JPH0643266B2 - High-density BZNT-based ferroelectric ceramic manufacturing method - Google Patents
High-density BZNT-based ferroelectric ceramic manufacturing methodInfo
- Publication number
- JPH0643266B2 JPH0643266B2 JP61168793A JP16879386A JPH0643266B2 JP H0643266 B2 JPH0643266 B2 JP H0643266B2 JP 61168793 A JP61168793 A JP 61168793A JP 16879386 A JP16879386 A JP 16879386A JP H0643266 B2 JPH0643266 B2 JP H0643266B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- precipitate
- aqueous solution
- niobium
- tantalum
- 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.)
- Expired - Lifetime
Links
- 239000000919 ceramic Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002244 precipitate Substances 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 150000001553 barium compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 11
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 150000003482 tantalum compounds Chemical class 0.000 claims description 10
- -1 fluoride ions Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 150000002822 niobium compounds Chemical class 0.000 claims description 8
- 150000003752 zinc compounds Chemical class 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001513 hot isostatic pressing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004529 TaF 5 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- WYGQZDSIRBBVTA-UHFFFAOYSA-D [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WYGQZDSIRBBVTA-UHFFFAOYSA-D 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VIFFBFSYCHETPB-UHFFFAOYSA-D tantalum(5+) pentacarbonate Chemical compound [Ta+5].[Ta+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O VIFFBFSYCHETPB-UHFFFAOYSA-D 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Control Of Motors That Do Not Use Commutators (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は誘電体共振器用の機能性セラミック、マイクロ
波集積回路などに使用される媒体用セラミック等多くの
用途に利用し得る高密度ＢＺＮＴ系強誘電体セラミック
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is a high density BZNT system that can be used in many applications such as functional ceramics for dielectric resonators and ceramics for media used in microwave integrated circuits. The present invention relates to a method for manufacturing a ferroelectric ceramic.
従来、ＢＺＮＴ系強誘電体セラミックの原料粉末は、乾
式法又は湿式共沈法で製造されていた。Conventionally, the raw material powder of the BZNT-based ferroelectric ceramic has been manufactured by a dry method or a wet coprecipitation method.
乾式法は構成成分の化合物粉末を混合し、これを仮焼す
る方法である。しかし、この方法では均一な組成の原料
粉末が得難く、またＢＺＮＴの生成反応を完逐させるた
めに仮焼温度を高くすることが必要であるので、これに
より粒子が粗大化して易焼結性になりにくい欠点があっ
た。The dry method is a method in which compound powders of the constituents are mixed and calcined. However, with this method, it is difficult to obtain a raw material powder having a uniform composition, and since it is necessary to raise the calcination temperature in order to complete the reaction for producing BZNT, this causes the particles to become coarse and easily sinterable. There was a drawback that it was hard to become.
湿式共沈法はＢＺＮＴの構成成分のすべての混合液を作
り、これにアルカリ等の沈殿形成液を添加して共沈さ
せ、乾燥、仮焼する方法である。しかし、この方法は均
一性の優れた粉末が得やすいが、その均一性なるが故に
沈殿形成時、乾燥時、また仮焼時に凝結して二次粒子を
形成し、易焼結性となりにくい欠点がある。The wet coprecipitation method is a method in which a mixed solution of all constituents of BZNT is prepared, and a precipitation forming solution such as an alkali is added to the mixture to coprecipitate, followed by drying and calcination. However, although this method makes it easy to obtain a powder with excellent uniformity, it is difficult to form a secondary particle by condensing to form secondary particles during precipitation formation, drying, and calcination because of its uniformity. There is.
