid solution is known as a typical ferroelectric ceramic used for applications such as Pb (M
(+173Nb)O-PbTiO3-PbZr
O3-based 2/3 3 solid solutions (Japanese Patent Publication No. 42-9716, etc.) and these solid solutions contain BaTiO, 5rTiO3 or C.
Ferroelectric ceramics containing a T i O3 are also known.
ところで、圧電材料をアクチュエータとして用いること
が検討されているが、この場合、圧電セラミックスによ
り、電気エネルギーを機械的エネルギーに変換し、この
機械的エネルギーによって圧電セラミックス自体が変位
する必要があるため、圧電セラミックスの圧電定数ｄを
大きくする必要がある。By the way, the use of piezoelectric materials as actuators is being considered, but in this case, piezoelectric ceramics must convert electrical energy into mechanical energy, and the piezoelectric ceramic itself must be displaced by this mechanical energy. It is necessary to increase the piezoelectric constant d of ceramics.
一般に、圧電定数ｄと、電気機械結合係数におよび比誘
電率εとの間には、
ｄ−ＣＫ Ｅ
なる関係があり、圧電室Ｒｄを大きくするためには、電
気機械結合係数におよび／または比誘電率εを大きくし
なければならない。Generally, there is a relationship d-CK E between the piezoelectric constant d, the electromechanical coupling coefficient, and the relative dielectric constant ε, and in order to increase the piezoelectric chamber Rd, the electromechanical coupling coefficient and/or The dielectric constant ε must be increased.
また、圧電セラミックスの機械的共振を利用したアクチ
ュエータ、たとえば超音波モータ等の用途においては圧
電定数ｄおよび機械的品質係数Ｑ１１のともに大である
ことが必要である。圧電セラミックスを超音波モータ等
の用途に用いる場合には、駆動周波数が高周波であるた
め、機械的品質係数Ｑｍが小さいと発熱し、自発分極の
減少、圧電定数の変化等が生じる。そこで、圧電セラミ
ックスのＲ械的品質係数Ｑｎが大であることは、圧電セ
ラミックスを超音波モータ等の用途に用いる場合には重
要なことである。Furthermore, in applications such as actuators that utilize the mechanical resonance of piezoelectric ceramics, such as ultrasonic motors, it is necessary that both the piezoelectric constant d and the mechanical quality factor Q11 be large. When piezoelectric ceramics are used for applications such as ultrasonic motors, the driving frequency is high, so if the mechanical quality factor Qm is small, heat is generated, resulting in a decrease in spontaneous polarization, a change in the piezoelectric constant, etc. Therefore, it is important that piezoelectric ceramics have a large R mechanical quality factor Qn when piezoelectric ceramics are used for applications such as ultrasonic motors.
Ｐｂ ＴｉＯ３−ＰｂｚｒＯ３系固溶体やｐｂ（Ｍｇ
Ｎｂ ）Ｏ−
１／３ ２／３ ３
Ｐｂ Ｔｉ ０３−Ｐｂ Ｚｒ Ｏ３系固溶体に対して
、ＭｎＯ２を含有させると機械的品質係数Ｑ１１を大き
くすることができるが、Ｍ ｎ Ｏ２の含有量の増加と
ともに圧電定数ｄが大幅に低下するという問題点があっ
た。したがって、ＭｎＯ２を含有させる前のベースとな
る固溶体としては、圧電定数ｄの十分大きなものが望ま
しい。Pb TiO3-PbzrO3 solid solution and pb(Mg
Nb ) O- 1/3 2/3 3 Pb Ti 03-Pb Zr When MnO2 is added to the O3-based solid solution, the mechanical quality factor Q11 can be increased, but the increase in the MnO2 content At the same time, there was a problem in that the piezoelectric constant d significantly decreased. Therefore, it is desirable that the solid solution serving as the base before incorporating MnO2 has a sufficiently large piezoelectric constant d.
