JPS63288960A - Production of (pb, bi) (zr, ti)o3 - Google Patents
Production of (pb, bi) (zr, ti)o3Info
- Publication number
- JPS63288960A JPS63288960A JP62122571A JP12257187A JPS63288960A JP S63288960 A JPS63288960 A JP S63288960A JP 62122571 A JP62122571 A JP 62122571A JP 12257187 A JP12257187 A JP 12257187A JP S63288960 A JPS63288960 A JP S63288960A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- pbzt
- contg
- soln
- zirconium
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920003254 poly(benzobisthiazole) Polymers 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 54
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 20
- 239000000470 constituent Substances 0.000 abstract description 8
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 4
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- -1 Tie Chemical compound 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007932 molded tablet Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はＰＢＺＴの製造方法に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing PBZT.
ＰＢＺＴは偏光素子、光シャッタ、画像記憶素子などの
オプトセラミックスとして広範囲の応用が期待されてい
る。PBZT is expected to have a wide range of applications as opto-ceramics such as polarizing elements, optical shutters, and image storage elements.
ＰＢＺＴの構成金属成分であるＰｂ 、 Ｂｉ 、 Ｚ
ｒ 、 Ｔｉの酸化物原料粉末の中で、ジルコニヤ原料
粉末は極めて凝集し易い、この様なジルコニヤ原料粉末
を使用して軟式法でＰＢＺＴ原料粉末を作成しても平均
粒径は１〜２μ鍮以上のものとなる。この程度の粒度の
１）［ｌＺＴ原料粉末を使用しても、高密度且つ透光性
が高く光学的に均一なＰ［ｌＺＴを得ることは難しい。The constituent metal components of PBZT are Pb, Bi, and Z.
r, Among Ti oxide raw material powders, zirconia raw material powders are extremely easy to agglomerate. Even if PBZT raw material powders are made by a soft method using such zirconia raw material powders, the average particle size is 1 to 2 μm. It becomes more than that. Even if 1) [lZT raw material powder with such a particle size is used, it is difficult to obtain optically uniform P[lZT with high density and high translucency.
本発明は前記のＰＢＺＴの乾式法による合成における欠
点を解消すべくなされたもので、その目的は、分散性の
良いサブミクロン級の変成ジルコニヤ原料粉末を作成し
、該粉末を用いて単なる乾式法によって易焼結性且つ高
嵩密度のＰＢＺＴ粉末をき成し、更にこの粉末を焼結し
て高密度且つ透光性が高く光学的に均一なＰＢＺＴを製
造する方法を提供することにある。The present invention was made in order to eliminate the drawbacks of the above-mentioned dry method synthesis of PBZT, and its purpose is to create a submicron grade modified zirconia raw material powder with good dispersibility, and to use this powder to perform a simple dry method synthesis. The object of the present invention is to provide a method for producing a PBZT powder that is easily sinterable and has a high bulk density, and further sintering this powder to produce a PBZT that has a high density, high translucency, and is optically uniform.
本発明者らは前記目的を達成すべく鋭意研究の結果、
一般式（Ｐｂ＋−ｘＢｉｘ） （Ｚｒ＋ −ｙＴｉｙ）
Ｉ−１／４０３ 。As a result of intensive research to achieve the above object, the present inventors found that the general formula (Pb+ -xBix) (Zr+ -yTiy)
I-1/403.
