JPS58172233A - Manufacture of spherical fine zirconia particle - Google Patents
Manufacture of spherical fine zirconia particleInfo
- Publication number
- JPS58172233A JPS58172233A JP57054544A JP5454482A JPS58172233A JP S58172233 A JPS58172233 A JP S58172233A JP 57054544 A JP57054544 A JP 57054544A JP 5454482 A JP5454482 A JP 5454482A JP S58172233 A JPS58172233 A JP S58172233A
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- fine particles
- particles
- spherical fine
- carbonaceous
- 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】
ジルコニア系固溶体の焼結多結晶体は耐火物のみならず
゛、最近は緻密なセラミックスとして酸素センサー、酸
素ポンプ等の機能材料や高強度高靭性構造材料として著
しい発展の途上にある。これらは何れも微細、均一な粒
径の、緻密な微構造の固溶体多結晶体であり、これを製
造するためには。[Detailed Description of the Invention] Sintered polycrystals of zirconia-based solid solutions are not only used as refractories, but have recently seen remarkable development as dense ceramics, functional materials for oxygen sensors, oxygen pumps, etc., and high-strength, high-toughness structural materials. It's on its way. All of these are solid solution polycrystals with fine, uniform particle sizes and dense microstructures, and in order to manufacture them.
微細、均一な粒径の微粒子を出発原料とすることが不可
欠である。また一般に出発微粉末は成形時緊密均−に粉
末充填されることが必要で、これによって焼結を促進す
るとともに変形を防ぎ２寸法の高精度が保たれるのであ
るが、このためには粉末は孤立した球状の粒子から成っ
ていることが望まれる。殆んどのジルコニア系微粉末は
乾燥と仮焼処理によって得られ、微粒子である程この乾
燥と仮焼の段階で相互連結、凝集を起し、成形物の不均
一性の原因となる。本発明は炭素質をジルコニア系微粒
子間に介在させて、熱処理を行ない。It is essential to use fine particles with a uniform particle size as a starting material. In addition, it is generally necessary to pack the starting fine powder tightly and evenly during molding, which promotes sintering, prevents deformation, and maintains high precision in two dimensions. It is desired that the particles consist of isolated spherical particles. Most of the zirconia-based fine powders are obtained by drying and calcining, and the finer the particles, the more they become interconnected and aggregate during the drying and calcining stages, causing non-uniformity of the molded product. In the present invention, carbonaceous material is interposed between zirconia fine particles and heat treatment is performed.
ジルコニア系微粒子を孤立化１球形化させることを重要
な要点とする。ここで炭素質とは有機高分子から完全な
炭素までの種々の段階の物質で何れも酸化燃焼後、気化
消滅するものを指すこととする。マタシルコニア系微粒
子とはジルコニアを主体とした化合物、および他の化合
物との固溶体。The important point is to isolate the zirconia-based fine particles into a single sphere. Here, the term "carbonaceous" refers to substances in various stages from organic polymers to complete carbon, all of which vaporize and disappear after oxidative combustion. Matasirconia-based fine particles are compounds mainly composed of zirconia and solid solutions with other compounds.
混合物などを総称する。A general term for mixtures, etc.
本発明ノーツは全く特異な方法によってジルコニウム水
酸化物の微粒子を孤立化、乾燥、仮焼することを特徴と
するものである。すなわち、ジルコニウムの塩水溶液９
例えば塩化ジルコニル（Ｚｒ０ＣＩ ２）の水溶液に適
量の過酸化水素およびジルコニウムを水酸化物とするに
十分量のアンモニア水、ならびにカラメル等炭素質の水
性高分子または微粒子を加え、この均一な混合液を加熱
濃縮。The notes of the present invention are characterized by isolating, drying, and calcining fine particles of zirconium hydroxide using a completely unique method. That is, zirconium salt aqueous solution 9
For example, an appropriate amount of hydrogen peroxide, a sufficient amount of ammonia water to make zirconium hydroxide, and a carbonaceous aqueous polymer or fine particles such as caramel are added to an aqueous solution of zirconyl chloride (Zr0CI2), and this homogeneous mixture is made. Heat concentration.
