JPS59196503A - Electrostrictive porcelain composition - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は磁器組成物、特に従来より低温で焼結でき、伸
び率の大きい′屯歪磁器糾成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a porcelain composition, and particularly to a strained porcelain composite which can be sintered at a lower temperature than conventionally and has a high elongation rate.

従来圧電性磁器としてＰｂ（Ｍｇ’４Ｎｂ２／３）Ｏ，
−ＰｂＴｉ０゜−ＰｂＺｒ０．やＰｂ　（Ｎｉ　’／３
　Ｎｂ２／３）０３−ＰｂＴｉ０３−　ＰｂＺ　ｒＯＢ
などが良く知られている。これらの材料を用いて微少変
位素子などに応用するとき特に、矩動電圧の低圧化を実
現するために積層形成歪素子を形成する場合には、磁器
の焼結温度以上の融点をもつ金属や合金が内部電極とし
て使用されねばならなかった。上記のような材料は焼結
温度が一般に１２００〜１３００℃という高温でありこ
のため内部電極として白金やパラジウム又はパラジウム
含量の多い嫁−パラジウム合金の適用されねばならない
。このうち白金は焼結時においても安定で、これらの材
料とも反応せず所望の特性が得られるが非常に高価であ
り、量産時のコストを考慮すると実用上その用途は著る
しく限定されてしまう。一方、パラジウムは白金に比べ
安価であり、しかも比重を考慮するとより実用性は高い
。しかしながらパラジウムは焼結中に一旦酸化された後
、還元して金属状となるため、これに応じて焼結中に一
旦膨張し、その後収縮する過程をとり、積層形素子に亀
裂や層はく離を発生しやすい問題がある。As conventional piezoelectric porcelain, Pb(Mg'4Nb2/3)O,
-PbTi0°-PbZr0. or Pb (Ni '/3
Nb2/3)03-PbTi03- PbZ rOB
etc. are well known. When applying these materials to minute displacement elements, etc., especially when forming laminated strain elements to achieve low rectangular voltage, metals or metals with a melting point higher than the sintering temperature of porcelain are used. Alloys had to be used as internal electrodes. The sintering temperature of the above-mentioned materials is generally as high as 1200 to 1300 DEG C. Therefore, platinum, palladium, or a metal-palladium alloy with a high palladium content must be used as the internal electrode. Of these, platinum is stable even during sintering and does not react with these materials and provides the desired properties, but it is extremely expensive, and its practical use is extremely limited when considering the cost of mass production. Put it away. On the other hand, palladium is cheaper than platinum, and moreover, it is more practical considering its specific gravity. However, palladium is oxidized during sintering and then reduced to a metallic state, so palladium expands during sintering and then contracts, causing cracks and delamination in the laminated element. There are some problems that can easily occur.

特に鉛を含むペロブスカイト型組成物とは高温で反応し
やすく、パラジウム又はパラジウムの含有量の多いパラ
ジウム−鉄系の適用は非常に困難であった。すなわちパ
ラジウムの酸化−還元による膨張−１ｐ／縮は銀−パラ
ジウム二成分系でも見られ、パラジウムの合量が多いと
その程度は大きく、逆に銀の含有量が多くなるとその程
度は小さくなシ、銀のみではこのようなことは全く起ら
ない。このため銀の含有量が多くなると、上記の現象が
起ってもその程度が小さいため焼結後の積層形素子には
亀裂や層はく離は全くみられなくな９良好な素子が得ら
れると共に、銀はパラジウムに比較し、更に安価である
ためコストの面からもより有利である。In particular, it is easy to react with perovskite compositions containing lead at high temperatures, and it has been extremely difficult to apply palladium or palladium-iron systems containing a large amount of palladium. In other words, the expansion -1p/condensation due to oxidation-reduction of palladium is also observed in silver-palladium binary systems, and the degree of expansion increases as the total amount of palladium increases, and conversely, the degree of expansion decreases as the silver content increases. , this kind of thing does not happen with silver alone. For this reason, when the silver content increases, even if the above phenomenon occurs, the degree of occurrence is small, so that no cracks or delaminations are observed in the multilayer element after sintering,9 and a good element can be obtained. Since silver is cheaper than palladium, it is more advantageous in terms of cost.