Ｏ＜Ｘ≦０．３．０≦Ｙ≦１．０．で示されるＰＢＺＴ
の乾式法による製造過程において、ジルコニウム以外の
少なくとも一金属成分の適量とジルコニウムとを含有す
る溶液と沈殿形成液を反応させて共沈体を形成すると系
の不均一のためＺ「含有粒子の凝集が起こりにくくなり
、その後乾燥を行ない、７００〜１３００°Ｃで仮焼す
ると、凝集の極めて少ないサブミクロン級の粉末（変成
ジルコニヤ粉末）と成し得ることが分った。これを原料
とし、目的とするＰＢＺＴ組成の残りの構成部分の化合
物を乾式法によって混合すれば、サブミクロン級の粉末
特性の優れた原料粉末が容易に得られ、これを成型して
焼結すると、ホットプレスやＩ−Ｉ Ｉ Ｐ （熱間ガ
ス圧焼結）などの操作を省略しても極めて高密度且つ透
光性が高く光学的に均一なｒ’ＢＺＴが容易に得られる
ことを究明し得た。この知見に基いて本発明を完成した
。O<X≦0.3.0≦Y≦1.0. PBZT denoted by
In the dry method manufacturing process, if a solution containing zirconium and an appropriate amount of at least one metal component other than zirconium is reacted with a precipitate-forming solution to form a coprecipitate, the system will be non-uniform and the particles will agglomerate. It was found that by drying and calcining at 700 to 1300°C, submicron-grade powder (modified zirconia powder) with extremely low agglomeration could be produced. If the remaining components of the PBZT composition are mixed by a dry method, a raw material powder with excellent submicron powder properties can be easily obtained, and when this is molded and sintered, hot press or I- It was found that r'BZT with extremely high density, high translucency, and optical uniformity can be easily obtained even if operations such as IIP (hot gas pressure sintering) are omitted.This knowledge The present invention was completed based on this.
本発明の要旨は次の３つの工程の組み合わせにある。The gist of the present invention lies in the combination of the following three steps.
（１） ＰＢＺＴを構成するジルコニウム以外の少なく
とも一成分の、共沈体の凝集を抑制に足る適量と、ジル
コニウムとを含有する溶液を作り、これと沈殿形成液と
を反応せしめ共沈体を形成し、乾９４ ｔｉｔ７００〜
１３００℃で仮焼する工程、この工程では共沈体の凝集
が避けられ、またＰＬＺＴ 、 ＰＺＴなどの製造にも
使用することができる変成ジルコニヤが製造される。(1) Prepare a solution containing zirconium and at least one component other than zirconium constituting PBZT in an appropriate amount sufficient to suppress agglomeration of the coprecipitate, and react this with a precipitate forming solution to form a coprecipitate. Shi, dry 94 tit700~
The process of calcination at 1300°C avoids agglomeration of the coprecipitate and produces modified zirconia that can also be used in the production of PLZT, PZT, etc.
（２） （１）の工程で得られた仮焼物と、目的とする
ＰＢＺＴ組成の残りの構成成分の化合物を混合して５０
０〜１３００℃で仮焼する工程。この工程では、残（３
） （２）の工程で得られた仮焼粉末を成型して１００
０〜１３００℃で焼結する工程。(2) Mix the calcined product obtained in step (1) with the remaining constituent compounds of the desired PBZT composition and
A process of calcination at 0-1300℃. In this process, the remaining (3
) The calcined powder obtained in step (2) is molded into 100
A process of sintering at 0 to 1300°C.
ジルコニウム溶液を作成するための化合物としては、オ
キシ塩化ジルコニウム、オキシ硝酸ジルコニウム、塩化
ジルコニウム、硝酸ジルコニウム、及び、金属ジルコニ
ウム等が挙げられる。ジルコニウム溶液の溶媒としては
上記化合物を溶解させる水またはアルコールを用いる。Examples of compounds for creating a zirconium solution include zirconium oxychloride, zirconium oxynitrate, zirconium chloride, zirconium nitrate, and metal zirconium. As a solvent for the zirconium solution, water or alcohol that dissolves the above compound is used.