これまで、たとえばＰｂ（Ｍ（ｌ Ｎｂ ）１
／３ ２／３
０３−Ｐｂ Ｔｉ ０３−Ｐｂ Ｚｒ ０３系固溶体な
らびにこれらの固溶体にＢａ ’Ｉ’ｉ ０３、Ｓｒ
ＴｉＯ３またはＣａ Ｔ’ ｉ ０３を含有させた固溶
体に、電気機械結合係数におよび／または比誘電率を大
きくすることによって［［定数ｄを大きくする目的で、
さらに各種酸化物を含有させた材料がいくつか提案され
ているが、圧電定数ｄの大きさは必ずしも満足のいくレ
ベルではない。たとえば、これら固溶体にＮｉＯをさら
に含有させた場合、ＮｉＯ含有量の増加とともに圧電定
数ｄが向上するが、限度を越してＮｉＯを含有させると
、圧電定数ｄは低下してしまう、これは、これら固溶体
において、Ｎ１イオンがＡＢＯ３で表わされるペロブス
カイト型結晶のＢサイトに選択的に入るため、限度を越
してＮｉＯを含有させると、Ａサイトのイオンが不足し
、ついには一部のＮｉＯがへロブスカイト結晶に取り込
まれなくなるためと考えられる。Until now, for example, Pb(M(l Nb )1
/3 2/3 03-Pb Ti 03-Pb Zr 03-based solid solution and Ba'I'i 03, Sr in these solid solutions
By increasing the electromechanical coupling coefficient and/or relative permittivity of a solid solution containing TiO3 or Ca T' i 03,
Furthermore, although some materials containing various oxides have been proposed, the magnitude of the piezoelectric constant d is not necessarily at a satisfactory level. For example, when these solid solutions further contain NiO, the piezoelectric constant d improves as the NiO content increases, but when NiO is added beyond the limit, the piezoelectric constant d decreases. In a solid solution, N1 ions selectively enter the B site of the perovskite crystal represented by ABO3, so if NiO is contained beyond the limit, ions at the A site will be insufficient, and some NiO will eventually become herovskite. This is thought to be because it is no longer incorporated into the crystal.
本発明者らは、このような知見に基づき、Ｂサイトに入
る金属イオンに加え、Ａサイトに入る金属イオンを併せ
て含有させることにより、これらの酸化物をすべてへロ
ブスカイト結晶中に取り込ませた場合、Ｂサイトに入る
金属イオンのみを含有させた場合に比べ、圧電定数ｄの
大きな強誘電性セラミックスが得られることを見出した
。さらに、上記の如き圧電定数ｄの大きな強誘電性セラ
ミックスを提供する固溶体にＭｎＯ２を含有させた場合
、圧電定数ｄおよび機械的品質係数Ｑ１１のともに大き
な強誘電体セラミックスが？）られることを見出し、本
発明を完成するに至った。Based on this knowledge, the present inventors incorporated all of these oxides into the herovskite crystal by including metal ions that enter the A site in addition to the metal ions that enter the B site. It has been found that in this case, a ferroelectric ceramic with a larger piezoelectric constant d can be obtained than when only metal ions entering the B site are contained. Furthermore, if MnO2 is contained in a solid solution that provides a ferroelectric ceramic with a large piezoelectric constant d as described above, will a ferroelectric ceramic with a large piezoelectric constant d and mechanical quality factor Q11 be obtained? ), and have completed the present invention.
几班ム旦追
本発明は、上記のような点に鑑みて完成されたものであ
って、圧電定数ｄおよびＲＩｉｉＩｉ的品質係数Ｑｎが
ともに大きく、圧電特性に優れた強誘電性セラミックス
を提供することを目的としている。SUMMARY OF THE INVENTION The present invention was completed in view of the above points, and provides a ferroelectric ceramic having a large piezoelectric constant d and a large RIiii quality factor Qn and excellent piezoelectric properties. The purpose is to
九肌Ａ月１
このような目的を達成するために、本発明に係る強誘電
性セラミックスは、Ｐｂ Ｍ−ａ ａ
（ＭＱ Ｎｂ ｙ
１／３ ２／３ ）ｘ” ”ｚＯ３［ただし、Ｍは
［３ａまたはＳｒであり、ｘ ＋ ｙ ＋ ７． ＝
１ ］で表わされ、
ａ＝Ｏ〜０．１０
ｘ＝０．０５〜０．７０
、ｙ＝０． ２５〜０．５０
ｚ＝０． ０５〜０．７０
であるペロブスカイト型固溶体に対し、下記のＡ群から
選ばれた少なくとも１種以上の酸化物と、下記のＢ群か
ら選ばれた少なくとも１種以上の酸化物とをともに含有
せしめ、さらにＭｎ Ｏ，を含有せしめてなるペロブス
カイト型固溶体であることを特徴としている。In order to achieve such an object, the ferroelectric ceramics according to the present invention has Pb M-a a (MQ Nb y 1/3 2/3)x""zO3 [However, M is [3a or Sr, x + y + 7. =
1 ], a=O~0.10 x=0.05~0.70, y=0. 25-0.50 z=0. 05 to 0.70, containing at least one or more oxides selected from the following Group A and at least one or more oxides selected from the following Group B. , and further contains Mn 2 O. It is characterized by being a perovskite solid solution.