市販のパラジウム−銀ペーストを内部電極ベーストに適
用するとパラジウムの割合が４０％以上では亀裂や層は
く蹄が起りやすく、３０チ以下ではとの現象がほとんど
みられ々かった。すなわちＡｇ　−Ｐｄ系二元合金図の
公知の状態図から見れば磁器の焼結温黒二を１１５０℃
以下、望ましくは１１００℃以下にすることが実用上極
めて重要なことである。When a commercially available palladium-silver paste was applied to an internal electrode base, cracks and delamination were likely to occur when the palladium content was 40% or more, and this phenomenon was hardly observed when the palladium content was 30% or less. In other words, from the known phase diagram of the Ag-Pd system binary alloy diagram, the sintering temperature of porcelain is 1150°C.
Hereinafter, it is practically extremely important to desirably lower the temperature to 1100°C or less.

本発明は従来より低温で焼結できかつ直流電界下で伸び
率の大きい槓層形区歪素子用磁器糾成物として優れた材
料を提供することを目的とする。An object of the present invention is to provide a material which can be sintered at a lower temperature than conventional materials and which has a high elongation rate under a direct current electric field and is excellent as a porcelain composite for a laminated strain element.

本発明の磁器組成物は（Ｐｂ（Ｆｅ珍へ）０３〕工（ｐ
ｂ（Ｎｔ’、４Ｎｂ２／３）０３１：ｌア［ＰｂＴｉＯ
３］、なる式で表現したとき〔ただしｘ　」ｙ＋ｚ＝１
．ｏｏ）、ｘ　＋　ｙ　＋　ｚがそれぞれで表わされる
次の組成点Ａ、Ｂ、Ｃ，Ｄ。The porcelain composition of the present invention is (Pb (Fe) 03)
b(Nt', 4Nb2/3)031:lA[PbTiO
3], when expressed by the formula [where x ''y+z=1
．． oo), x + y + z are respectively represented by the following composition points A, B, C, and D.

Ａ　：　（ｘ＝０．ｏｌ　　ｙ＝０．７８　　ｚ　＝０
．２１　　）Ｂ　：　（ｘ−０，２０ｙ＝０．７０　　
ｚ＝０．１０　　）Ｃ：（ｘ−０，２０ｙ＝０．５０　
　ｚ　＝０．３０　　）Ｄ：（ｘ＝０．０５　　ｙ＝０
．５０　　ｚ＝０．４５　　）を結ぶ線上およびこの線
に囲まれる範囲内にある　　　　０ことを特徴とする。A: (x=0.ol y=0.78 z=0
．． 21) B: (x-0,20y=0.70
z=0.10)C:(x-0,20y=0.50
z = 0.30) D: (x = 0.05 y = 0
．． 50 z=0.45 ) and within the range surrounded by this line.

以下本発明を実施例にて詳細に説明する。The present invention will be explained in detail below with reference to Examples.

出発原料として酸化鉛（ｐｂｏ）　、酸化鉄（ＦｅｔＯ
＋）　。Lead oxide (pbo) and iron oxide (FetO) are used as starting materials.
+).

酸化タングステン（ＷＯ，）、酸化ニッケル（Ｎｔｏ）
、酸化ニオブ（Ｎｂ２０．）および酸化チタン（Ｔｉ０
２）を使用し、表に示す各配合比となるように秤量し、
これをボールミル中で湿式混合する。ヂ過、乾燥後との
粉末を７５０〜８５０℃で仮焼きし、この粉末を再度ボ
ールミル中で湿式混合する。沖過、乾燥、粉砕した後、
０．７ｔｏｎ／−の圧力で厚さ５．０龍の円柱を２本成
形し、９８０〜１１００℃で焼結した。得られた円柱の
厚さを測定した後銀電極を焼付けた。リード線ヲ両面に
はんだ付けした後厚さ方向に電界強度Ｉ　ＫＶ／ｍｔｓ
になるまで電圧を印加しその時の厚みと電界強度を零に
戻した時の厚みを歪測定器で測定した。伸び率は目Ｖ−
の電界下での厚みと電界を零に戻した時の厚みの差をこ
の電界を零に戻した時の厚みで割ったもので求めた。Tungsten oxide (WO,), nickel oxide (Nto)
, niobium oxide (Nb20.) and titanium oxide (Ti0.
2), and weighed to achieve each compounding ratio shown in the table,
This is wet mixed in a ball mill. After passing and drying, the powder is calcined at 750 to 850°C, and this powder is wet-mixed again in a ball mill. After clearing, drying and crushing,
Two cylinders with a thickness of 5.0 mm were molded under a pressure of 0.7 ton/- and sintered at 980 to 1100°C. After measuring the thickness of the resulting cylinder, a silver electrode was baked. After soldering both sides of the lead wire, the electric field strength in the thickness direction is I KV/mts.
A voltage was applied until the voltage was applied, and the thickness at that time and the thickness when the electric field strength was returned to zero were measured using a strain meter. The elongation rate is V-
The difference between the thickness under the electric field and the thickness when the electric field is returned to zero was calculated by dividing the thickness by the thickness when the electric field is returned to zero.