上記化合物はすべて水に可溶であり、オキシ塩化ジルコ
ニウム、塩化ジルコニウムおよび四塩化チタンはエタノ
ールに可溶である。さらに、ジルコニウム溶液を作製す
るために、金属ジルコニウムを王水、ＨＦで溶解して用
いることもできる。ジルコニウム以外の少なくとも一成
分の溶液を作製するための化合物としては、Ｐｂ（ＮＯ
ｓ）ｚ 、 Ｔｉ（ＮＯｓ）４． Ｔ：ＣＩ＜ 。All of the above compounds are soluble in water; zirconium oxychloride, zirconium chloride and titanium tetrachloride are soluble in ethanol. Furthermore, in order to prepare a zirconium solution, metal zirconium can be dissolved in aqua regia or HF. As a compound for preparing a solution containing at least one component other than zirconium, Pb(NO
s)z, Ti(NOs)4. T: CI<.
Ｔｉ（Ｓｏ、）ｚ 、 １３ｉｚ（ＳＯ−）ｓが挙げら
れる。この溶液の溶媒としては水またはアルコールを用
いる。ジルコニウム溶液とジルコニウム以外の溶液は別
々に調製してもよく、また同一の溶媒に各化合物を溶解
させて調整してもよい。Examples include Ti(So,)z and 13iz(SO-)s. Water or alcohol is used as the solvent for this solution. The zirconium solution and the solution other than zirconium may be prepared separately, or may be prepared by dissolving each compound in the same solvent.
沈殿形成液作成のための試薬としては、例えばアンモニ
ヤ、炭酸アンモニウム、苛性アルカリ、しゅう酸、しゅ
う酸アンモニウムやアミン、オキシン等の有機試薬が挙
げられる。沈殿形成反応は常温で行なうことができる。Examples of reagents for preparing the precipitate-forming solution include organic reagents such as ammonia, ammonium carbonate, caustic alkali, oxalic acid, ammonium oxalate, amines, and oxine. The precipitate formation reaction can be carried out at room temperature.
共沈体の状態はゾル状ないしスラリー状である。共沈体
はろ過および洗浄により回収する。The coprecipitate is in a sol or slurry state. The coprecipitate is recovered by filtration and washing.
ジルコニウム溶液に溶解されるＰＢＺＴの構成成分の種
類とその量は、構成成分の添加によって最終的に得られ
るジルコニヤ粉末の凝集を有効に抑制し得られるものが
好ましい、得られな共沈体の仮焼温度は、７００〜１３
００℃である。仮焼温度が７００℃より低いと凝集が顕
著に起り、１３００℃を超えると粒子が粗大化する傾向
がある。この様にして得られたものに、ジルコニウム以
外の構成成分の不足分を加えて混合する。勿論、ジルコ
ニヤに添加した成分の不足分も補充する必要がある。こ
の場合、いずれの化合物粉末（主として酸化物）の粒度
もサブミクロン級のものを使用する。ただし、酸化鉛粉
末は粗大粒径のものを使用しても、得られるＰＢＺＴ粉
末の特性に殆んど影響を与えない。The type and amount of the PBZT component dissolved in the zirconium solution is preferably one that can effectively suppress the agglomeration of the zirconia powder that is finally obtained by adding the component. Baking temperature is 700-13
It is 00℃. When the calcination temperature is lower than 700°C, agglomeration occurs significantly, and when it exceeds 1300°C, the particles tend to become coarse. To the thus obtained mixture, the remaining components other than zirconium are added and mixed. Of course, it is also necessary to replenish the missing components added to zirconia. In this case, the particle size of any compound powder (mainly oxide) used is submicron class. However, even if lead oxide powder with a coarse particle size is used, it will hardly affect the properties of the obtained PBZT powder.
これら混合物の仮焼温度は、Ｔｉを含む場き、Ｂｉを含
む場合、ＴｉとＢｉを含む場合とで、５００〜１３００
℃の範囲で大幅に変化する。要は、固相反応がほぼまた
は完全に完了する最低温度以上で、顕著な粒子成長が生
じない最高温度範囲内であることが必要であり、５００
〜１３００℃の範囲がよい。The calcination temperature of these mixtures is 500 to 1300 when containing Ti, when containing Bi, and when containing Ti and Bi.