乾燥固化させ、これを４００’Ｃ程度で仮焼して水酸化
ジルコニウムをジルコニアに変え共存するアンモニア化
合物は熱分解により、また炭素質は酸化燃焼によって除
去することを特徴とするものである。It is characterized in that it is dried and solidified, then calcined at about 400'C to change the zirconium hydroxide to zirconia, and the coexisting ammonia compounds are removed by thermal decomposition and carbonaceous substances are removed by oxidative combustion.
加える過酸化水素の量は溶液中に含まれるジルコニウム
と等モル程度以上が適当であるが、それ以下でも効果が
ある。アンモニア水は溶液中のジルコニウムを沈澱させ
るに十分量が必要である。The amount of hydrogen peroxide to be added is suitably at least equimolar to the amount of zirconium contained in the solution, but it is effective even if the amount is less than that. A sufficient amount of ammonia water is required to precipitate the zirconium in the solution.
過酸化水素の存在は生成する水酸化物の相互連結を阻止
し、孤立化、超微粒子化させることが判明した。従って
添加の順序は過酸化水素を加えた後アンモニア水を添加
するのが効果的である。カラメル等水性有機高分子また
は微粒子は水酸化ジルコニウムの乾燥又は仮焼時に孤立
微粒子が相互連結するのを空間的に阻止するもので、こ
れによって仮焼後、成形型内に充填容易な孤立球状微粒
子から成る微粉末が得られる。It has been found that the presence of hydrogen peroxide prevents the interconnection of the generated hydroxides, causing them to become isolated and become ultrafine particles. Therefore, it is effective to add hydrogen peroxide and then add aqueous ammonia. Aqueous organic polymers or fine particles such as caramel spatially prevent isolated fine particles from interconnecting when drying or calcining zirconium hydroxide, thereby forming isolated spherical fine particles that can be easily filled into a mold after calcining. A fine powder consisting of
本発明は勿論純粋なジルコニア粉末の製造に限定される
ものではない。上記方法をイ、ソトリウム。The invention is of course not limited to the production of pure zirconia powder. Using the above method, Sotrium.
カルシウム、あるいはその他のイオンの共存下で実施す
れば、仮焼後、同様に孤立した固溶体化合物または混合
酸化物の球状微粒子粉末を得ることができる。When carried out in the coexistence of calcium or other ions, spherical fine particle powders of isolated solid solution compounds or mixed oxides can similarly be obtained after calcination.
本発明は水酸化物の孤立化のみに限定されるものではな
い。本発明はジルコニウム化合物の孤立微粒子２例えば
塩化ジルコニルを加熱加水分解して生成する水和ジルコ
ニア微粒子ゾルに適用できる。すなれちこれらの微粒子
を炭素質を介在させて互に孤立分散した状態とし、仮焼
の段階でジルコニア系微粒子を緻密球形化させると同時
に炭素質を酸化燃焼させて除去する方法を含む。The present invention is not limited to isolation of hydroxide. The present invention can be applied to a hydrated zirconia fine particle sol produced by heating and hydrolyzing isolated fine particles 2 of a zirconium compound, such as zirconyl chloride. In other words, it includes a method in which these fine particles are made to be isolated and dispersed with carbonaceous matter interposed therebetween, and the zirconia-based fine particles are made into dense spherical shapes in the calcining stage, and at the same time, the carbonaceous matter is oxidized and burned to be removed.
また本発明の最も重要な特徴は水蒸気の作用に関する点
であり、炭素質の酸化燃焼前に水蒸気の作用下で３００
°Ｃ以上に熱処理する工程を加える方法を含む。この水
蒸気処理によってジルコニア系微粒子の球形化は一層促
瘉され、比較的低温でほとんど理想的な球形微粒子を得
ることが可能となる。The most important feature of the present invention is that it is related to the action of water vapor.
This includes a method of adding a step of heat treatment to a temperature of .degree. C. or higher. This steam treatment further promotes spherical formation of the zirconia-based fine particles, making it possible to obtain almost ideal spherical fine particles at a relatively low temperature.