更にまた、ＢＺＮＴはバリウムとニオブ及びタンタルを
含有しているので、これを共沈させる場合、ニオブ及び
タンタル原料として工業的に利用可能なフッ化ニオブ、
フッ化タンタルの水溶液を使用すると、フッ化ニオブ、
フッ化タンタルのフッ素イオンがバリウムと反応してフ
ッ化バリウムの白色沈殿を生成するため、フッ化ニオ
ブ、フッ化タンタルを使用し得ない。このため、特性の
優れた湿式共沈法によるＢＺＮＴ系強誘電体セラミック
が製造できないという問題があった。Furthermore, since BZNT contains barium, niobium and tantalum, when coprecipitating this, niobium and niobium fluoride industrially usable as a tantalum raw material,
Using an aqueous solution of tantalum fluoride, niobium fluoride,
Niobium fluoride and tantalum fluoride cannot be used because the fluorine ion of tantalum fluoride reacts with barium to produce a white precipitate of barium fluoride. Therefore, there is a problem that a BZNT-based ferroelectric ceramic having excellent characteristics cannot be manufactured by the wet coprecipitation method.
本発明は、上記のような従来の諸問題を解決し、ニオブ
及びタンタル原料として工業的に利用可能なフッ化ニオ
ブ、フッ化タンタルを使用し、高密度でしかも特性の優
れたＢＺＮＴ系強誘電体セラミックを製造し得る方法を
提供することにある。The present invention solves the above-described conventional problems, uses niobium fluoride and tantalum fluoride that are industrially applicable as raw materials for niobium and tantalum, and has a high density and excellent characteristics. It is to provide a method by which a body ceramic can be produced.
即ち、本発明の高密度ＢＺＮＴ系強誘電体セラミックの
製造方法は、組成式 ３ＢａＯ・ｘＺｎＯ・（１−ｙ）Ｎｂ2Ｏ5・ｙＴａ2Ｏ5 （但し、0.6≦ｘ≦2.0、０＜ｙ＜１の範囲である。） におけるＢａ／（Ｚｎ＋Ｎｂ＋Ｔａ）のモル比が1.0近
傍の組成を有するＢＺＮＴ系強誘電体を製造するに際
し、バリウム化合物水溶液、亜鉛化合物水溶液，フッ化
ニオブ水溶液及びフッ化タンタル水溶液を調製し、これ
ら４種の水溶液とするかあるいは亜鉛化合物水溶液をバ
リウム化合物水溶液、フッ化ニオブ水溶液、フッ化タン
タル水溶液またはフッ化ニオブとフッ化タンタルの混合
水溶液のいずれかに混合して３種または２種の水溶液と
し、それらの水溶液と過剰の沈殿形成液とを均一に混合
することによりニオブ化合物及びタンタル化合物を逐次
沈殿させるかまたは共沈させ、その後フッ素イオンを除
去し、更にその後、ニオブ化合物及びタンタル化合物沈
殿物の存在下でバリウム化合物を含む水溶液と過剰の沈
殿形成液とを均一に混合して沈殿物を形成させ、亜鉛化
合物を含む水溶液と過剰の沈殿形成液との均一混合をニ
オブ化合物沈殿物またはタンタル化合物沈殿物の形成
前、ニオブ化合物沈殿物またはタンタル化合物沈殿物の
形成と同時、フッ素イオンの除去前、バリウム化合物沈
殿物の形成前、バリウム化合物沈殿物の形成と同時又は
バリウム化合物沈殿物の形成後の任意の段階で実施して
全成分の均密沈殿物を形成し、該沈殿物を５００〜１２
００℃で仮焼した後、成形物を空気中又は酸素雰囲気
中、１０００〜１６００℃で焼結させるか、又は不活性
雰囲気で熱間静水圧加圧により高密度化し、更に大気中
で焼結させることを特徴とする。That is, the manufacturing method of high density BZNT based ferroelectric ceramics of the present invention, the composition formula 3BaO · xZnO · (1-y ) Nb 2 O 5 · yTa 2 O 5 ( where, 0.6 ≦ x ≦ 2.0,0 <y In the case of producing a BZNT-based ferroelectric substance having a composition in which the molar ratio Ba / (Zn + Nb + Ta) in <1) is around 1.0, an aqueous barium compound solution, an aqueous zinc compound solution, an aqueous niobium fluoride solution, and tantalum fluoride are used. An aqueous solution is prepared, and these four types of aqueous solutions are prepared, or the zinc compound aqueous solution is mixed with either a barium compound aqueous solution, a niobium fluoride aqueous solution, a tantalum fluoride aqueous solution, or a mixed aqueous solution of niobium fluoride and tantalum fluoride. Or two kinds of aqueous solutions, and the niobium compound and the tantalum compound are sequentially precipitated by uniformly mixing the aqueous solution and the excess precipitation-forming solution. Or coprecipitate the solution, and