JPS62138329A - Ultrathin sheet-like zirconia fine crystal powder and production thereof - Google Patents
Ultrathin sheet-like zirconia fine crystal powder and production thereofInfo
- Publication number
- JPS62138329A JPS62138329A JP60278527A JP27852785A JPS62138329A JP S62138329 A JPS62138329 A JP S62138329A JP 60278527 A JP60278527 A JP 60278527A JP 27852785 A JP27852785 A JP 27852785A JP S62138329 A JPS62138329 A JP S62138329A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- sheet
- fine crystal
- thin plate
- thin
- 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
Abstract
Description
【発明の詳細な説明】
本発明は本発明者によって既に出願された昭和６０年特
許願第１４７２３８号の追加の発明であり１発明の目的
、用途はほぼ同じであるが一層完全な超薄板状の厚さが
２００Å以下の特徴を持つ、正方または立方型ジルコニ
ア微結晶からなる粉末ならびにその製造方法に関するも
のである。Detailed Description of the Invention The present invention is an additional invention of Patent Application No. 147238 filed in 1985 by the present inventor. 1 The purpose and application of the invention are almost the same, but a more perfect ultra-thin plate is obtained. The present invention relates to a powder consisting of square or cubic zirconia microcrystals having a thickness of 200 Å or less, and a method for producing the same.
ジルコニア（Ｚｒ０２およびその固溶体をここではジル
コニアと総称する）は高耐火性酸化物でファインセラミ
ックスとして各柿の応用がある。一般にセラミックス用
ジルコニア原料粉末は微粒子のものが使用されるが、従
来薄板状ジルコニア微結晶からなる粉末は製造すること
ができず、使用もされていない。Zirconia (Zr02 and its solid solution are collectively referred to as zirconia here) is a highly refractory oxide and has various applications as fine ceramics. Generally, fine particles of zirconia raw material powder for ceramics are used, but powder made of thin plate-like zirconia microcrystals has not been able to be produced and has not been used.
本発明者は既に本発明者によって出願された発明をさら
に改良して一層完全な超薄板状ジルコニア微結晶粉末の
製造に成功した。すなわち、可溶性ジルコニウム塩をＺ
ｒとしてＯ０１〜１．０ダ・ａｔｏｍ／、ｊ。The present inventor further improved the invention already filed by the present inventor and succeeded in producing a more perfect ultra-thin plate-shaped zirconia microcrystalline powder. That is, the soluble zirconium salt is Z
r as O01~1.0 da atom/, j.
ＳＯ！−イオンを０．２〜２．ＯＬｊ−ｉｏｎ／ｌ含有
するＰＨ２，０以下の酸性水溶液を１００〜３００℃に
熱処理して先ず薄板状の含ＳＯキージルコニア微結晶を
生成させ。SO! - 0.2 to 2. An acidic aqueous solution containing OLj-ion/l and having a pH of 2.0 or lower is heat-treated at 100 to 300°C to first produce thin plate-shaped SO-containing zirconia microcrystals.
この微結晶をＰＨ８．０以上の塩基性水溶液中で熟成し
てＳＯ？−の大部分をＯＨ−で置換して薄板状含水ジル
コニア微結晶に変え、さらにこれを４００℃以上の温度
で仮焼することによって生成するものである。These microcrystals are aged in a basic aqueous solution with a pH of 8.0 or higher and SO? It is produced by replacing most of - with OH- to turn it into a thin plate-like hydrated zirconia microcrystal, and then calcining this at a temperature of 400°C or higher.
生成物は極めて特異なもので、 Ｙ２Ｏ３、Ｃａｂ、
ＭｇＯ等の安定化剤を添加しない場合でも、正方型また
は立方型の結晶格子を持つジルコニアそのもので。The products are very unique and include Y2O3, Cab,
Even when a stabilizer such as MgO is not added, zirconia itself has a square or cubic crystal lattice.