〔実施例１〕
試薬塩化ジルコニル（ＺｒＯＣｌ２・８Ｈ２０） ９ｆ
、 蒸留水４００ｍ１に過酸化水素水（３１％）２
０ｍｌ を加え、これに稀アンモニア水（２，８％）
をｇＱｍｌ加え９次いでカラメル液（砂糖８０Ｆりを加
え均一に混合し、加熱、濃縮、乾燥し、黒色固体を得た
。これを空気中４００°Ｃ，２時間熱処理したところ、
白色の多孔塊状物を得、これは容易に指頭で崩解し微粉
状となった。これは電子顕微鏡で観察すると直径８０Ａ
。[Example 1] Reagent zirconyl chloride (ZrOCl2.8H20) 9f
, Hydrogen peroxide solution (31%) in 400ml of distilled water2
Add 0ml and add dilute ammonia water (2.8%) to this.
Added 9gQml of caramel liquid (80F sugar) and mixed uniformly, heated, concentrated and dried to obtain a black solid.This was heat treated in air at 400°C for 2 hours,
A white porous mass was obtained, which easily disintegrated on the tip of a finger into a fine powder. When observed with an electron microscope, it has a diameter of 80A.
.
のほぼ球状となった互に孤立した超微粒子から成ってい
た。Ｘ線回折によればこれは正方型のジルコニア微結晶
であった。It consisted of isolated ultrafine particles that were almost spherical. According to X-ray diffraction, this was a square zirconia microcrystal.
〔実施例２〕
試薬塩化ジルコニル（Ｚ ｒＱＣＩ ２・８Ｈ２０）約
２Ｏｆを蒸留水３００ｍ１に溶解して約０．２ｍＯ１／
ｌの溶液とし、イオン交換樹脂（アンバーライトＩＲ−
４５）で処理して溶液のＰＨを２．０とし、この溶液を
還流冷却器付フラスコ中で４０時間煮沸して水和ジルコ
ニア微粒子の懸濁液を得た。次いでこれにカラメル液（
砂糖１００ｇ）を加え均一に混合し、加熱、濃縮、乾燥
し、黒色固体を得た。これを空気中６００”Ｃ，２時間
熱処理したところ白色の多孔塊状物を得、これは容易に
指で崩れ微粉状となった。これは電子顕微鏡によれば直
径約１ｏｏｏＡの球状の孤立微粒子から成っていた。Ｘ
線回折によれば単斜型のジルコニア結晶であった。[Example 2] Approximately 2Of reagent zirconyl chloride (Z rQCI 2.8H20) was dissolved in 300 ml of distilled water to a concentration of approximately 0.2 mO1/
solution of ion exchange resin (Amberlite IR-
45) to adjust the pH of the solution to 2.0, and this solution was boiled for 40 hours in a flask equipped with a reflux condenser to obtain a suspension of hydrated zirconia fine particles. Next, add caramel liquid (
100 g of sugar was added and mixed uniformly, heated, concentrated and dried to obtain a black solid. When this was heat-treated in air at 600"C for 2 hours, a white porous mass was obtained, which easily crumbled with fingers and became a fine powder. According to an electron microscope, this was composed of spherical isolated fine particles with a diameter of about 100A. It was.X
According to line diffraction, it was a monoclinic zirconia crystal.
〔実施例３〕
実施例２と同様にして黒色固体とした後これを摩砕して
粉状とし、アルゴン中で６００°Ｃに加熱し。[Example 3] A black solid was obtained in the same manner as in Example 2, and this was ground into powder and heated to 600°C in argon.
次いで雰囲気を水蒸気に変えて１時間保持、さらに空気
を導入して炭素質物質を酸化燃焼させて白色粉末を得た
。これはＸ線的には単斜ジルコニアであり、電子顕微鏡
によれば実施例２に比較して一層理想球形に近い微粒子
から成っていた。Next, the atmosphere was changed to water vapor and maintained for 1 hour, and then air was introduced to oxidize and burn the carbonaceous material to obtain a white powder. This was confirmed by X-rays to be monoclinic zirconia, and by electron microscopy, it was found to consist of fine particles having a shape closer to an ideal sphere than in Example 2.