Varies significantly over the °C range. In short, it is necessary that the temperature be at least the minimum temperature at which the solid phase reaction is almost or completely completed, and within the maximum temperature range at which no significant particle growth occurs;
The temperature range is preferably from 1300°C to 1300°C.
この様にして得られた粉末を成型する。焼結温度は前記
の混合物の仮焼温度と同様にその構成成分の種類によっ
て異なるが、一般に１０００〜１３００℃の範囲である
。１０００℃より低いと焼結が不十分で高密度が得られ
ず、１３００℃を超えると粒子が粗大化したり、あるい
はｐｂの揮発が促進される。The powder thus obtained is molded. The sintering temperature, like the calcination temperature of the mixture described above, varies depending on the types of constituent components, but is generally in the range of 1000 to 1300°C. If it is lower than 1000°C, sintering is insufficient and high density cannot be obtained, and if it exceeds 1300°C, the particles become coarse or the volatilization of PB is promoted.
・実施例１
四塩化チタン水溶液（０，８０ｍｏｌ／／濃度）４０．
０ｃｃとオキシ硝酸ジルコニウム水溶液（０，８０ｍｏ
ｌ／ｊ！濃度）１６０、Ｏｃｃを混合しな。この、混合
水溶液を撹拌している６規定アンモニヤ水ｌｌ中に徐々
に添加して、Ｔｉ４＋とＺｒ４＋の水酸化物共沈体を得
た。これを洗浄、乾燥した後１１００℃で仮焼して（Ｚ
ｒｏ、５Ｔｉｏ、２）０２粉末を作成した。- Example 1 Titanium tetrachloride aqueous solution (0.80 mol//concentration) 40.
0cc and zirconium oxynitrate aqueous solution (0.80mo
l/j! Concentration) 160, do not mix Occ. This mixed aqueous solution was gradually added to 1 liter of stirring 6N ammonia water to obtain a hydroxide coprecipitate of Ti4+ and Zr4+. After washing and drying this, it was calcined at 1100℃ (Z
ro, 5Tio, 2)02 powders were created.
この粉末の平均粒径は０．３２μ鏑であった。The average particle size of this powder was 0.32μ.
該粉末３０．３３ｇｒと市販のＴｉＯ□微粉末５．５７
ｇｒ、 ＰｂＯ粉末（平均粒径１５μ輸）６７．７０ｇ
ｒ、ＢｉｚＯ−微粉末６．９９ｇｒとを、ボールミルで
一昼夜混合した後、８５０℃で２時間仮焼して
（ＰｂＱ、ｌｌＢ１０．０９）（Ｚｒ０．６５ＴｉＯ，
３５）ａ、！７７５０３粉末を得た。その平均粒径は０
．３２μ端であった。該粉末を１ ｔｏｎ／ ｃｔｍ２
で成型したタブレットを、鉛蒸気、酸素ガス共存雰囲気
下、１２００℃で１０時ｒｒＲ焼結した。The powder 30.33g and commercially available TiO□ fine powder 5.57g
gr, PbO powder (average particle size 15μ) 67.70g
r, 6.99g of BizO-fine powder were mixed in a ball mill for a day and night, and then calcined at 850°C for 2 hours to produce (PbQ, 11B10.09) (Zr0.65TiO,
35) a,! 77503 powder was obtained. Its average particle size is 0
．． It was at the 32μ end. 1 ton/ctm2 of the powder
The molded tablet was subjected to rrR sintering at 1200° C. for 10 hours in an atmosphere coexisting with lead vapor and oxygen gas.
得られたものの密度は７．８４に達し、透光率は波長６
００ ｎｍを用いサンプル厚み２．５１１Ｍの場合的４
５％であった。The density of the obtained product reaches 7.84, and the transmittance is at wavelength 6
Case 4: 00 nm and sample thickness 2.511M
It was 5%.
