JPH06100363A - Piezoelectric porcelain composition - Google Patents
Piezoelectric porcelain compositionInfo
- Publication number
- JPH06100363A JPH06100363A JP4251453A JP25145392A JPH06100363A JP H06100363 A JPH06100363 A JP H06100363A JP 4251453 A JP4251453 A JP 4251453A JP 25145392 A JP25145392 A JP 25145392A JP H06100363 A JPH06100363 A JP H06100363A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- piezoelectric
- amount
- oxide
- added
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001845 chromium compounds Chemical class 0.000 claims 1
- 150000002506 iron compounds Chemical class 0.000 claims 1
- 150000002697 manganese compounds Chemical class 0.000 claims 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 9
- 229910052787 antimony Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はチタン酸ジルコン酸鉛を
主成分とする圧電磁器組成物に関するものであり、特に
圧電特性が大であると共に、絶縁性能に優れた高温下で
使用可能な圧電磁器組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition containing lead zirconate titanate as a main component, and in particular, it has excellent piezoelectric characteristics and is excellent in insulation performance and can be used at high temperatures. The present invention relates to a porcelain composition.
【０００２】[0002]
【従来の技術】圧電体磁器は、鉛、ジルコニウム、チタ
ンの酸化物で構成されたチタン酸ジルコン酸鉛を主成分
としているが、これに様々な微量酸化物を添加すると圧
電特性が著しく向上することは広く知られている。例え
ば、酸化ニオブ、酸化タンタル、酸化ランタン、酸化タ
ングステン、酸化アンチモン等を添加すると圧電性が向
上し、機械的品質係数ＱM並びに電気的品質係数ＱE（１
／ｔａｎδ）の値は小さくなる。一方、酸化鉄、酸化ク
ロム、酸化マンガン等を添加するとＱM並びにＱEの値は
大きくなる。近年、この圧電磁器が積層圧電素子等のア
クチュエータに用いられるようになってきた。2. Description of the Related Art Piezoelectric porcelain contains lead zirconate titanate, which is composed of oxides of lead, zirconium, and titanium, as a main component, and addition of various trace oxides to this significantly improves piezoelectric characteristics. It is widely known. For example, when niobium oxide, tantalum oxide, lanthanum oxide, tungsten oxide, antimony oxide, etc. are added, the piezoelectricity is improved, and the mechanical quality factor Q M and the electrical quality factor Q E (1
The value of / tan δ) becomes smaller. On the other hand, when iron oxide, chromium oxide, manganese oxide, etc. are added, the values of Q M and Q E increase. In recent years, this piezoelectric ceramic has come to be used for actuators such as laminated piezoelectric elements.
【０００３】[0003]
【発明が解決しようとする課題】上記アクチュエータ用
圧電磁器組成物の例として例えばＰｂ（Ｎｉ1/3Ｎ
ｂ2/3）Ｏ3−ＰｂＺｒＯ3−ＰｂＴｉＯ3系、あるいはＰ
ｂ（Ｎｉ1/2Ｗ1/2）Ｏ3−ＰｂＺｒＯ3−ＰｂＴｉＯ3系
等が知られている。しかしながら、前記圧電磁器組成物
はキュリー温度が比較的低く、このため、２００℃以上
の高温下で駆動されるアクチュエータ、例えば、燃料噴
射弁用アクチュエータ、高温用マスフローコントローラ
弁駆動用アクチュエータ等に使用することが困難であっ
た。また、前記圧電磁器組成物は電気抵抗率が比較的小
さく、このため例えば、積層型圧電素子のように一層の
厚みが１００μｍ前後の素子に前記圧電磁器組成物が使
用された場合、印加できる電圧が小さく充分な性能が引
き出せない、あるいは使用中に絶縁破壊してしまう等、
信頼性が低いという問題があった。本発明は上記従来技
術に存在する問題点を解決し、圧電特性が大であると共
に、キュリー温度が高く、かつ電気抵抗率が大で高温用
アクチュエータ用材料、特に高温用積層型圧電素子用材
料に適した圧電磁器組成物を提供することを目的とす
る。As an example of the above piezoelectric ceramic composition for actuator, for example, Pb (Ni 1/3 N)
b 2/3 ) O 3 -PbZrO 3 -PbTiO 3 system, or P
The b (Ni 1/2 W 1/2 ) O 3 -PbZrO 3 -PbTiO 3 system and the like are known. However, since the piezoelectric ceramic composition has a relatively low Curie temperature, it is used for an actuator driven at a high temperature of 200 ° C. or higher, such as a fuel injection valve actuator or a high temperature mass flow controller valve driving actuator. Was difficult. In addition, the piezoelectric ceramic composition has a relatively low electrical resistivity, and therefore, when the piezoelectric ceramic composition is used for an element having a thickness of about 100 μm such as a laminated piezoelectric element, a voltage that can be applied. Is small and sufficient performance cannot be obtained, or dielectric breakdown occurs during use, etc.