Ａ群（［ａ２０３、Ｎｄ２０３）
Ｂ群（ＺｎＯ１Ｓ００２）
このような本発明に係る強誘電性セラミックスは、ＡＢ
Ｏ３で表わされるペロブスカイト型結晶におけるＡ、８
両サイトに上記のような金属酸化物の金属イオンをそれ
ぞれ含有させるようにした上で、ＭｎＯ２を含有せしめ
ていることから、従来既知の強誘電性セラミックスと比
較した場合、はぼ同等のａｌ械的品質係数Ｑｎを持ちな
がら、より大きな圧電定数ｄを有している。したがって
、本発明に係る強誘電性セラミックスは、超音波モータ
等を含む機械的共振を利用したアクチュエータ等の用途
に用いた場合に両れな特性を示ず６九胛立且体煎盈泗
以下本発明に係る強誘電性セラミックスについて具体的
に説明する。Group A ([a203, Nd203) Group B (ZnO1S002) Such ferroelectric ceramics according to the present invention are AB
A, 8 in perovskite crystal represented by O3
Since both sites contain the metal ions of the metal oxides mentioned above, and MnO2 is also included, when compared with conventionally known ferroelectric ceramics, it is almost the same as the Al material. It has a larger piezoelectric constant d while having a high quality factor Qn. Therefore, when the ferroelectric ceramics according to the present invention are used in applications such as actuators that utilize mechanical resonance, including ultrasonic motors, etc., the ferroelectric ceramics do not exhibit either of these characteristics, and the ferroelectric ceramics exhibit less than 69 degrees of strength. The ferroelectric ceramic according to the present invention will be specifically explained.
本発明に係る強誘電性セラミックスは、Ｐｂ Ｍ
（Ｍｇ Ｎｂ ） Ｔｉ１−ａ ａ
１／３ ２／３ ｘ ＶＺｒ２０３ ［ただ
し、ＭはＢａまたはｓｒであり、Ｘ ＋ ｙ ＋ ｚ
＝ １ ］で表わされ、ａ、ｘ、ｙ、ｚは下記の範囲に
あり、
ａ＝ Ｏ〜０．１０、好ましくは０．０１〜０，０７ｘ
＝ ０．０５〜０．７０、好ましくは０．１０〜０．
６０ｙ＝０．２５〜０．５０、好ましくは０．３０〜０
．４５ｚ＝０．０５〜０．７０、好ましくは０．１０〜
０．６０とのペロブスカイト型固溶体に対し、下記のＡ
群から選ばれた少なくとも１稲以上の酸化物と、下記の
Ｂ群から選ばれた少なくとも１種以上の酸化物をともに
含有せしめ、さらにＭｎＯ２を含有せしめてなるペロブ
スカイト型固溶体である。The ferroelectric ceramic according to the present invention includes PbM
(MgNb) Ti1-a a
1/3 2/3 x VZr203 [However, M is Ba or sr, and X + y + z
= 1 ], a, x, y, z are in the following range, a = O ~ 0.10, preferably 0.01 ~ 0.07x
= 0.05-0.70, preferably 0.10-0.
60y=0.25-0.50, preferably 0.30-0
．． 45z=0.05~0.70, preferably 0.10~
For the perovskite solid solution with 0.60, the following A
This is a perovskite-type solid solution that contains at least one oxide selected from the group B, at least one oxide selected from the following group B, and further contains MnO2.