then remove the fluoride ion. Then, in the presence of the niobium compound and tantalum compound precipitates, the aqueous solution containing the barium compound and the excess precipitate forming solution are uniformly mixed to form precipitates. A uniform mixture of an aqueous solution containing a zinc compound and an excess precipitation-forming solution is formed before the formation of the niobium compound precipitate or the tantalum compound precipitate, and at the same time as the formation of the niobium compound precipitate or the tantalum compound precipitate, the removal of the fluorine ion. Before the formation of the barium compound precipitate, at the same time as the formation of the barium compound precipitate, or at any stage after the formation of the barium compound precipitate to form a homogeneous precipitate of all components, ~ 12
After calcination at 00 ° C, the molded product is sintered at 1000 to 1600 ° C in air or oxygen atmosphere, or densified by hot isostatic pressing in an inert atmosphere, and further sintered in air. It is characterized by
本発明においては、フッ化バリウムの白色沈殿の生成を
防止するためには、ニオブ化合物及びタンタル化合物を
先に沈殿せしめ、沈殿分散液に存在するフッ素イオンを
除去してからバリウム化合物の沈殿を形成せしめること
が必須である。しかし、亜鉛化合物の沈殿を形成させる
段階は任意である。本発明においては、具体的には、例
えば、第１図（Ａ）〜（Ｄ）に示した沈殿形成の順序で
均密沈殿を作ることができる。In the present invention, in order to prevent the formation of a white precipitate of barium fluoride, the niobium compound and the tantalum compound are precipitated first, and the fluoride ions present in the precipitate dispersion are removed, and then the barium compound precipitate is formed. It is indispensable to do it. However, the step of forming a precipitate of the zinc compound is optional. In the present invention, specifically, for example, a uniform precipitate can be produced in the order of precipitate formation shown in FIGS. 1 (A) to (D).
本発明においては、高密度ＢＺＮＴ系強誘電体セラミッ
クの焼結性や特性を制御するために、微量成分、例え
ば、Ｃａ、Ｓｒ、Ｔｉ、Ｓｎ、Ｍｎ、Ａｌ、Ｃｓ、Ｇ
ｅ、Ｖ、Ｂｉ、Ｆｅ、Ｃｒ、Ｎｉ、Ｉｒ、Ｒｈ、Ｎａ、
Ｉｎ、Ｋ、Ｇａ、Ｔｌ、Ｗ、Ｔｈ、希土類などの化合物
を添加してもよい。この場合、水溶液中に共存させても
よく、ＢＺＮＴ系粉末の作製後、乾式または湿式により
添加してもよい。In the present invention, in order to control the sinterability and characteristics of the high-density BZNT-based ferroelectric ceramic, trace components such as Ca, Sr, Ti, Sn, Mn, Al, Cs, and G are used.
e, V, Bi, Fe, Cr, Ni, Ir, Rh, Na,
Compounds such as In, K, Ga, Tl, W, Th, and rare earths may be added. In this case, they may be allowed to coexist in an aqueous solution, or may be added by a dry method or a wet method after the BZNT-based powder is prepared.
ＢＺＮＴ系の構成成分の水溶液を作るのに用いる成分化
合物としては、それら成分の水酸化物、オキシ塩化物、
炭酸塩、オキシ硝酸塩、硫酸塩、硝酸塩、酢酸塩、フッ
化物、ギ酸塩、シュウ酸塩、塩化物、酸化物等が挙げら
れる。これらが水に可溶でない場合は、鉱酸等を添加し
て可溶とすることができる。The component compounds used to make an aqueous solution of BZNT-based constituent components include hydroxides, oxychlorides,
Examples thereof include carbonates, oxynitrates, sulfates, nitrates, acetates, fluorides, formates, oxalates, chlorides and oxides. When these are not soluble in water, mineral acid or the like can be added to make them soluble.