There was a problem of low reliability. The present invention solves the problems existing in the above-mentioned prior art, and has a high piezoelectric characteristic, a high Curie temperature, and a high electric resistivity, and is a material for a high temperature actuator, particularly a material for a high temperature laminated piezoelectric element. An object of the present invention is to provide a piezoelectric ceramic composition suitable for.
【０００４】[0004]
【問題を解決するための手段】上記問題を解決するため
に、本発明においては、Ｐｂ（ＺｒxＴｉy）Ｏ3（但しx
＋y＝１）で表される組成をもって基本組成とし、０．
５２≦x≦０．５９の範囲内の組成から成りＰｂ原子の
２〜１０モル％をＣａ、Ｓｒ及びＢａの少なくとも１種
で置換し、これにＳｂをＳｂ2Ｏ3に換算して０．１〜
２．０重量％含有し、かつＭｎ、Ｆｅ、Ｃｒの少なくと
も一種をそれぞれ酸化物に換算して０．０１〜０．５重
量％含有する、という技術的手段を採用した。In order to solve the above problems, in the present invention, Pb (Zr x Ti y ) O 3 (however, x
+ Y = 1) is used as the basic composition, and 0.
52 ≦ x ≦ 0.59, 2 to 10 mol% of Pb atoms are replaced with at least one of Ca, Sr and Ba, and Sb is converted into Sb 2 O 3 to give a value of 0. 1 to
The technical means of containing 2.0% by weight and containing 0.01 to 0.5% by weight of at least one of Mn, Fe, and Cr in terms of oxide.
【０００５】[0005]
【作用】本発明においては、チタン酸鉛とジルコン酸鉛
の相境界近傍の組成においてＰｂをＣａ、Ｓｒ及びＢａ
の少なくとも一種で置換し、かつＳｂをＳｂ2Ｏ3の形で
適量添加することで高いキュリー温度を維持し、かつ大
なる圧電定数を確保し、さらに、Ｍｎ、Ｆｅ、Ｃｒの少
なくとも一種を極微量加えることにより、電気抵抗率の
向上を計ることでアクチュエータ用材料に適した圧電磁
器組成物を提供するものである。なお、添加するＭｎ、
Ｆｅ、Ｃｒはいずれも極微量であることから溶液状で他
の固体粉末状原料に加えると効果的に混合できる。In the present invention, in the composition near the phase boundary between lead titanate and lead zirconate, Pb is added to Ca, Sr and Ba.
To maintain a high Curie temperature and to secure a large piezoelectric constant by adding Sb in the form of Sb 2 O 3 in an appropriate amount, and at least one of Mn, Fe and Cr is polar. It is intended to provide a piezoelectric ceramic composition suitable as a material for an actuator by improving the electric resistivity by adding a trace amount. In addition, Mn to be added,
Since both Fe and Cr are extremely small in amount, they can be effectively mixed when added in solution form to other solid powder raw materials.