Ａ群（［ａ２０３、Ｎｄ２０３）
Ｂ群（２ｎＯ１Ｓｎ０２）
本発明に係る強誘電性セラミックスを構成するペロブス
カイト型結晶をＡＢＯ３で表わした場合、本発明では、
ＡサイトにはＡ群から選ばれた少なくとも１種以上の金
属酸化物が下記のような金属イオンの形態で入っており
、ＢサイトにはＢ群から選ばれた少なくとも１種以上の
金属酸化物が、下記のような金属イオンの形態で入って
いる。Group A ([a203, Nd203) Group B (2nO1Sn02) When the perovskite crystal constituting the ferroelectric ceramic according to the present invention is represented by ABO3, in the present invention,
The A site contains at least one metal oxide selected from group A in the form of metal ions as shown below, and the B site contains at least one metal oxide selected from group B. is present in the form of metal ions as shown below.
３＋ ３＋
Ａ群（Ｌａ 、Ｎｄ ）
Ｂ群（Ｚｎ 、 Ｓｎ ”）
２十
ここで、上記のＰｂ Ｍ （Ｍｇ１／３１−ａ
ａ
Ｎｂ ） Ｔｉ Ｚｒ２Ｏ３［ただし、Ｍは２
／３ｘｙ
ＢａまたはＳｒ］なる固溶体に対し、Ａ群の金属イオン
は該固溶体中のｐｂおよびＭ（ＭはＢａまたはＳｒ）の
合計原子当量１００原子当量に対し、０．５〜５．０原
子当量の量で存在していることが望ましく、この範囲で
圧電定数ｄの向上効果がＡｉ’ ｎＡｉ、ｎＢｊは各々
、Ａ群、Ｂ群の金属イオンの原子価を表わし、χＡｉ、
χＢｊは各々、Ａ群、Ｂ群の金属イオンの原子当社を表
わす）となる量で存在していることが望ましく、この範
囲で圧電定数ｄの向上効果が特に著しい。3+ 3+ Group A (La, Nd) Group B (Zn, Sn'') 20 Here, the above Pb M (Mg1/31-a
a Nb ) Ti Zr2O3 [However, M is 2
/3xy Ba or Sr], the group A metal ion is 0.5 to 5.0 atomic equivalents per 100 atomic equivalents of the total atomic equivalents of pb and M (M is Ba or Sr) in the solid solution. It is desirable that the amount of metal ions present in this range is Ai', and the effect of improving the piezoelectric constant d is Ai'.
It is preferable that χBj is present in an amount such that the number of atoms of metal ions of group A and group B, respectively, is 0.1, and the effect of improving the piezoelectric constant d is particularly remarkable within this range.
さらに含有させるＭｎＯ２の量は０．１〜２．０重量％
とするのが好ましく、この範囲で機械的品質係数Ｑｎが
向上すると共に圧電定数ｄも十分大きな値に保持するこ
とができる。Further, the amount of MnO2 to be included is 0.1 to 2.0% by weight.
It is preferable that the mechanical quality factor Qn is improved within this range, and the piezoelectric constant d can also be maintained at a sufficiently large value.
このような本発明の組成を有した強誘電性セラミックス
は、焼結した際に各金属酸化物成分を提供しうるような
金属化合物たとえば金属酸化物あるいは金属塩などを粉
末状で用い、これを焼結することにより製造することが
できる。これらの粉末状の金属化合物の製法は、特に限
定されるものではなく、液相法、同相法など種々の公知
の方法を用いることができる。たとえば、液相法におい
ては沈澱法、共沈法、アルコキシド法、ゾルゲル法など
が適用でき、固相法においてはシュウ酸塩分解法、酸化
物混合法などが適用できる。以上いずれかの方法で得ら
れた粉末を８００〜１０００°Ｃで仮焼し、この仮焼体
をボールミル粉砕したのち乾燥する。これを５００〜１
５００ｋｇ／−の圧力でプレス成形し、１０００〜１３
００℃で焼成すれば、目的とする強誘電性セラミックス
が得られる。The ferroelectric ceramic having the composition of the present invention is produced by using powdered metal compounds such as metal oxides or metal salts that can provide each metal oxide component when sintered. It can be manufactured by sintering. The method for producing these powdered metal compounds is not particularly limited, and various known methods such as a liquid phase method and a same phase method can be used. For example, in the liquid phase method, precipitation method, coprecipitation method, alkoxide method, sol-gel method, etc. can be applied, and in the solid phase method, oxalate decomposition method, oxide mixing method, etc. can be applied. The powder obtained by any of the above methods is calcined at 800 to 1000°C, and the calcined body is ground in a ball mill and then dried. This is 500-1
Press molded with a pressure of 500 kg/-, 1000~13
By firing at 00°C, the desired ferroelectric ceramic can be obtained.