厚さが２００八以下の超薄片状微粒子からなる粉末であ
る。仮焼時に少量のＹ２Ｏ３、ＣａＯ、ＭｇＯ等が共存
すれば超薄板状ジルコニアの形状を保持したまま、正方
または立方型のジルコニア固溶体の微結晶粉末が得られ
る。また、加°熱熟成後の生成物の乾燥は極性有機溶媒
による水の置換あるいは凍結乾燥法による脱水によって
、一層凝集のない孤立化した超薄板状微粒子の粉末とな
る。It is a powder consisting of ultra-flake-like fine particles with a thickness of 200 mm or less. If a small amount of Y2O3, CaO, MgO, etc. coexists during calcination, a microcrystalline powder of a square or cubic zirconia solid solution can be obtained while maintaining the shape of ultra-thin plate-like zirconia. Further, the product after heating and aging is dried by replacing water with a polar organic solvent or dehydrating by freeze-drying, so that it becomes a powder of isolated ultra-thin plate-like fine particles without further agglomeration.
本発明の超薄板状ジルコニア微結晶粉末はその形状の特
徴によって、薄膜状もしくはシート状セラミックスの主
原料、あるいは副原料として好適である。ともに成形時
、平面方向に配列し易く。The ultra-thin plate-shaped zirconia microcrystalline powder of the present invention is suitable as a main raw material or an auxiliary raw material for thin film or sheet-shaped ceramics, depending on its shape characteristics. Both are easy to arrange in the plane direction during molding.
極めて薄い膜に対しても成形強度を与え、かつ焼成時面
積方向の収縮を軽減して亀裂や反りなどの発生を防ぐか
らである。またＰＺＴなどの圧電性セラミックスの原料
として特異な効果を持ち、ジルコニアと反応して生成す
る圧電結晶はジルコニアの薄板性によって配向し、その
性能を高める。またこれらの微粒子を懸濁したゾルまた
は泥漿は固体面への塗布によって面方向に配向するので
、セラミックスへの表面処理の他、一般にコーティング
材、塗料充填材、化粧品、防錆塗料、耐酸化耐熱塗料な
どとしても極めて価値の高いものである。This is because it provides molding strength even to extremely thin films, reduces shrinkage in the area direction during firing, and prevents cracks and warpage. It also has a unique effect as a raw material for piezoelectric ceramics such as PZT, and the piezoelectric crystals produced by reacting with zirconia are oriented due to the thin plate nature of zirconia, improving its performance. In addition, the sol or slurry in which these fine particles are suspended is oriented in the surface direction when applied to a solid surface, so in addition to surface treatment of ceramics, it is generally used for coating materials, paint fillers, cosmetics, anti-corrosion paints, and oxidation- and heat-resistant paints. It is also extremely valuable as a paint.
実施例 １
試薬炭酸ジルコニルを硫酸に溶解して硫酸ジルコニウム
水溶液を調製した。溶液濃度はＺｒとして約ｏ、 ２５
ｒｒｏ Ｉ ／ｌ 、Ｈ２Ｓｏ ａとして約０．５ｍ
ｏｌ ／ｌ ”℃、ＰＨは２．０以下であった。これを
テフロン容器中に密閉し、オートクレーブ中で２００℃
に２日間加熱処理を行い白色の析出沈澱物を得た。これ
はＺｒｌ原子当り５Ｏ２−を約０４モル含有する含硫酸
層状化合物である４ Ｎの稀薄アンモニア水中に懸濁し
て９７℃に２昼夜熟成した。Example 1 A zirconium sulfate aqueous solution was prepared by dissolving the reagent zirconyl carbonate in sulfuric acid. The solution concentration is approximately o, 25 as Zr.
rro I/l, about 0.5 m as H2So a
ol/l"℃ and pH were below 2.0. This was sealed in a Teflon container and heated at 200℃ in an autoclave.
A heat treatment was performed for 2 days to obtain a white precipitate. This is a sulfuric acid-containing layered compound containing about 04 moles of 5O2- per Zrl atom, and was suspended in 4N dilute ammonia water and aged at 97°C for two days and nights.
生成物を６００℃に仮焼した粉末のＸ線回折図形は正方
もしくは立方型ジルコニアのそれと完全に一致し、透過
電子顕微鏡観察によれば粒子は超薄板状で、板の厚さは
粉末Ｘ線回折図形の半価幅から求めた値とも一致して２
００Å以下であった。The X-ray diffraction pattern of the powder obtained by calcining the product at 600°C completely matches that of square or cubic zirconia, and according to transmission electron microscopy, the particles are ultra-thin plate-like, and the thickness of the plate is similar to that of powder X. It also agrees with the value obtained from the half width of the line diffraction pattern.
It was less than 00 Å.