配合比と焼結温度および伸び率の結果を表に示す。なお
伸び率の測定には同一配合比の試料を２個用い、その平
均値をもって代表値とした。The results of the compounding ratio, sintering temperature, and elongation rate are shown in the table. In addition, two samples with the same compounding ratio were used to measure the elongation rate, and the average value was taken as the representative value.

表を見ると明らかなように本発明の磁器組成物は１１０
０℃以下の低温で焼、結できると共に伸び率が２×１０
　以上を示す積層形電歪素子として優れた材料を提供す
るものである。表の各組成点と本発明の請求の組成範囲
を図に示した。As is clear from the table, the porcelain composition of the present invention has 110
Can be sintered and sintered at low temperatures below 0℃, and has an elongation rate of 2×10
The present invention provides an excellent material for a laminated electrostrictive element having the above characteristics. Each composition point in the table and the composition range claimed in the present invention are shown in the figure.

なお本発明の組成範囲外では焼結温度が１１００℃を越
えるか、伸び率が低下するため実用性が少くなる。If the composition is outside the composition range of the present invention, the sintering temperature will exceed 1100°C or the elongation rate will decrease, making it less practical.

【図面の簡単な説明】[Brief explanation of drawings]

図面は本発明の磁器組成物の組成範囲を示す三角図であ
る。 Ｐｂ　（Ｆｅｉ　ＶＶ’／３　）　０３１３The drawing is a triangular diagram showing the composition range of the porcelain composition of the present invention. Pb (Fei VV'/3) 0313

Claims (1)

【特許請求の範囲】 鉄・タングステン酸鉛［ｐｂ（ｐｅ％ｗＸ／３）Ｏｓ〕
＋　ニッケルニオブ酸鉛（Ｐｂ（Ｎｉ職Ｎｂ２／３）０
３）、　ｆタン酸鉛（ｐｂＴｉｏｓ〕から彦る三成分磁
器組成物を［Ｐｂ（Ｆｅ２／３Ｗ　！／３　）０３　］
　、ＣＰｂ　（Ｎ　ｉ　！／３　Ｎｂ”３　）０３　］
　、［Ｐｂ　Ｔ　ｉ　０３　、］　２と表現したとき（
ただしｘ＋ｙ＋ｚ＝１．ｏＯ）、配合比ｘ、ｙ。 ２がこの三成分紡成図において、以下の胎成点Ａ。 Ｂ、Ｃ，Ｄ Ａ　：　（Ｘ＝Ｏ，ｌ）１　　ｙ＝０．７８　　ｚ＝０
．２１　　）　。 Ｂ　：　（Ｘ＝０．２０　　ｙ＝ｏ、７０　　ｚ＝０．
１０　　）　。 Ｃ：（Ｘ＝０．２０　　ｙ＝０．５ｏ　　ｚ＝０．３０
　　）−Ｄ　：　（ｘ＝０．０５　　ｙ＝ｏ、５０　　
Ｚ＝０．４５　１を結ぶ線上およびこの線に囲まれる組
成範囲にあることを％敵とする電歪磁器１成物。[Claims] Iron/lead tungstate [pb(pe%wX/3)Os]
+ Nickel lead niobate (Pb (Ni occupation Nb2/3) 0
3) A three-component porcelain composition derived from lead tannate (pbTios) [Pb(Fe2/3W!/3)03]
, CPb (N i !/3 Nb"3 )03 ]
, [Pb T i 03 ,] 2 When expressed as (
However, x+y+z=1. oO), blending ratio x, y. 2 is the following embryonic point A in this three-component spinogram. B, C, D A: (X=O,l)1 y=0.78 z=0
．． 21). B: (X=0.20 y=o, 70 z=0.
10). C: (X=0.20 y=0.5o z=0.30
)-D: (x=0.05 y=o, 50
An electrostrictive porcelain 1 product that is on the line connecting Z=0.45 1 and within the composition range surrounded by this line.