沈殿形成剤としては、アンモニア、炭酸アンモニウム、
苛性ソーダ、苛性カリ、炭酸ソーダ、シュウ酸、シュウ
酸アンモニウム及びオキシンやアミン等の有機試薬等の
水溶液が挙げられる。アンモニアガスを用いてもよい。Precipitating agents include ammonia, ammonium carbonate,
Examples thereof include aqueous solutions of caustic soda, caustic potash, sodium carbonate, oxalic acid, ammonium oxalate, and organic reagents such as oxine and amine. Ammonia gas may be used.
構成成分の沈殿を形成するには、液を攪拌しながら行な
うことが望ましい。また、フッ素イオンを除去するため
に、沈殿物の生成後にロ液を分離し、沈殿物を洗浄した
後、この沈殿物を再分散させ、残りの成分を沈殿させ
る。In order to form a precipitate of the constituents, it is desirable to carry out the stirring of the liquid. Further, in order to remove the fluorine ions, the filtrate is separated after the precipitate is formed, the precipitate is washed, and then the precipitate is redispersed to precipitate the remaining components.
沈殿物の洗浄に関しては、エタノール等のアルコール類
を用いると、以後の乾燥、仮焼工程で沈殿物の凝結が抑
制されて好結果が得られる。Regarding the washing of the precipitate, if alcohols such as ethanol are used, coagulation of the precipitate is suppressed in the subsequent drying and calcination steps, and good results are obtained.
得られた沈殿物を乾燥し、５００〜１２００℃で仮焼す
る。仮焼温度が５００℃未満の場合にはＢＺＮＴの生成
範囲や脱ガスが完結せず、また、得られるＢＺＮＴ粉末
の嵩密度が低くなる。仮焼温度が１２００℃を越えると
ＢＺＮＴ粉末粒子が粗大化して焼結性が悪くなる。The obtained precipitate is dried and calcined at 500 to 1200 ° C. If the calcination temperature is lower than 500 ° C., the production range of BZNT and degassing will not be completed, and the bulk density of the BZNT powder obtained will be low. If the calcination temperature exceeds 1200 ° C., the BZNT powder particles become coarse and the sinterability deteriorates.
次に、成形・焼結する。焼結は空気中か酸素雰囲気中
で、ホット・プレスか常圧で焼結する。焼結温度が１０
００℃より低いと焼結が不十分であり、１６００℃を越
えるとＺｎＯなどの飛散が顕著になるので、１０００〜
１６００℃で行なうのが望ましい。尚、焼結は、不活性
雰囲気で熱間静水圧加圧により高密度化した後、大気中
で焼成することにより行なうこともできる。Next, it is molded and sintered. Sintering is performed by hot pressing or atmospheric pressure in air or an oxygen atmosphere. Sintering temperature is 10
If the temperature is lower than 00 ° C, the sintering is insufficient, and if the temperature exceeds 1600 ° C, the scattering of ZnO and the like becomes remarkable.
It is desirable to carry out at 1600 ° C. The sintering can also be performed by densifying by hot isostatic pressing in an inert atmosphere and then firing in the atmosphere.