［実施例］
以下本発明を実施例によって説明するが、本発明はこれ
ら実施例に限定されるものではない。[Examples] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
なお、径方向振動の電気殿様結合係数（Ｋｐ）、比誘電
率（ε）、圧電定数（ｄ３１）およびｔｉ械的品質係数
（Ｑｌ）の測定は電子材料工業会標準規格（Ｅ）ＩＡｓ
）に定められた方法に準拠して行なった。The electrical coupling coefficient (Kp), dielectric constant (ε), piezoelectric constant (d31), and mechanical quality factor (Ql) of radial vibration are measured in accordance with the Electronic Materials Industries Association Standard (E) IAs.
).
−一 施 １〜３ 上
１ｐｂｏ、Ｚ ｒ Ｏ、Ｔ ｉ ０２ 、ＭｇＣＯ３、
Ｎｂ Ｏ、ＳｒＣＯ３、Ｌａ２Ｏ３、ｚｎＯ１ＳｎＯお
よびＭｎＯ２を表１に示す組成を有するような量比に秤
量し、ボールミルにて粉砕混合した。得られた粉末を８
００〜１０００℃で１〜２時間仮焼し、この仮焼体をボ
ールミル粉砕したのち乾燥したにれを１０００ ｋｇ／
ａｌｌの圧力で直径２５＋＋ｍの円板にプレス成形し、
１０５０〜１２５０°Ｃで１〜２時間焼成した。かくし
て得られた焼結体を厚さ０．５市まで研磨したのち、両
面に銀電極を塗布し、焼き付けた。さらに、シリコンオ
イル中で２０〜４０ＫＶ、’ｏの直流電界を印加するこ
とにより分極処理を施したのち、１２時間エージングし
た試料を電気特性の測定に供した。-1 1～3 top
1pbo, Z r O, T i 02 , MgCO3,
Nb 2 O, SrCO 3 , La 2 O 3 , znO 1 SnO and MnO 2 were weighed to have the composition shown in Table 1, and ground and mixed in a ball mill. 8 of the obtained powder
The calcined body was calcined at 00 to 1000°C for 1 to 2 hours, and the calcined body was ground in a ball mill.
Press molded into a disc with a diameter of 25++ m at a pressure of all
It was baked at 1050-1250°C for 1-2 hours. After polishing the sintered body thus obtained to a thickness of 0.5 mm, silver electrodes were coated on both sides and baked. Further, the sample was subjected to polarization treatment by applying a DC electric field of 20 to 40 KV, 'o in silicone oil, and then aged for 12 hours. The sample was then subjected to measurement of electrical properties.
結果を表１に示す。The results are shown in Table 1.
表中、ａ、ｘ、ｙ、ｚは式Ｐｂ ５ｒ１−ａ
ａ
（Ｍａ Ｎｂ 。In the table, a, x, y, z are the formula Pb 5r1-a
a (MaNb.
１／３ ２／３ ）ｘ ” ” ｚ ０３ 「Ｘ
＋ｙ＋ｚ＝１コの各係数を表わし、ｐ、ｑ、ｒはｐｂお
よびＳ「の合計原子当ｆｆ１ｌｏｏ原子当是に各々、Ａ
群、Ｂ群の金属イオンの原子価を表わし、χＡｉ、χＢ
ｊは各々、Ａ群、Ｂ群の金属イオンの原子当量を表わす
）で定義される値を表わす。1/3 2/3) x ” z 03 “X
+y+z=1 represents each coefficient, and p, q, r are the total atoms of pb and S'', respectively, A
represents the valence of metal ions of group B, χAi, χB
j represents the atomic equivalent of metal ions of group A and group B, respectively).
