JPH05147943A - Production of thin stabilized zirconia film - Google Patents
Production of thin stabilized zirconia filmInfo
- Publication number
- JPH05147943A JPH05147943A JP3039154A JP3915491A JPH05147943A JP H05147943 A JPH05147943 A JP H05147943A JP 3039154 A JP3039154 A JP 3039154A JP 3915491 A JP3915491 A JP 3915491A JP H05147943 A JPH05147943 A JP H05147943A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- zirconium
- chloride
- substrate
- coprecipitate
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、安定化ジルコニア薄膜
の製造方法に関する。更に詳しくは、酸素センサ、固体
電解質型燃料電池などに用いられる安定化ジルコニア薄
膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a stabilized zirconia thin film. More specifically, it relates to a method for producing a stabilized zirconia thin film used in oxygen sensors, solid oxide fuel cells, and the like.
【０００２】[0002]
【従来の技術】ジルコニア薄膜(酸化ジルコニウム薄膜)
は、従来気相法、ゾル-ゲル法などにより製造されてい
る。2. Description of the Related Art Zirconia thin film (zirconium oxide thin film)
Has been conventionally produced by a vapor phase method, a sol-gel method, or the like.
【０００３】ジルコニアのプラズマ溶射またはスパッタ
リングなどによって行われる気相法では緻密な薄膜が得
難く、また組成の均質性にも乏しいという欠点がみられ
る。The gas phase method which is carried out by plasma spraying or sputtering of zirconia has the drawbacks that it is difficult to obtain a dense thin film and the composition is poor in homogeneity.
【０００４】また、金属アルコキシドを用いたゾル-ゲ
ル法(窯業協会誌第95巻第10号第942頁、1987年)では、
組成の均質性の点ではすぐれた薄膜が得られるが、乾
燥、焼成時にひび割れを生じ易く、また原料が非常に高
価であるという問題を有している。Further, in the sol-gel method using a metal alkoxide (Ceramics Industry Association, Vol. 95, No. 10, p. 942, 1987),
Although a thin film excellent in terms of compositional homogeneity can be obtained, it has a problem that cracks easily occur during drying and firing, and the raw material is very expensive.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、組成
が均質で、緻密な安定化ジルコニア薄膜を廉価に製造し
得る方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method capable of inexpensively producing a dense stabilized zirconia thin film having a uniform composition.
【０００６】[0006]
【課題を解決するための手段】かかる本発明の目的は、
塩化イットリウムを含有する塩化ジルコニウム水溶液と
アンモニア水とを同時に滴下して水酸化ジルコニウムと
水酸化イットリウムとを共沈させ、ロ別した共沈物の水
希釈液を加圧下に150〜200℃に加熱処理し、得られた立
方晶ジルコニア粒子のスラリーを分散処理してゾルを形
成させ、形成されたゾルを緻密質基板上にコーティング
後あるいは多孔質基板上でロ過してジルコニア粒子を堆
積させた後焼成し、安定化ジルコニア薄膜を製造するこ
とによって達成される。The object of the present invention is as follows.
An aqueous solution of zirconium chloride containing yttrium chloride and aqueous ammonia are simultaneously added dropwise to coprecipitate zirconium hydroxide and yttrium hydroxide, and the co-precipitated water-diluted solution is heated to 150 to 200 ° C under pressure. The resulting cubic zirconia particle slurry was dispersed to form a sol, and the formed sol was coated on a dense substrate or filtered on a porous substrate to deposit zirconia particles. This is achieved by post-baking to produce a stabilized zirconia thin film.
【０００７】塩化イットリウムを含有する塩化ジルコニ
ウム水溶液としては、ZrO2・Y2O3換算で塩化イットリウ
ムを約3〜10モル%、好ましくは8モル%含有するオキシ塩
化ジルコニウムを約0.03〜0.09モルの濃度で溶解させた
水溶液が用いられる。オキシ塩化ジルコニウムは、水溶
液中では塩化ジルコニウムに変換される。As the zirconium chloride aqueous solution containing yttrium chloride, zirconium oxychloride containing about 3 to 10 mol% of yttrium chloride, preferably 8 mol% in terms of ZrO 2 .Y 2 O 3 , and about 0.03 to 0.09 mol of zirconium oxychloride is contained. An aqueous solution dissolved at a concentration is used. Zirconium oxychloride is converted to zirconium chloride in aqueous solution.
【０００８】これとの中和反応は、塩化ジルコニウム水
溶液とアンモニア水とを同時に滴下することにより行わ
れる。The neutralization reaction with this is carried out by simultaneously dropping an aqueous zirconium chloride solution and aqueous ammonia.
【０００９】このような中和反応の結果、水酸化ジルコ
ニウムと水酸化イットリウムとが共沈する。共沈物は、
ロ別した後、水で約0.1〜1モル%、好ましくは約0.3〜0.