・実施例２
四塩化チタン水溶液（０，８０鋤ｏ１／１濃度）８６．
１５ｃｃ、硝酸ビスマス水溶液（Ｏ，ＳＯ輸ｏ！／１濃
度） ２２．６６ｃｃとオキシ硝酸ジルコニウム水溶液
＜０．８０ｍｏｌ／ １濃度）１８０ｃｃを混合した。- Example 2 Titanium tetrachloride aqueous solution (0.80 o1/1 concentration) 86.
15 cc, 22.66 cc of bismuth nitrate aqueous solution (O,SO 0!/1 concentration), and 180 cc of zirconium oxynitrate aqueous solution (<0.80 mol/1 concentration) were mixed.
この混合水溶液を撹拌している６規定アンモニヤ水１１
中に徐々に添加して、［１ｉ’＋とＴｉ４＋とＺｒ’＋
の水酸化物共沈体を得な。これを洗浄、乾燥した？＆１
１００℃で仮焼してＤｉｏ’、ｏｓ（Ｚｒｏ、５ｓＴｉ
ｏ、：＋ｓ ） ｏ、５ｔｔｓＯｚ、ｏｓ粉末を作成し
た。6N ammonia water 11 stirring this mixed aqueous solution
[1i'+, Ti4+ and Zr'+
Obtain a hydroxide coprecipitate of Did you wash and dry this? &1
Calcinate at 100℃ to obtain Dio', os(Zro, 5sTi)
o, :+s) o, 5ttsOz, os powder was created.
この粉末の平均粒径は０．３２μ−であった。The average particle size of this powder was 0.32μ.
該粉末１２．６６ ｇｒと市販のＰｂＯ粉末（平均粒径
１５μｍ１ ） ２０．３１ｇｒとをボールミルで一昼
夜混合した後、８５０℃で２時間仮焼して（Ｐｂｏ、＊
１［１＋６．。、）（Ｚｒｏ、５ｓＴｉｏ、５ｓ）ｏ、
５ｔ７ｓＯ＋粉末を得た。その平均粒径は０．３５μ嬶
であった。該粉末を１ｔｏｎ／ａｍ２で成型したタブレ
ットを、鉛蒸気、酸素ガス共存雰囲気下、１２００℃で
１０時間焼結した。得られたものの密度は７．８１に達
し、透光率は波長６００ ｎｍを用いサンプル厚み２．
５ｍｓ＋の場合的４０％であった。After mixing 12.66 gr of this powder and 20.31 gr of commercially available PbO powder (average particle size 15 μm1) in a ball mill for a day and night, they were calcined at 850°C for 2 hours (Pbo, *
1[1+6. . , ) (Zro, 5sTio, 5s)o,
5t7sO+ powder was obtained. The average particle size was 0.35 μm. A tablet formed from the powder at 1 ton/am2 was sintered at 1200° C. for 10 hours in an atmosphere coexisting with lead vapor and oxygen gas. The density of the obtained product reached 7.81, and the light transmittance was determined using a wavelength of 600 nm and a sample thickness of 2.
5ms+ was 40% of the time.
・実施例３
硝酸ビスマス水溶液（０、８０ａ＋ｏ Ｉ ／ ｌ濃度
）１８．４１ ｃｃとオキシ硝酸ジルコニウム水溶液（
０，８０ｍｏｌ／ １濃度）１６０ｃｃを混きした。こ
の混合水溶液を撹拌している６規定アンモニヤ水１１中
に徐々に添加して、Ｂｉ１２とＺｒ’＋の水酸化物共沈
体を得た。これを洗浄、乾燥したｆ＆１１００℃で仮焼
してＢｉｏ 、ｏｓＺｒｏ 、ａ５ｓＯ＋ 、４０５粉
末を得た。・Example 3 Bismuth nitrate aqueous solution (0,80a+o I/L concentration) 18.41 cc and zirconium oxynitrate aqueous solution (
0.80 mol/1 concentration) 160 cc was mixed. This mixed aqueous solution was gradually added to stirring 6N ammonia water 11 to obtain a hydroxide coprecipitate of Bi12 and Zr'+. This was washed, dried, and calcined at f&1100°C to obtain Bio, osZro, a5sO+, and 405 powders.