【０００６】[0006]
【実施例】以下、実施例により、本発明の効果を具体的
に説明する。EXAMPLES The effects of the present invention will be specifically described below with reference to examples.
【０００７】（実施例１）酸化鉛（ＰｂＯ）、炭酸スト
ロンチウム（ＳｒＣＯ3）、酸化チタン（ＴｉＯ2）、酸
化ジルコニウム（ＺｒＯ2）、酸化アンチモン（Ｓｂ2Ｏ
3）及び酸化マンガン（ＭｎＯ2）を化学式（Ｐｂ1-xＳ
ｒx）（ＺｒyＴｉ1-y）Ｏ3＋zwt％Ｓｂ2Ｏ3＋Wwt％Ｍｎ
Ｏ2となるように秤量し、これを溶媒にエチルアルコー
ルを用いてボールミルで２時間混合した。得られた混合
物を１００℃で５時間乾燥し、仮成形後、空気中におい
て８５０℃で２時間仮焼し、更にボールミルで２時間粉
砕した。これを造粒後プレス成形により直径２０ｍｍ長
さ１５ｍｍの成形体を作成した。この成形体をアルミナ
若しくはマグネシアからなる容器内に密閉した状態で酸
素中１２６０℃５時間の焼結を行った。得られた焼結体
を切断、研磨加工により、直径１６ｍｍ、厚さ０．８ｍ
ｍの素子にし、両端面にＣｒ−Ａｕからなる電極を形成
し、シリコンオイル中において３ｋＶ／ｍｍの直流電圧
を印加して分極処理を行った。Example 1 Lead oxide (PbO), strontium carbonate (SrCO 3 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), antimony oxide (Sb 2 O)
3 ) and manganese oxide (MnO 2 ) having the chemical formula (Pb 1-x S
r x ) (Zr y Ti 1-y ) O 3 + zwt% Sb 2 O 3 + Wwt% Mn
It was weighed so as to be O 2, and this was mixed in a ball mill for 2 hours using ethyl alcohol as a solvent. The obtained mixture was dried at 100 ° C. for 5 hours, pre-molded, then calcined in air at 850 ° C. for 2 hours, and further pulverized with a ball mill for 2 hours. After granulating this, a molded product having a diameter of 20 mm and a length of 15 mm was prepared by press molding. Sintering was performed in oxygen at 1260 ° C. for 5 hours in a state where the molded body was hermetically sealed in a container made of alumina or magnesia. The obtained sintered body is cut and polished to have a diameter of 16 mm and a thickness of 0.8 m.
An element made of Cr-Au was formed on both end faces, and a direct current voltage of 3 kV / mm was applied in silicon oil to perform polarization treatment.
【０００８】図１には、（Ｐｂ0.98Ｓｒ0.02）（Ｚｒ
0.55Ｔｉ0.45）Ｏ3+xwt%Ｓｂ2Ｏ3＋0.05wt%ＭｎＯ2系の
Ｓｂ2Ｏ3添加量とキュリー温度Ｔｃの関係を示す。図１
より明らかなように、Ｓｂ2Ｏ3添加量が増加するとキュ
リー温度は低下するが、添加量が２．０ｗｔ％までは２
５０℃以上の高いキュリー温度を維持している。図２に
は、（Ｐｂ1-xＳｒx）（Ｚｒ0.55Ｔｉ0.45）Ｏ3＋０．
３wt％Ｓｂ2Ｏ3＋0.05wt%ＭｎＯ2系のＳｒ置換量とキュ
リー温度Ｔｃの関係を示す。図２に示すようにＳｒ置換
量が増加するとキュリー温度は低下するが置換量が１０
モル％以下では２５０℃以上の高いキュリー温度を維持
している。In FIG. 1, (Pb 0.98 Sr 0.02 ) (Zr
The relationship between the amount of Sb 2 O 3 added and the Curie temperature Tc of 0.55 Ti 0.45 ) O 3 + xwt% Sb 2 O 3 +0.05 wt% MnO 2 system is shown. Figure 1
As is clearer, the Curie temperature decreases as the amount of Sb 2 O 3 added increases, but it becomes 2
A high Curie temperature of 50 ° C or higher is maintained. In FIG. 2, (Pb 1-x Sr x ) (Zr 0.55 Ti 0.45 ) O 3 +0.