以下実施例を示して、本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ Ｎｂ53.8ｇ及びＴａＦ522.5ｇを含有する水溶液１
に、重炭酸アンモニウム５ｇを含有する５Ｎアンモニア
水0.2を加えてタンタル化合物の沈殿物を生成させ、
これらを濾過し、更にその沈殿物を水洗して沈殿物から
フッ素イオンを除去した。Ｂａ（ＮＯ3）239.9ｇ、Ｚｎ
（ＮＯ3）210.6ｇ（Ｚｎは以下の沈殿操作により１０％
が損失することが分かっている。このため理論量の1.1
倍量を用いた。）を含有する水溶液１調製し、この水
溶液に上記のフッ素イオンを除去した沈殿物を分散させ
た。この分散液と、重炭酸アンモニウム２５ｇを含有す
る５Ｎアンモニア0.1とを均一に混合してバリウム、
亜鉛、ニオブ、タンタルの炭酸塩、水酸化物の均密沈殿
物を得た。ロ過、水洗、乾燥後、１１００℃で２時間仮
焼して、Ｂａ（Ｚｎ0.33Ｎｂ0.14Ｔａ0.53）Ｏ3の組成
のＢＺＮＴ原料粉末を得た。得られた仮焼粉末を電子顕
微鏡で観察したところ、平均0.2μｍの均一微粒子であ
ることが認められた。該粉末を１ｔ／cm2の圧力下で直
径３０mm、厚み３mmに成形し、空気中で常圧下、１４０
０℃で２時間焼結した。Example 1 Aqueous solution 1 containing 3.8 g of Nb 5 and 22.5 g of TaF 5
To this, 0.2 of 5N aqueous ammonia containing 5 g of ammonium bicarbonate was added to form a precipitate of tantalum compound,
These were filtered, and the precipitate was washed with water to remove fluorine ions from the precipitate. Ba (NO 3 ) 2 39.9 g, Zn
(NO 3 ) 2 10.6 g (Zn is 10% by the following precipitation operation
Are known to lose. Therefore, the theoretical amount of 1.1
Double volume was used. 1) was prepared, and the precipitate from which the above-mentioned fluorine ions were removed was dispersed in this aqueous solution. This dispersion was uniformly mixed with 0.1 of 5N ammonia containing 25 g of ammonium bicarbonate to obtain barium,
A uniform precipitate of zinc carbonate, niobium carbonate, tantalum carbonate, and hydroxide was obtained. After filtration, washing with water, drying, and calcination at 1100 ° C. for 2 hours, a BZNT raw material powder having a composition of Ba (Zn 0.33 Nb 0.14 Ta 0.53 ) O 3 was obtained. When the obtained calcined powder was observed with an electron microscope, it was confirmed that the fine particles were 0.2 μm on average. The powder was molded into a powder having a diameter of 30 mm and a thickness of 3 mm under a pressure of 1 t / cm 2 , and the powder was compressed to 140 mm under normal pressure in air.
Sintered for 2 hours at 0 ° C.
比較例１ 市販のＢａＣＯ3、ＺｎＯ、Ｎｂ2Ｏ5、Ｔａ2Ｏ5の各粉
末をＢａ（Ｚｎ0.33Ｎｂ0.14Ｔａ0.53）Ｏ3の組成にな
るように配合し、ボールミルで混合後、１１００℃で２
時間仮焼後、再びボールミルで粉砕した。この粉末を電
子顕微鏡で観察したところ、二次粒子を含んだ平均粒径
約1.8μｍの不揃いの粒子から構成されていた。該粉末
を１ｔ／cm2の圧力下で直径３０mm、厚み３mmに成形
し、空気中で常圧下、１４００℃で２時間焼結した。Comparative Example 1 Commercially available powders of BaCO 3 , ZnO, Nb 2 O 5 and Ta 2 O 5 were blended so as to have a composition of Ba (Zn 0.33 Nb 0.14 Ta 0.53 ) O 3 , mixed with a ball mill and then mixed at 1100 ° C. In 2
After calcination for an hour, it was crushed again with a ball mill. When the powder was observed with an electron microscope, it was composed of irregular particles having an average particle diameter of about 1.8 μm including secondary particles. The powder was molded under a pressure of 1 t / cm 2 to a diameter of 30 mm and a thickness of 3 mm, and was sintered in air at 1400 ° C. for 2 hours under normal pressure.
上記実施例１、比較例１について、焼結体の焼結密度、
誘電率及び誘電損失を測定した結果を第１表に示す。For the above-mentioned Example 1 and Comparative Example 1, the sintered density of the sintered body,
Table 1 shows the measurement results of the dielectric constant and the dielectric loss.
上記のデータから明らかなように、本発明の製造方法に
より調製した粉末を用いた焼結体は、従来法により得ら
れた焼結体よりＱ値、εr及び焼結密度の点で優れてい
ることは明らかである。 As is apparent from the above data, the sintered body using the powder prepared by the manufacturing method of the present invention is superior to the sintered body obtained by the conventional method in terms of Q value, ε r and sintered density. It is clear that
また、Ｘ線回析法により上記実施例１、比較例１の仮焼
粉末の組成変動を測定した結果、本発明の製造方法によ
る粉末は組成変動が少なく、均密な粉体であるこが分っ
た。In addition, as a result of measuring the compositional variation of the calcined powders of the above-mentioned Example 1 and Comparative Example 1 by the X-ray diffraction method, it was found that the powder produced by the production method of the present invention had a small compositional variation and was a dense powder. It was.