実施例１〜３の結果より、ｐｂ ｓｒＯ，９５０，
０５
（Ｍ” Ｎｂ２／３）０．３７５Ｔｉ０．３７５１
／３
” ０．２５００３なる組成を有する強誘電性セラミッ
クス（Ｉ）に、Ａサイトへ入るＬａ ”ｌ Ｂす２土
イトへ入る（Ｚｎ 、 Ｓｎ ”）とを併せて含有さ
せた強誘電性セラミックスにおいて、Ｍｎ Ｏ，、の含
有量を増やしていくと、機械的品質係数Ｑｎが大きくな
る一方圧電定数ｄ３１が低下することが分かる。しかし
ながら、実施例の強誘電性セラミックスは、強誘電性セ
ラミックス（１）にＭｎＯ２のみを加えた比較例１のセ
ラミックスに比べ、はぼ同等の値まで機械的品質係数Ｑ
ｌを大きくしても、より大きな圧電定数ｄ３１を示すこ
とが確認された。From the results of Examples 1 to 3, pb srO,950,
05 (M”Nb2/3)0.375Ti0.3751
A ferroelectric ceramic (I) having a composition of 0.25003 and ferroelectric ceramic (I) containing (Zn, Sn) which enters the A site, La "l" which enters the A site, and (Zn, Sn") which enters the B site. It can be seen that as the content of Mn O, . increases, the mechanical quality factor Qn increases while the piezoelectric constant d31 decreases.However, the ferroelectric ceramics of the example Compared to the ceramic of Comparative Example 1 in which only MnO2 was added to 1), the mechanical quality coefficient Q
It was confirmed that even if l was increased, a larger piezoelectric constant d31 was exhibited.
実施例４
実施例２でＬａ２Ｏ３の代わりにＮｄ２Ｏ３を使用した
以外は、実施例２と同様の方法で強誘電性セラミックス
を作製し、電気特性を測定した。Example 4 Ferroelectric ceramics were produced in the same manner as in Example 2, except that Nd2O3 was used instead of La2O3, and the electrical properties were measured.
結果を表２に示す。The results are shown in Table 2.
−・ ５〜７ ２〜４
Ｐｂ Ｓｒ （Ｍ（］ Ｎｂ ）
Ｔｉ１−ａ ａ １／３ ２／３ ｘ
ＶＺｒ７０３ ［ｘ＋ｙ＋ｚ＝１］の各係数が実施
例１〜４とは異なる強誘電性セラミックスにＬａ２Ｏ３
、ｚｎＯ，５ｎｏ２およびＭ ｎ Ｏ２を所定量含有さ
せた強誘電性セラミックスを実施例１と同様の方法で作
製し、電気特性を測定した。-・5~7 2~4 Pb Sr (M(]Nb)
Ti1-a a 1/3 2/3 x
VZr703 Each coefficient of [x+y+z=1] is a ferroelectric ceramic with different coefficients from Examples 1 to 4, and La2O3
, znO, 5no2, and MnO2 in predetermined amounts were produced in the same manner as in Example 1, and their electrical properties were measured.
結果を表２に示す。The results are shown in Table 2.
実施例２および比較例１でＳ ｒ ＣＯ３の代わりにＢ
ａＣＯ３を使用した以外は、実施例２および比較例１と
同様の方法で強誘電性セラミックスを作製し、電気特性
を測定した。In Example 2 and Comparative Example 1, B was used instead of S r CO3.
Ferroelectric ceramics were produced in the same manner as in Example 2 and Comparative Example 1, except that aCO3 was used, and the electrical properties were measured.
結果を表２に示す。The results are shown in Table 2.
土工！と１米
以上の説明から明らかなように、本発明に係る強誘電性
セラミックスは、ＡＢＯ３で表わされるペロブスカイト
型結晶におけるＡ、８両サイトに各々入り得る金属イオ
ンを含有させ、これらの酸化物をすべてへロブスカイト
結晶中に取り込ませた上で、ＭｎＯ２を含有せしめてい
ることから、従来既知の強誘電性セラミックスと比教し
た場合、はぼ同等の機械的品質係数Ｑｎを持ちながら、
より大きな圧電定数ｄを有している。したがって、本発
明に係る強誘電性セラミックスは、超音波モータ等を含
む機械的共振を利用したアクチュエータ等の用途に用い
た場合に優れた特性を示すことができる。Earthworks! As is clear from the above description, the ferroelectric ceramic according to the present invention contains metal ions that can enter both the A and 8 sites of the perovskite crystal represented by ABO3, and these oxides. Since all of the herovskite crystals are incorporated and MnO2 is included, when compared with conventionally known ferroelectric ceramics, it has a mechanical quality factor Qn that is almost the same as that of conventionally known ferroelectric ceramics.