The relationship between the Sr substitution amount of 3 wt% Sb 2 O 3 +0.05 wt% MnO 2 system and the Curie temperature Tc is shown. As shown in FIG. 2, when the Sr substitution amount increases, the Curie temperature decreases, but the substitution amount is 10
If it is less than mol%, a high Curie temperature of 250 ° C. or higher is maintained.
【０００９】表１に（Ｐｂ1-xＳｒx）（ＺｒyＴｉ1-y）
Ｏ3＋zwt％Ｓｂ2Ｏ3＋0.05wt％ＭｎＯ2系の特性を示
す。アクチュエータの変位量は材料の圧電歪定数に比例
する。Ｎｏ．１〜５のデータよりＰｂの一部をＳｒに置
換することにより圧電歪定数が大きくなることがわか
る。Ｓｒの置換量がＰｂの２モル％未満ではその効果が
小さく、圧電歪定数−ｄ31も１５０×１０ー12ｍ／Ｖ以
下と小さく、アクチュエータ用圧電材料としては不適で
ある。置換量が１０モル％を越えるとキュリー温度が低
下し、２００℃以上の高温の用途に適さなくなる。Ｎ
ｏ．６〜１０よりＳｂ2Ｏ3の添加もＳｒの置換と同様の
効果があることがわかる。また、Ｎｏ．１１〜１６より
ｙが０．５２≦ｙ≦０．５９の範囲で−ｄ31が１５０×
１０ー12ｍ／Ｖ以上の大きな値を確保できることがわか
る。In Table 1, (Pb 1-x Sr x ) (Zr y Ti 1-y )
The characteristics of the O 3 + zwt% Sb 2 O 3 +0.05 wt% MnO 2 system are shown. The displacement of the actuator is proportional to the piezoelectric strain constant of the material. No. It can be seen from the data of 1 to 5 that the piezoelectric strain constant is increased by replacing a part of Pb with Sr. If the substitution amount of Sr is less than 2 mol% of Pb, the effect is small, and the piezoelectric strain constant −d 31 is small as 150 × 10 −12 m / V or less, which is unsuitable as a piezoelectric material for actuators. If the amount of substitution exceeds 10 mol%, the Curie temperature will decrease, making it unsuitable for high temperature applications of 200 ° C. or higher. N
o. From 6 to 10, it is understood that addition of Sb 2 O 3 has the same effect as substitution of Sr. In addition, No. From 11 to 16, y is in the range of 0.52 ≦ y ≦ 0.59 and −d 31 is 150 ×.
It can be seen that can ensure a large value of more than 10 @ 12 m / V.
【表１】 ※は本発明外 また表２に示すように（Ｐｂ0.95Ｓｒ0.05）（Ｚｒ0.55
Ｔｉ0.45）Ｏ3+0.3wt%Ｓｂ2Ｏ3＋0.05wt%ＭｎＯ2でＳｒ
の代わりにアルカリ土類金属であるＢａ、Ｃａを用いて
も同様の効果が得られることがわかる。[Table 1] * Is outside the present invention. Also, as shown in Table 2, (Pb 0.95 Sr 0.05 ) (Zr 0.55
Ti 0.45 ) O 3 + 0.3wt% Sb 2 O 3 + 0.05wt% MnO 2 Sr
It can be seen that the same effect can be obtained by using alkaline earth metals Ba and Ca instead of.