9モル%の濃度に希釈した上で用いられる。水による希釈
を行い、水の存在下で加圧加熱を行わないと、無定形の
ジルコニア粒子が得られ、所望の立方晶粒子が得られな
い。As a result of such a neutralization reaction, zirconium hydroxide and yttrium hydroxide coprecipitate. Coprecipitate
(B) After separating, about 0.1-1 mol% with water, preferably about 0.3-0.
It is used after diluting to a concentration of 9 mol%. Unless diluted with water and heated under pressure in the presence of water, amorphous zirconia particles are obtained and desired cubic crystal particles cannot be obtained.
【００１０】共沈物の水希釈液の加圧加熱は、ステンレ
ス鋼製などの耐圧容器内で約150〜200℃に約10〜48時間
加熱することによって行われ、Y2O3がZrO2に固溶した立
方晶ジルコニアが約100Å以下の粒子状で分散したスラ
リーがそこに得られる。Pressurization and heating of the water-diluted solution of the coprecipitate is carried out by heating in a pressure vessel such as stainless steel at about 150 to 200 ° C. for about 10 to 48 hours, and Y 2 O 3 is converted to ZrO 2 A cubic zirconia solid solution is dispersed in the form of particles having a particle size of about 100Å or less.
【００１１】この立方晶ジルコニア粒子のスラリーは、
そこに超音波を照射する方法などで更に分散処理するこ
とにより、解膠剤や分散剤を含まない、透明性の高いゾ
ルとして得られる。The slurry of cubic zirconia particles is
By subjecting it to further dispersion treatment by a method of irradiating with ultrasonic waves, a highly transparent sol containing no peptizer or dispersant can be obtained.
【００１２】得られたゾルは、緻密質基板上にコーティ
ング後焼成するか、あるいは多孔質基板上でロ過してジ
ルコニア粒子を堆積させた後焼成することにより、基質
上に安定化ジルコニア薄膜を形成させる。The sol thus obtained is coated on a dense substrate and then calcined, or filtered on a porous substrate to deposit zirconia particles and then calcined to form a stabilized zirconia thin film on the substrate. Let it form.
【００１３】緻密質基板としては、アルミナ基板などの
セラミックス基板が用いられ、そこへのゾルのコーティ
ングは、浸漬、吹き付け、刷毛塗りなどの各種手段で行
われる。それの焼成は、約1100〜1400℃で約1〜10時間
行われ、緻密質基板上に所望の膜厚の安定化ジルコニア
薄膜を形成させるために、必要に応じてコーティングお
よび焼成の一連の工程が複数回くり返して行われる。As the dense substrate, a ceramic substrate such as an alumina substrate is used, and the sol coating is performed by various means such as dipping, spraying or brush coating. The baking thereof is performed at about 1100-1400 ° C. for about 1-10 hours, and if necessary, a series of coating and baking steps are performed to form a stabilized zirconia thin film having a desired film thickness on a dense substrate. Is repeated multiple times.
【００１４】また、多孔質基板としては、やはりアルミ
ナ基板などのセラミックス基板であって、平均細孔径が
約0.2〜1μm程度の多孔質体が用いられる。そこにゾル
を注いでロ過し、所望の厚さのジルコニア粒子を堆積さ
せた後、上記の如き焼成条件での焼成が行われ、安定化
ジルコニア薄膜を多孔質基板上に形成させる。As the porous substrate, a ceramic substrate such as an alumina substrate having a mean pore size of about 0.2 to 1 μm is used. After pouring the sol therein and filtering to deposit zirconia particles having a desired thickness, the zirconia thin film is fired under the firing conditions as described above to form a stabilized zirconia thin film on the porous substrate.
【００１５】[0015]
【発明の効果】本発明方法により、次のような効果が奏
せられる。 (1)共沈物を水の存在下で加圧加熱することにより、立
方晶のジルコニア粒子のスラリーが生成する。相転移時
の体積変化などによるひび割れなどを考慮すると、立方
晶粒子が好ましい。 (2)この立方晶ジルコニア粒子は、約100Å以下の粒径で
均一に分散したスラリーを形成している。粒子が均一に
分散していないスラリーを用いた場合には、異常粒成長
などがみられる。 (3)SEM、EPMAで分析した限りでは、組成が均質にして緻
密な安定化ジルコニア薄膜が形成されている。 (4)廉価なオキシ塩化ジルコニウムが用いられているた
め、コスト的に有利に安定化ジルコニア薄膜を製造する
ことができる。The method of the present invention has the following effects. (1) By heating the coprecipitate under pressure in the presence of water, a slurry of cubic zirconia particles is produced. Cubic grains are preferable in view of cracking due to volume change at the phase transition. (2) The cubic zirconia particles form a slurry having a particle size of about 100 Å or less and uniformly dispersed. When using a slurry in which particles are not uniformly dispersed, abnormal grain growth and the like are observed. (3) As far as it is analyzed by SEM and EPMA, a stabilized stabilized zirconia thin film having a uniform composition is formed. (4) Since inexpensive zirconium oxychloride is used, the stabilized zirconia thin film can be manufactured cost effectively.