この粉末の平均粒径は０．３２μ講であった。The average particle size of this powder was 0.32 μm.
該粉末９．９２１ｇｒと市販のＴｉ０ｚ微粉末２．７３
３ｇｒとＰｂＯ粉末（平均粒径１５ ｉｔ ｎ＋）２０
．３１１ｇｒとをボールミルで一昼夜混合した後、８５
０℃で２時間仮焼して（Ｐｂ０．ｅｌ［１ｉ０．。＊）
（Ｚｒ。、５５Ｔｉｏ、ｏｓ）。−１７７５０３粉末を
得た。その平均粒径は０．４１μ紬であった。該粉末を
１ ｔｏｎ／ ｃｍ２で成型したタブレットを、鉛蒸気
、酸素ガス共存雰囲気下、１２００℃で１０時間焼結し
た３得られたものの密度は７．８０に達し、透光率は波
長６００ｎｍを用いサンプル厚み２．５１１１ｍの場合
的３６％であった。9.921 gr of the powder and 2.73 gr of commercially available Ti0z fine powder
3gr and PbO powder (average particle size 15 it n+) 20
．． After mixing with 311gr in a ball mill for a day and night, 85gr.
Calcined at 0℃ for 2 hours (Pb0.el[1i0..*)
(Zr., 55Tio, os). -177503 powder was obtained. The average particle size was 0.41 μm. A tablet made of 1 ton/cm2 of the powder was sintered at 1200°C for 10 hours in an atmosphere coexisting with lead vapor and oxygen gas.3 The density of the obtained product reached 7.80, and the transmittance at a wavelength of 600 nm. In the case of the used sample thickness of 2.5111 m, it was 36%.
・比較例
市販ＰｂＯ、Ｔｉｅ、 、 ＺｒＯ２、Ｂｉ、０．粉末
を（ＰｂＯ，ｌｌＢ１０−０９）（Ｚｒ０１ＳＴ１０１
５）Ｏ−１１７７５０ｆｆの組成になるように配合し、
ボールミルで１昼夜混合したｆ＆９００℃で２時間仮焼
した。この粉末をｉｔ／ｃｍ２で成型し、実施例１，２
．３と同じ条件下で焼結した。・Comparative example Commercially available PbO, Tie, ZrO2, Bi, 0. Powder (PbO, llB10-09) (Zr01ST101
5) Blend to have a composition of O-117750ff,
The mixture was mixed in a ball mill for one day and then calcined at f&900°C for 2 hours. This powder was molded at it/cm2, and Examples 1 and 2
．． It was sintered under the same conditions as 3.
得られたＰＢＺＴの密度は７．６程度であったが、透明
な焼結体にならなかった。なお仮焼時の粉末の平均粒径
は２．８μ鍋であった。Although the density of the obtained PBZT was about 7.6, it did not become a transparent sintered body. The average particle size of the powder during calcination was 2.8 μm.
本発明の方法によると、第１工程によりＰＢＺＴの構成
成分の一種以上を含むジルコニヤ粉末（変成ジルコニヤ
粉末）は、二次粒子の極めて少ないサブミクロン粒子と
なし得、これを使用することによって、以後通常の圧粉
工程と焼結工程よりなる単なる乾式法によって、容易に
サブミクロン級のＰＢＺＴ原料粉末が得られ、更にこれ
を原料として透光性が良く高密度のｐｏｚＴが得られる
、という優れた効果を奏し得られる。そのほか次のよう
な効果も奏し得られる。According to the method of the present invention, the zirconia powder (modified zirconia powder) containing one or more of the constituent components of PBZT in the first step can be made into submicron particles with extremely few secondary particles. Submicron grade PBZT raw material powder can be easily obtained by a simple dry method consisting of a normal powder compaction process and a sintering process, and furthermore, it is possible to obtain pozT with good translucency and high density using this as a raw material. It can be effective. In addition, the following effects can also be achieved.