【表２】 表３には（Ｐｂ0.95Ｓｒ0.05）（Ｚｒ0.55Ｔｉ0.45）Ｏ
3+0.3wt%Ｓｂ2Ｏ3＋Wwt%ＭｎＯ2系の特性を示す。[Table 2] Table 3 shows (Pb 0.95 Sr 0.05 ) (Zr 0.55 Ti 0.45 ) O.
3 + shows the 0.3wt% Sb 2 O 3 + Wwt % MnO 2 system characteristics of.
【表３】 ※は本発明外 表３から明らかなように微量のＭｎを添加することによ
り電気抵抗率が２桁程度大きくなることがわかる。特に
本発明のＭｎ添加量がＭｎＯ2に換算して０．０１から
０．５重量％では電気抵抗率が大きく、かつ、-ｄ31も
大きくアクチュエータ、特に積層型圧電素子に最適の圧
電磁器組成物であることがわかる。また、Ｍｎの添加量
がＭｎＯ2に換算して０．０１重量％未満ではＭｎの添
加効果が不十分で電気抵抗率が大きくならない。一方、
Ｍｎの添加量がＭｎＯ2に換算して０．５重量％を越え
ると比誘電率εT 33、および電気機械結合係数ＫPの低下
が著しく、圧電歪定数-ｄ31が小さくなりすぎる。[Table 3] As is clear from Table 3 outside the present invention, it can be seen that the electrical resistivity increases by about two digits by adding a small amount of Mn. In particular, when the amount of Mn added in the present invention is 0.01 to 0.5% by weight in terms of MnO 2 , the electric resistivity is large and -d 31 is large, and the piezoelectric ceramic composition is most suitable for the actuator, especially the laminated piezoelectric element. It turns out that it is a thing. If the amount of Mn added is less than 0.01 wt% in terms of MnO 2 , the effect of adding Mn is insufficient and the electrical resistivity does not increase. on the other hand,
When the amount of Mn added exceeds 0.5 wt% in terms of MnO 2 , the relative permittivity ε T 33 and the electromechanical coupling coefficient K P are remarkably lowered, and the piezoelectric strain constant −d 31 becomes too small.
【００１０】（実施例２）実施例１の方法と同様の方法
により、試料を作成し評価した。（Ｐｂ0.95Ｓｒ 0.05）
（Ｚｒ0.55Ｔｉ0.45）Ｏ3+0.3wt%Ｓｂ2Ｏ3にＦｅ、Ｃｒ
を添加することにより、表４から表５の特性が得られ
る。Ｆｅ、Ｃｒの添加によりＭｎの添加と同様の効果が
得られることがわかる。(Second Embodiment) A method similar to the method of the first embodiment.
A sample was prepared and evaluated according to. (Pb0.95Sr 0.05)
(Zr0.55Ti0.45) O3+ 0.3wt% Sb2O3Fe, Cr
The characteristics shown in Tables 4 to 5 are obtained by adding
It Adding Fe and Cr has the same effect as adding Mn.
You can see that you can get it.
【表４】 ※は本発明外[Table 4] * Is outside the invention
【表５】 ※は本発明外[Table 5] * Is outside the invention
【００１１】（実施例３）酸化鉛（ＰｂＯ）、炭酸スト
ロンチウム（ＳｒＣＯ3）、酸化チタン（ＴｉＯ2）、酸
化ジルコニウム（ＺｒＯ2）、酸化アンチモン（Ｓｂ2Ｏ
3）を化学式（Ｐｂ0 .95Ｓｒ0.05）（Ｚｒ0.55Ｔ
ｉ0.45）Ｏ3+0.3wt%Ｓｂ2Ｏ3となるように秤量し、これ
にＭｎ、Ｆｅ、ＣｒをそれぞれＭｎ（ＯＣ2Ｈ5）2、Ｆ
ｅ（ＯＣ2Ｈ5）3、Ｃｒ（ＯＣ2Ｈ5）3でそれぞれの酸化
物に換算して０．０１wt％加え、混合溶媒であるエチル
アルコール中に溶解した。実施例１の方法と同様の方法
により、試料を作成し、表６の特性を得た。表６より添
加量が微量であるＭｎ、Ｆｅ、Ｃｒの出発原料を溶液状
で添加することにより良好な特性が得られることがわか
る。Example 3 Lead oxide (PbO), strontium carbonate (SrCO 3 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), antimony oxide (Sb 2 O)
3) The chemical formula (Pb 0 .95 Sr 0.05) ( Zr 0.55 T
i 0.45 ) O 3 +0.3 wt% Sb 2 O 3 was weighed, and Mn, Fe, and Cr were added to Mn (OC 2 H 5 ) 2 and F, respectively.