【００１６】[0016]
【実施例】次に、実施例について本発明を説明する。EXAMPLES The present invention will now be described with reference to examples.
【００１７】実施例１ 塩化イットリウムをYとしてZrに対して8モル%含有する
塩化ジルコニウム水溶液[オキシ塩化ジルコニウムを水
に溶解させたもの](濃度0.06モル)500mlとアンモニア水
(濃度0.5重量%)500mlとを、撹拌しながら同時に滴下し
て、水酸化ジルコニウムと水酸化イットリウムとを共沈
させた。Example 1 500 ml of an aqueous zirconium chloride solution containing yttrium chloride as Y and 8 mol% with respect to Zr [zirconium oxychloride dissolved in water] (concentration 0.06 mol) and ammonia water.
500 ml (concentration 0.5% by weight) was simultaneously added dropwise with stirring to coprecipitate zirconium hydroxide and yttrium hydroxide.
【００１８】得られた共沈物をロ過、水洗後、水で0.6
モル濃度に希釈し、この水希釈液をステンレス鋼製耐圧
容器内で180℃、24時間の加熱処理を施し、粒径約30〜7
0Åの立方晶ジルコニア粒子をスラリー状態で形成させ
た。このジルコニア粒子が立方晶であることは、X線回
析により確認された。その後、このスラリーに超音波を
照射することにより、解膠剤や分散剤を含まない、透明
性の高いゾルを調製した。The coprecipitate thus obtained was filtered, washed with water, and then washed with water to a volume of 0.6.
Dilute to a molar concentration and subject this water-diluted liquid to heat treatment in a stainless steel pressure vessel at 180 ° C for 24 hours to give a particle size of approximately 30-7.
0Å cubic zirconia particles were formed in a slurry state. It was confirmed by X-ray diffraction that the zirconia particles were cubic crystals. Then, the slurry was irradiated with ultrasonic waves to prepare a highly transparent sol containing no peptizer or dispersant.
【００１９】このゾル中に緻密質アルミナ基板をディッ
プコーティング後、1250℃で2時間焼成した。このよう
なディップコーティングおよび焼成する操作を5回くり
返し、膜厚1μmの緻密な安定化ジルコニア薄膜を基板上
に形成させた。A dense alumina substrate was dip-coated in this sol and then baked at 1250 ° C. for 2 hours. The operations of dip coating and firing were repeated 5 times to form a dense stabilized zirconia thin film having a film thickness of 1 μm on the substrate.
【００２０】実施例２ ロートの中に円板状の多孔質アルミナ基板(平均細孔径
0.2μm)を設置してロ過面を形成させ、そこに実施例１
のゾルを注いでロ過し、ジルコニア粒子を堆積させた。Example 2 A disk-shaped porous alumina substrate (average pore size) was placed in a funnel.
0.2 μm) was installed to form a filtration surface, and Example 1 was formed there.
Was poured and filtered to deposit zirconia particles.
【００２１】その後、多孔質アルミナ基板部分を取り出
し、1250℃で2時間焼成し、基板上に安定化ジルコニア
薄膜を形成させた。After that, the porous alumina substrate portion was taken out and baked at 1250 ° C. for 2 hours to form a stabilized zirconia thin film on the substrate.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年３月２９日[Submission date] March 29, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】[0009]
【課題を解決するための手段】かかる本発明の目的は、
アルキル(メタ)アクリレートと一般式[Ｉ]CH2＝CR1COOR
2またはCH2＝CR1COO(CH2)nOR2(ここで、R1は水素原子ま
たはメチル基であり、R2はジシクロペンテニル基であ
り、nは1または2である)で表わされるジシクロペンテニ
ル(メタ)アクリレートまたはジシクロペンテニルオキシ
アルキル(メタ)アクリレートとの共重合体および一般式
[II]CH2＝C(CH3)CO(OCH2CHR3)mOCOC(CH3)＝CH2(ここ
で、R3は水素原子またはメチル基であり、mは1〜10の整
数である)で表わされるジメタクリレート化合物を含有
する透明性アクリルゴム組成物によって達成される。The object of the present invention is as follows.