手続補正書（自発）（ハ）
昭和６１年７り！７日
１、事件の表示
昭和６０年特許願第２７８５２７号
２、発明の名称
超薄板状ジルコニア微結晶粉末および製造方法３、補正
をする者
事件との関係 出願人
住所 愛知県愛知郡長久手町大字熊張字早稲田９５６
明細書の特許請求の範囲並びに発明の詳細な説明の欄（
１） 明細書の特許請求の範囲を下記のように訂正し
ます。Procedural amendment (voluntary) (c) July 1986! 7th 1, Display of the case 1985 Patent Application No. 278527 2 Name of the invention Ultra-thin zirconia microcrystalline powder and manufacturing method 3 Person making the amendment Relationship to the case Applicant address Nagakute-cho, Aichi-gun, Aichi Prefecture Oaza Kumahari character Waseda 956
The scope of claims and detailed description of the invention in the specification (
1) The scope of claims in the specification will be corrected as follows.
１）正方型または立方型の結晶格子を持ち、薄板状で厚
さが２００Å以下の超微粒子からなることを特徴とする
超薄板状ジルコニア微結晶粉末。1) Ultra-thin plate-like zirconia microcrystalline powder characterized by having a square or cubic crystal lattice and consisting of thin plate-like ultrafine particles with a thickness of 200 Å or less.
２）可溶性ジルコニウム塩をＺｒとして０．１〜１．５
ｆ −ａｔｏｍ ／ （１、ＳＯｊイオンを０．２〜３
．Ｏｆ−ｉｏｎ／ｌ含有するＰ Ｈ２，０以下の酸性水
溶液を１００〜３００℃に熱処理して先ず薄板状の含Ｓ
Ｏニージルコニア微結晶を生成させ、この微結晶をＰＨ
８，０以上の塩基性水溶液中で熟成してＳＯ２−４の大
部分をＯＨ−で置換して薄板状含水ジルコニア微結晶に
変え、さらにこれを４００℃以上の温度で仮焼すること
を特徴とする超薄板状ジルコニア徹結晶粉末の製造方法
。2) 0.1 to 1.5 soluble zirconium salt as Zr
f -atom / (1, SOj ion 0.2-3
．． A thin plate-like S-containing solution is first heat-treated at 100 to 300°C to form an acidic aqueous solution containing P H2.0 or less.
O-nee zirconia microcrystals are generated, and these microcrystals are PH
It is characterized by aging in a basic aqueous solution of 8.0 or higher, replacing most of SO2-4 with OH-, turning it into a thin plate-like hydrated zirconia microcrystal, and then calcining this at a temperature of 400°C or higher. A method for producing ultra-thin plate-like zirconia crystalline powder.
（Ｉｌ） 明細書の発明の詳細な説明を下記のように
訂正します。(Il) The detailed description of the invention in the specification is corrected as follows.
１）明細書第２頁第１３行目［Ｚｒとして０．１〜１．
Ｏｆ−ａｔｏｍ／ ｌ 、 Ｓｏニーイオンを０．２〜
２．Ｏｆ−ｉｏｎ／ｌＪを「Ｚｒとして０．１〜１．５
ダ・ａｔｏｍ／ ｌ 、 ＳＯニーイオンを０．２〜３
．０１−ｉｏｎ／６ Ｊに訂正。1) Specification, page 2, line 13 [Zr is 0.1 to 1.
Of-atom/l, So knee ion from 0.2 to
2. Of-ion/lJ is 0.1 to 1.5 as Zr.
da atom/l, SO knee ion 0.2-3
．． 01-ion/6 Corrected to J.
＋１） 明細書第４頁第１６行目ｒ６００’のを「７
００℃」に訂正。+1) Change r600' on page 4, line 16 of the specification to "7"
Corrected to 00℃.