１）仮焼によって得られる変成ジルコニヤ粉末が十分分
散されたものが得られるため、仮焼物の粉砕工程を特に
必要としないで、原料粉末として供給し得られる。1) Since the modified zirconia powder obtained by calcining is sufficiently dispersed, it can be supplied as a raw material powder without the need for a particular pulverization step of the calcined product.
２） 該仮焼変成ジルコニヤ粉末から乾式法で得られる
ＰＩ３ＺＴ粉末も単分散状態で得られ、従って粉砕工程
を除いても十分易焼結性且つ高密度の特性を有する。2) PI3ZT powder obtained from the calcined modified zirconia powder by a dry process is also obtained in a monodisperse state, and therefore has characteristics of sufficiently easy sinterability and high density even without the pulverization step.
３〉 極めて高密度且つ光学的高均一性を要求されるオ
プトエレクトロニクス用ＰＩＩＺＴをホットプレスやＨ
ＩＰ（熱間ガス圧焼結）なとの操作を省略して単なる固
相焼結によって、理論密度に極めて近い高密度で得るこ
とができる。3) PIIZT for optoelectronics, which requires extremely high density and high optical uniformity, is processed by hot pressing or H
A high density extremely close to the theoretical density can be obtained by simply solid-phase sintering, omitting an operation such as IP (hot gas pressure sintering).
４） 優れた粉末特性を有する変成ジルコニヤ粉末を大
量生産することによって、ｆｔ意の組成のＰ［３ＺＴを
極めて安価に供給し得る。4) By mass producing modified zirconia powder with excellent powder properties, P[3ZT having the desired composition can be supplied at an extremely low cost.
Claims (3)
も一金属成分の適量と、ジルコニウムとを含有する溶液
及び沈殿形成液を反応させて共沈体を形成し、共沈体を
乾燥後７００〜１３００℃で仮焼する工程、(1) A coprecipitate is formed by reacting an appropriate amount of at least one metal component other than zirconium constituting PBZT with a solution containing zirconium and a precipitate forming solution, and the coprecipitate is dried at 700 to 1300°C. the process of calcining;
構成成分の化合物を混合して５００〜１３００℃で仮焼
する工程、(2) a step of mixing this calcined product with compounds of the remaining components of the desired PBZT composition and calcining at 500 to 1300°C;
℃で焼結する工程からなることを特徴とするＰＢＺＴの
製造方法。(3) The obtained calcined powder is molded to a size of 1000 to 1300
A method for producing PBZT, comprising a step of sintering at °C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122571A JPS63288960A (en) | 1987-05-21 | 1987-05-21 | Production of (pb, bi) (zr, ti)o3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122571A JPS63288960A (en) | 1987-05-21 | 1987-05-21 | Production of (pb, bi) (zr, ti)o3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63288960A true JPS63288960A (en) | 1988-11-25 |
Family
ID=14839198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62122571A Pending JPS63288960A (en) | 1987-05-21 | 1987-05-21 | Production of (pb, bi) (zr, ti)o3 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63288960A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005150694A (en) * | 2003-10-23 | 2005-06-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
| JP2005159309A (en) * | 2003-11-05 | 2005-06-16 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
| JP2006066795A (en) * | 2004-08-30 | 2006-03-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet type record head, ink-jet printer, surface elastic wave element, frequency filter, oscillator, electronic circuit, thin-film piezoelectric resonator and electronic device |
| JP2009062207A (en) * | 2007-09-05 | 2009-03-26 | Fujifilm Corp | Perovskite type oxide, ferroelectric film, process for producing same, ferroelectric device, and liquid discharge apparatus |
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| JPS6051664A (en) * | 1983-08-30 | 1985-03-23 | 日本特殊陶業株式会社 | Manufacture of lead zirconate titanate ceramic |