本発明の製造方法によれば、ＢＺＮＴの原料成分のうち
バリウムとニオブ及びタンタルとを共沈させることがな
いので、ニオブ及びタンタル原料として、工業的に安価
なフッ化ニオブ水溶液及びフッ化タンタル水溶液が使用
でき、従って、安価な工業的生産の実用化を達成するこ
とができる。また、ＢＺＮＴの構成成分の全部を共沈さ
せることなく、多重沈殿を生成させるため、これらの沈
殿は相互分散された状態となり、高嵩密度の易焼結性の
ものが得られる。更に、多重沈殿生成を行なうため、各
成分に適した沈殿剤の種類及び濃度を選択でき、目的組
成のＢＺＮＴが容易に得られる。そして、従来の乾式法
におけるような組成成分の不均一性のない、高密度で均
一なＢＺＮＴが容易に得られる。According to the production method of the present invention, barium, niobium, and tantalum are not coprecipitated among the raw material components of BZNT. Therefore, as a niobium and tantalum raw material, an industrially inexpensive niobium fluoride aqueous solution and tantalum fluoride aqueous solution are used. Can be used, and thus a low-cost industrial production can be achieved. In addition, since multiple precipitates are generated without coprecipitating all the constituent components of BZNT, these precipitates are in a mutually dispersed state, and a highly bulky and easily sinterable product is obtained. Furthermore, since multiple precipitations are generated, the type and concentration of the precipitating agent suitable for each component can be selected, and BZNT having the target composition can be easily obtained. Further, it is possible to easily obtain a high density and uniform BZNT without the nonuniformity of the composition components as in the conventional dry method.
第１図（Ａ）〜（Ｄ）は、それぞれ本発明の製造方法を
実施する場合の具体的な沈殿形成の順序を示した説明図
である。FIGS. 1 (A) to (D) are explanatory views showing a specific order of precipitation formation when the production method of the present invention is carried out.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 古澤 孝幸 福岡県大牟田市歴木1626 平野寮 (72)発明者 多木 宏光 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (56)参考文献 特開 昭62−143859（ＪＰ，Ａ) 特開 昭62−3004（ＪＰ，Ａ) 特開 昭62−3005（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takayuki Furusawa 1626 Hirano Dormitory, Omuta City, Fukuoka Prefecture (72) Inventor Hiromitsu Taki 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References Kai 62-143859 (JP, A) JP 62-3004 (JP, A) JP 62-3005 (JP, A)
Claims (1)
Ｏ５ （但し、0.6≦ｘ≦2.0、０＜ｙ＜１の範囲である。） におけるＢａ／（Ｚｎ＋Ｎｂ＋Ｔａ）のモル比が1.0近
傍の組成を有するＢＺＮＴ系強誘電体を製造するに際
し、バリウム化合物水溶液、亜鉛化合物水溶液，フッ化
ニオブ水溶液及びフッ化タンタル水溶液を調製し、これ
ら４種の水溶液とするかあるいは亜鉛化合物水溶液をバ
リウム化合物水溶液、フッ化ニオブ水溶液、フッ化タン
タル水溶液またはフッ化ニオブとフッ化タンタルの混合
水溶液のいずれかに混合して３種または２種の水溶液と
し、それらの水溶液と過剰の沈殿形成液とを均一に混合
することによりニオブ化合物及びタンタル化合物を逐次
沈殿させるかまたは共沈させ、その後フッ素イオンを除
去し、更にその後、ニオブ化合物及びタンタル化合物沈
殿物の存在下でバリウム化合物を含む水溶液と過剰の沈
殿形成液とを均一に混合して沈殿物を形成させ、亜鉛化
合物を含む水溶液と過剰の沈殿形成液との均一混合をニ
オブ化合物沈殿物またはタンタル化合物沈殿物の形成
前、ニオブ化合物沈殿物またはタンタル化合物沈殿物の
形成と同時、フッ素イオンの除去前、バリウム化合物沈
殿物の形成前、バリウム化合物沈殿物の形成と同時又は
バリウム化合物沈殿物の形成後の任意の段階で実施して
全成分の均密沈殿物を形成し、該沈殿物を５００〜１２
００℃で仮焼した後、成形物を空気中又は酸素雰囲気
中、１０００〜１６００℃で焼結させるか、又は不活性
雰囲気で熱間静水圧加圧により高密度化し、更に大気中
で焼結させることを特徴とする高密度ＢＺＮＴ系強誘電
体セラミックの製造方法。1. A composition formula 3BaO · xZnO · (1-y ) Nb 2 O 5 · yTa 2
In producing a BZNT-based ferroelectric having a composition in which the molar ratio of Ba / (Zn + Nb + Ta) in O 5 (where 0.6 ≦ x ≦ 2.0 and 0 <y <1) is near 1.0, a barium compound is used. An aqueous solution, a zinc compound aqueous solution, a niobium fluoride aqueous solution, and a tantalum fluoride aqueous solution are prepared, and these four types of aqueous solutions are prepared, or the zinc compound aqueous solution is used as a barium compound aqueous solution, a niobium fluoride aqueous