Claims (1)
さが２００Å以下の超微粒子からなることを特徴とする
超薄板状ジルコニア微結晶粉末。 ２）可溶性ジルコニウム塩をＺｒとして０．１〜１．０
ｇ・ａｔｏｍ／ｌ、ＳＯ＾２＾−＿４イオンを０．２〜
２．０ｇ・ｉｏｎ／ｌ含有するＰＨ２．０以下の酸性水
溶液を１００〜３００℃に熱処理して先ず薄板状の含Ｓ
Ｏ＾２＾−＿４ジルコニア微結晶を生成させ、この微結
晶をＰＨ８．０以上の塩基性水溶液中で熟成してＳＯ＾
２＾−＿４の大部分をＯＨ＾−で置換して薄片状含水ジ
ルコニア微結晶に変え、さらにこれを４００℃の温度で
仮焼することを特徴とする超薄板状ジルコニア微結晶粉
末の製造方法。[Scope of Claims] 1) Ultra-thin plate-like zirconia microcrystalline powder characterized by having a square or cubic crystal lattice and consisting of thin plate-like ultrafine particles with a thickness of 200 Å or less. 2) 0.1 to 1.0 soluble zirconium salt as Zr
g・atom/l, SO^2^-_4 ion from 0.2
First, an acidic aqueous solution containing 2.0 g ion/l and having a pH of 2.0 or less is heat-treated at 100 to 300°C to form a thin plate-like S-containing solution.
O^2^-_4 zirconia microcrystals are generated, and these microcrystals are aged in a basic aqueous solution with a pH of 8.0 or higher to produce SO^
Production of ultra-thin zirconia microcrystal powder characterized by replacing most of 2^-_4 with OH^- to turn it into flaky hydrated zirconia microcrystals, which is further calcined at a temperature of 400°C. Method.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60278527A JPS62138329A (en) | 1985-12-10 | 1985-12-10 | Ultrathin sheet-like zirconia fine crystal powder and production thereof |
| DE86108797T DE3688153T2 (en) | 1985-07-03 | 1986-06-27 | Scale-like fine crystals of the zirconium oxide type and process for their production. |
| EP86108797A EP0207469B1 (en) | 1985-07-03 | 1986-06-27 | Flaky zirconia type fine crystals and method for producing them |
| KR1019860005359A KR920007598B1 (en) | 1985-07-03 | 1986-07-02 | Flaky zirconia type fine crystals and methods of producing the same |
| CN86104600A CN1008997B (en) | 1985-07-03 | 1986-07-02 | The production method of flaky zirconia type fine crystals |
| AU59718/86A AU591141B2 (en) | 1985-07-03 | 1986-07-03 | Flaky zirconia fine crystals and methods of producing them |
| US06/881,812 US4765970A (en) | 1985-07-03 | 1986-07-03 | Flaky zirconia type fine crystals and methods of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60278527A JPS62138329A (en) | 1985-12-10 | 1985-12-10 | Ultrathin sheet-like zirconia fine crystal powder and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62138329A true JPS62138329A (en) | 1987-06-22 |
Family
ID=17598516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60278527A Pending JPS62138329A (en) | 1985-07-03 | 1985-12-10 | Ultrathin sheet-like zirconia fine crystal powder and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62138329A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337472A2 (en) * | 1988-04-14 | 1989-10-18 | ISTITUTO GUIDO DONEGANI S.p.A. | Process for preparing submicronic powders of zirconium oxide stabilized with yttrium oxide |
| JPH0559749U (en) * | 1992-01-17 | 1993-08-06 | 橋本 幸夫 | Terminal connection device |
| JPH10330116A (en) * | 1996-12-20 | 1998-12-15 | Basf Ag | Zirconium dioxide of monoclinic system having huge surface area |
| JP2011057531A (en) * | 2009-09-14 | 2011-03-24 | Sumitomo Osaka Cement Co Ltd | Alkaline earth metal oxide-doped zirconia nanoparticle and method for producing the same |
-
1985
- 1985-12-10 JP JP60278527A patent/JPS62138329A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337472A2 (en) * | 1988-04-14 | 1989-10-18 | ISTITUTO GUIDO DONEGANI S.p.A. | Process for preparing submicronic powders of zirconium oxide stabilized with yttrium oxide |
| AU609280B2 (en) * | 1988-04-14 | 1991-04-26 | Istituto Guido Donegani S.P.A. | Process for preparing submicronic powders of zirconium oxide stabilized with yttrium oxide |
| JPH0559749U (en) * | 1992-01-17 | 1993-08-06 | 橋本 幸夫 | Terminal connection device |
| JPH10330116A (en) * | 1996-12-20 | 1998-12-15 | Basf Ag | Zirconium dioxide of monoclinic system having huge surface area |
| JP2011057531A (en) * | 2009-09-14 | 2011-03-24 | Sumitomo Osaka Cement Co Ltd | Alkaline earth metal oxide-doped zirconia nanoparticle and method for producing the same |
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