0.01 wt% of e (OC 2 H 5 ) 3 and Cr (OC 2 H 5 ) 3 in terms of each oxide was added and dissolved in ethyl alcohol as a mixed solvent. A sample was prepared in the same manner as in Example 1 and the characteristics shown in Table 6 were obtained. It can be seen from Table 6 that good characteristics can be obtained by adding the starting materials of Mn, Fe, and Cr, which are added in a small amount, in a solution state.
【表６】 [Table 6]
【００１２】[0012]
【発明の効果】以上説明したように、本発明はキュリー
温度が高く、圧電歪定数が大きく、かつ、電気抵抗率も
大きいことから、高温用アクチュエータ、特に高温用積
層型圧電素子用材料として極めて有用である。As described above, the present invention has a high Curie temperature, a large piezoelectric strain constant, and a large electrical resistivity, and therefore is extremely useful as a material for high temperature actuators, especially high temperature laminated piezoelectric elements. It is useful.
【図１】本発明におけるキュリー温度ＴｃのＳｂ2Ｏ3添
加量依存性を示す図FIG. 1 is a graph showing the dependence of Curie temperature Tc on the amount of Sb 2 O 3 added in the present invention.
【図２】本発明におけるキュリー温度ＴｃのＳｒ添加量
依存性を示す図FIG. 2 is a graph showing the dependency of Curie temperature Tc on the amount of Sr added in the present invention.
Claims (2)
１）で表される組成をもって基本組成とし、０．５２≦
x≦０．５９の範囲内の組成から成りＰｂ原子の２〜１
０モル％をＣａ、Ｓｒ及びＢａの少なくとも一種で置換
し、これにＳｂをＳｂ2Ｏ3に換算して０．１〜２．０重
量％含有し、かつＭｎ、Ｆｅ、Ｃｒの少なくとも一種を
それぞれ酸化物に換算して０．０１〜０．５重量％含有
することを特徴とする圧電磁器組成物。1. Pb (Zr x Ti y ) O 3 (where x + y =
The composition represented by 1) is defined as a basic composition, and 0.52 ≦
2 to 1 of Pb atoms having a composition within the range of x ≦ 0.59
Substituting 0 mol% of at least one of Ca, Sr, and Ba, and containing 0.1 to 2.0 wt% of Sb in terms of Sb 2 O 3 , and at least one of Mn, Fe, and Cr. A piezoelectric ceramic composition containing 0.01 to 0.5 wt% of each oxide.
状のマンガン化合物、鉄化合物、クロム化合物の少なく
とも一種を用いる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 of a manganese compound, an iron compound and a chromium compound in solution is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4251453A JPH06100363A (en) | 1992-09-21 | 1992-09-21 | Piezoelectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4251453A JPH06100363A (en) | 1992-09-21 | 1992-09-21 | Piezoelectric porcelain composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06100363A true JPH06100363A (en) | 1994-04-12 |
Family
ID=17223056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4251453A Pending JPH06100363A (en) | 1992-09-21 | 1992-09-21 | Piezoelectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06100363A (en) |
-
1992
- 1992-09-21 JP JP4251453A patent/JPH06100363A/en active Pending
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