Alkyl (meth) acrylate and general formula [I] CH 2 ＝ CR 1 COOR
2 or CH 2 = CR 1 COO (CH 2 ) nOR 2 (wherein R 1 is a hydrogen atom or a methyl group, R 2 is a dicyclopentenyl group, and n is 1 or 2 ) Copolymer with dicyclopentenyl (meth) acrylate or dicyclopentenyloxyalkyl (meth) acrylate and general formula
[II] CH 2 ═C (CH 3 ) CO (OCH 2 CHR 3 ) mOCOC (CH 3 ) ═CH 2 (wherein R 3 is a hydrogen atom or a methyl group, and m is an integer of 1 to 10) ) Is achieved by a transparent acrylic rubber composition containing a dimethacrylate compound.
Claims (4)
ニウム水溶液とアンモニア水とを同時に滴下して水酸化
ジルコニウムと水酸化イットリウムとを共沈させ、ロ別
した共沈物の水希釈液を加圧下に150〜200℃に加熱処理
し、得られた立方晶ジルコニア粒子のスラリーを分散処
理してゾルを形成させ、形成されたゾルを緻密質基板上
にコーティング後焼成することを特徴とする安定化ジル
コニア薄膜の製造方法。1. A zirconium chloride aqueous solution containing yttrium chloride and ammonia water are simultaneously added dropwise to coprecipitate zirconium hydroxide and yttrium hydroxide, and a co-precipitated aqueous dilution of 150 is added under pressure. Stabilized zirconia thin film, characterized in that it is heat-treated to ~ 200 ° C, the obtained slurry of cubic zirconia particles is dispersed to form a sol, and the formed sol is coated on a dense substrate and then baked. Manufacturing method.
ニウム水溶液として、塩化イットリウムを含有するオキ
シ塩化ジルコニウムの水溶液が用いられる請求項１記載
の安定化ジルコニア薄膜の製造方法。2. The method for producing a stabilized zirconia thin film according to claim 1, wherein an aqueous solution of zirconium oxychloride containing yttrium chloride is used as the aqueous zirconium chloride solution containing yttrium chloride.
ニウム水溶液とアンモニア水とを同時に滴下して水酸化
ジルコニウムと水酸化イットリウムとを共沈させ、ロ別
した共沈物の水希釈液を加圧下に150〜200℃に加熱処理
し、得られた立方晶ジルコニア粒子のスラリーを分散処
理してゾルを形成させ、形成されたゾルを多孔質基板上
でロ過してジルコニア粒子を堆積させた後焼成すること
を特徴とする安定化ジルコニア薄膜の製造方法。3. A zirconium chloride aqueous solution containing yttrium chloride and ammonia water are simultaneously added dropwise to coprecipitate zirconium hydroxide and yttrium hydroxide, and a co-precipitated water-diluted solution of 150 is added under pressure. Heat treatment to ~ 200 ℃, dispersion treatment of the obtained cubic zirconia particles slurry to form a sol, the formed sol is filtered on a porous substrate to deposit zirconia particles and then fired A method for producing a stabilized zirconia thin film, comprising:
ニウム水溶液として、塩化イットリウムを含有するオキ
シ塩化ジルコニウムの水溶液が用いられる請求項３記載
の安定化ジルコニア薄膜の製造方法。4. The method for producing a stabilized zirconia thin film according to claim 3, wherein an aqueous solution of zirconium oxychloride containing yttrium chloride is used as the aqueous zirconium chloride solution containing yttrium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3039154A JPH05147943A (en) | 1991-02-08 | 1991-02-08 | Production of thin stabilized zirconia film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3039154A JPH05147943A (en) | 1991-02-08 | 1991-02-08 | Production of thin stabilized zirconia film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05147943A true JPH05147943A (en) | 1993-06-15 |
Family
ID=12545193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3039154A Pending JPH05147943A (en) | 1991-02-08 | 1991-02-08 | Production of thin stabilized zirconia film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05147943A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012026579A1 (en) | 2010-08-26 | 2012-03-01 | エム・テクニック株式会社 | Method for manufacturing isolatable oxide microparticles or hydroxide microparticles |
| WO2021171745A1 (en) | 2020-02-27 | 2021-09-02 | ユニマテック株式会社 | Fluorine-containing alcohol composite |
-
1991
- 1991-02-08 JP JP3039154A patent/JPH05147943A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012026579A1 (en) | 2010-08-26 | 2012-03-01 | エム・テクニック株式会社 | Method for manufacturing isolatable oxide microparticles or hydroxide microparticles |
| US9005567B2 (en) | 2010-08-26 | 2015-04-14 | M. Technique Co., Ltd. | Method for producing isolatable oxide microparticles or hydroxide microparticles |
| WO2021171745A1 (en) | 2020-02-27 | 2021-09-02 | ユニマテック株式会社 | Fluorine-containing alcohol composite |
| KR20220141860A (en) | 2020-02-27 | 2022-10-20 | 유니마테크 가부시키가이샤 | Fluorinated Alcohol Composite |
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