| JPS6153114A (en) * | 1984-08-18 | 1986-03-17 | Natl Inst For Res In Inorg Mater | Production of powdery raw material of easily sintering perovskite solid solution |
| JPS61247607A (en) * | 1985-04-22 | 1986-11-04 | Natl Inst For Res In Inorg Mater | Preparation of raw material powder of compound having perovskite structure |
| JPS62191465A (en) * | 1985-09-24 | 1987-08-21 | 科学技術庁無機材質研究所長 | Manufacture of perovskite ceramics containing zirconium |
| JPS63156057A (en) * | 1986-12-19 | 1988-06-29 | 科学技術庁無機材質研究所長 | Manufacture of high density perovskite ceramics |
| JPS63218514A (en) * | 1987-03-06 | 1988-09-12 | Seitetsu Kagaku Co Ltd | Production of perovskite ceramic powder containing zirconium |
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| JPS50151910A (en) * | 1974-05-31 | 1975-12-06 | ||
| JPS6051664A (en) * | 1983-08-30 | 1985-03-23 | 日本特殊陶業株式会社 | Manufacture of lead zirconate titanate ceramic |
| JPS6153114A (en) * | 1984-08-18 | 1986-03-17 | Natl Inst For Res In Inorg Mater | Production of powdery raw material of easily sintering perovskite solid solution |
| JPS61247607A (en) * | 1985-04-22 | 1986-11-04 | Natl Inst For Res In Inorg Mater | Preparation of raw material powder of compound having perovskite structure |
| JPS62191465A (en) * | 1985-09-24 | 1987-08-21 | 科学技術庁無機材質研究所長 | Manufacture of perovskite ceramics containing zirconium |
| JPS63156057A (en) * | 1986-12-19 | 1988-06-29 | 科学技術庁無機材質研究所長 | Manufacture of high density perovskite ceramics |
| JPS63218514A (en) * | 1987-03-06 | 1988-09-12 | Seitetsu Kagaku Co Ltd | Production of perovskite ceramic powder containing zirconium |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005150694A (en) * | 2003-10-23 | 2005-06-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
| JP2005159309A (en) * | 2003-11-05 | 2005-06-16 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet recording head, ink-jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic apparatus |
| JP4600650B2 (en) * | 2003-11-05 | 2010-12-15 | セイコーエプソン株式会社 | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink jet recording head, ink jet printer, surface acoustic wave element, thin film piezoelectric resonator, frequency filter, oscillator, electronic circuit, and electronic equipment |
| JP2006066795A (en) * | 2004-08-30 | 2006-03-09 | Seiko Epson Corp | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink-jet type record head, ink-jet printer, surface elastic wave element, frequency filter, oscillator, electronic circuit, thin-film piezoelectric resonator and electronic device |
| JP4600647B2 (en) * | 2004-08-30 | 2010-12-15 | セイコーエプソン株式会社 | Piezoelectric film, piezoelectric element, piezoelectric actuator, piezoelectric pump, ink jet recording head, ink jet printer, surface acoustic wave element, frequency filter, oscillator, electronic circuit, thin film piezoelectric resonator, and electronic device |
| JP2009062207A (en) * | 2007-09-05 | 2009-03-26 | Fujifilm Corp | Perovskite type oxide, ferroelectric film, process for producing same, ferroelectric device, and liquid discharge apparatus |
| EP2034040A3 (en) * | 2007-09-05 | 2012-07-25 | FUJIFILM Corporation | Perovskite type oxide, ferroelectric film, process for producing same, ferroelectric device, and liquid discharge apparatus |
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