solution, a tantalum fluoride aqueous solution, or niobium fluoride aqueous solution. A niobium compound and a tantalum compound are successively precipitated by mixing with any one of the mixed aqueous solutions of tantalum fluoride to form three or two kinds of aqueous solutions, and uniformly mixing these aqueous solutions with an excess precipitation-forming solution, or Coprecipitation followed by removal of fluoride ions followed by flash in the presence of niobium and tantalum compound precipitates. The aqueous solution containing the zinc compound and the excess precipitation-forming liquid are uniformly mixed to form a precipitate, and the aqueous solution containing the zinc compound and the excess precipitation-forming liquid are uniformly mixed to form a niobium compound precipitate or a tantalum compound precipitate. Any before formation, at the same time as formation of the niobium compound precipitate or tantalum compound precipitate, before removal of fluoride ions, before formation of the barium compound precipitate, simultaneously with formation of the barium compound precipitate or after formation of the barium compound precipitate Performed in stages to form a homogenous precipitate of all components, which precipitate is 500-12
After calcination at 00 ° C, the molded product is sintered at 1000 to 1600 ° C in air or oxygen atmosphere, or densified by hot isostatic pressing in an inert atmosphere, and further sintered in air. A method for producing a high-density BZNT-based ferroelectric ceramic, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61168793A JPH0643266B2 (en) | 1986-07-17 | 1986-07-17 | High-density BZNT-based ferroelectric ceramic manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61168793A JPH0643266B2 (en) | 1986-07-17 | 1986-07-17 | High-density BZNT-based ferroelectric ceramic manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6325265A JPS6325265A (en) | 1988-02-02 |
| JPH0643266B2 true JPH0643266B2 (en) | 1994-06-08 |
Family
ID=15874576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61168793A Expired - Lifetime JPH0643266B2 (en) | 1986-07-17 | 1986-07-17 | High-density BZNT-based ferroelectric ceramic manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643266B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5722299A (en) * | 1994-06-30 | 1998-03-03 | Fuji Kiko Co., Ltd. | Adjustable steering column assembly for a vehicle |
| DE102011010346B4 (en) * | 2011-02-04 | 2014-11-20 | H.C. Starck Gmbh | Process for the production of a homogeneous multi-substance system, ceramic material based on the homogeneous multi-substance system and its use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS623004A (en) * | 1985-06-28 | 1987-01-09 | Ube Ind Ltd | Production of easily sintering perovskite raw material powder by wet method |
| JPS623005A (en) * | 1985-06-28 | 1987-01-09 | Ube Ind Ltd | Production of easily sintering perovskite raw material powder by powder dispersing |
| JPS62143859A (en) * | 1985-12-17 | 1987-06-27 | 科学技術庁無機材質研究所長 | Manufacture of high density ba(zn1/3(ta and/or nb)2/3)03 perovskite ceramics |
-
1986
- 1986-07-17 JP JP61168793A patent/JPH0643266B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6325265A (en) | 1988-02-02 |
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