It has a larger piezoelectric constant d. Therefore, the ferroelectric ceramic according to the present invention can exhibit excellent characteristics when used in applications such as actuators that utilize mechanical resonance, including ultrasonic motors and the like.
代理人 弁理士 鈴 木 俊一部Agent: Patent Attorney: Shunbetsu Suzuki
Claims (2)
＿２＿／＿３）＿ｘＴｉ＿ｙＺｒ＿ｚＯ＿３［ただし、
ＭはＢａまたはＳｒであり、ｘ＋ｙ＋ｚ＝１］で表わさ
れ、 ａ＝０〜０．１０ ｘ＝０．０５〜０．７０ ｙ＝０．２５〜０．５０ ｚ＝０．０５〜０．７０ であるペロブスカイト型固溶体に対し、下記のＡ群から
選ばれた少なくとも１種以上の酸化物と、下記のＢ群か
ら選ばれた少なくとも１種以上の酸化物とをともに含有
せしめ、さらにＭｎＯ＿２を含有せしめてなるペロブス
カイト型固溶体であることを特徴とする強誘電性セラミ
ックス。 Ａ群（Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３） Ｂ群（ＺｎＯ、ＳｎＯ＿２）(1) Pb_1_-_aM_a(Mg_1_/_3Nb
_2_/_3)_xTi_yZr_zO_3 [However,
M is Ba or Sr, and is represented by x+y+z=1], a=0-0.10 x=0.05-0.70 y=0.25-0.50 z=0.05-0. 70 containing at least one or more oxides selected from the following group A and at least one or more oxides selected from the following group B, and further containing MnO_2. A ferroelectric ceramic characterized by being a perovskite-type solid solution containing a perovskite-type solid solution. Group A (La_2O_3, Nd_2O_3) Group B (ZnO, SnO_2)
る請求項第１項に記載の強誘電性セラミックス。(2) The ferroelectric ceramic according to claim 1, wherein the content of MnO_2 is 0.1 to 2.0% by weight.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63129800A JP2580258B2 (en) | 1988-05-27 | 1988-05-27 | Ferroelectric ceramics |
| MYPI89000688A MY104020A (en) | 1988-05-27 | 1989-05-23 | Ferroelectric ceramic material. |
| US07/356,216 US4948767A (en) | 1988-05-27 | 1989-05-24 | Ferroelectric ceramic material |
| AT89305333T ATE125522T1 (en) | 1988-05-27 | 1989-05-25 | FERROELECTRIC CERAMIC MATERIAL. |
| DE68923579T DE68923579T2 (en) | 1988-05-27 | 1989-05-25 | Ferroelectric ceramic material. |
| EP89305333A EP0344000B1 (en) | 1988-05-27 | 1989-05-25 | Ferroelectric ceramic material |
| CA000600773A CA1335932C (en) | 1988-05-27 | 1989-05-26 | Ferroelectric ceramic material |
| KR1019890007124A KR910009893B1 (en) | 1988-05-27 | 1989-05-27 | Ferroelectric ceramic material |
| CN89103701A CN1018226B (en) | 1988-05-27 | 1989-05-27 | Ferroelectric ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63129800A JP2580258B2 (en) | 1988-05-27 | 1988-05-27 | Ferroelectric ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01298063A true JPH01298063A (en) | 1989-12-01 |
| JP2580258B2 JP2580258B2 (en) | 1997-02-12 |
Family
ID=15018540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63129800A Expired - Lifetime JP2580258B2 (en) | 1988-05-27 | 1988-05-27 | Ferroelectric ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2580258B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023223682A1 (en) * | 2022-05-17 | 2023-11-23 | パナソニックＩｐマネジメント株式会社 | Dielectric material and functional element |
-
1988
- 1988-05-27 JP JP63129800A patent/JP2580258B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023223682A1 (en) * | 2022-05-17 | 2023-11-23 | パナソニックＩｐマネジメント株式会社 | Dielectric material and functional element |
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| Publication number | Publication date |
|---|---|
| JP2580258B2 (en) | 1997-02-12 |
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