〔実施例４〕
試薬塩化ジルコニル（ＺｒＯＣＩ□・８Ｈ２０）約２０
９および塩化イツトリウム（ＹＣＩｌｌ）約０．４ｆを
蒸留水３００ｍ１に溶解し、これにカラメル液（砂糖１
００ ｆ ）を加えた液をＡとし、別に２Ｎアンモニア
水１００ｍ１とカラメル液（砂糖５０ｆ）の混合液をＢ
とし、ＡとＢを混合後、これを加熱濃縮、乾燥し、黒色
固体を得た。これを摩砕後アルゴン中６００°Ｃに加熱
し。[Example 4] Reagent zirconyl chloride (ZrOCI□・8H20) approx. 20
9 and about 0.4 f of yttrium chloride (YCIll) were dissolved in 300 ml of distilled water, and added with caramel liquid (sugar 1
00f) was added to the liquid as A, and a separate mixture of 100ml of 2N ammonia water and caramel liquid (50f of sugar) was B.
After mixing A and B, this was concentrated and dried by heating to obtain a black solid. After grinding, this was heated to 600°C in argon.
次いで雰囲気を水蒸気に変えて１時間保持、さらに空気
を導入して炭素質物質を酸化燃焼させて白色粉末を得た
。これはＸ線的には正方型ジルコニア固溶体であり、電
子顕微鏡によれば約１０ＯＡの球状微粒子であった。Next, the atmosphere was changed to water vapor and maintained for 1 hour, and then air was introduced to oxidize and burn the carbonaceous material to obtain a white powder. This was a square zirconia solid solution according to X-rays, and was found to be spherical fine particles of about 10 OA according to an electron microscope.
手続補正書（方式）
１、事件の表示 昭ｆ１１ｍ５７年特許願第０５４５４
４号２、発明の名称
ジルコニア系球状微粒子粉末
３ 補正する者
事件との関係 特許出願人
住所 愛知県愛知郡長久手町大字熊張宇早稲田５６
昭和５７年７月９日
５、補正の対象
願書及び明細書
６、補正の内容
別紙の通り（内容に変更なし）Procedural amendment (method) 1. Indication of case Patent application No. 05454, filed in 1982.
No. 4 No. 2, Name of the invention Zirconia-based spherical fine particle powder 3 Relationship with the case of the person making the amendment Patent applicant address 56 Kumahari Uwaseda, Nagakute-machi, Aichi-gun, Aichi Prefecture July 9, 1981 5. Application and details to be amended Book 6, contents of amendment as per attached sheet (no change in contents)
Claims (1)
Ｈナラびに炭素質の水性高分子または微粒子を加え、こ
の混合液を加熱濃縮、乾燥固化させ、これを仮焼して不
要部分を分解、燃焼によって除去することを特徴とする
ジルコニア系球状微粒子粉末の製造方法。 ■ ジルコニア系微粒子を炭素質を介在させて互に孤立
分散した状態とし、非酸化性雰囲気下で４００”Ｃ以上
で熱処理を行ない９次いでこの炭素質を酸化燃焼させて
除去することを特徴とするジルコニア系球状微粒子粉末
の製造方法。 （３） ジルコニア系微粒子を炭素質を介在させて互
に孤立分散した状態とし、水蒸気の作用下で３００”Ｃ
以上に熱処理を行ない、しかる後この炭素質を酸化燃焼
させて除りすることを特徴とするジルコニア系球状微粒
子粉末の製造方法。[Claims] (1) H, O□, NH4O in the zirconium salt aqueous solution
A zirconia-based spherical fine particle powder characterized by adding a carbonaceous aqueous polymer or fine particles to H-oak, heating the mixture, concentrating it, drying and solidifying it, and calcining it to decompose and remove unnecessary parts by burning. manufacturing method. ■ The zirconia-based fine particles are isolated and dispersed with carbonaceous matter interposed between them, and then heat treated at 400"C or higher in a non-oxidizing atmosphere to oxidize and burn the carbonaceous matter to remove it. Method for producing zirconia-based spherical fine particles. (3) Zirconia-based fine particles are isolated and dispersed from each other with carbonaceous matter interposed therebetween, and heated to 300"C under the action of water vapor.
A method for producing zirconia-based spherical fine particle powder, which comprises performing the heat treatment as described above, and then oxidizing and burning the carbon to remove it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57054544A JPS58172233A (en) | 1982-03-31 | 1982-03-31 | Manufacture of spherical fine zirconia particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57054544A JPS58172233A (en) | 1982-03-31 | 1982-03-31 | Manufacture of spherical fine zirconia particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58172233A true JPS58172233A (en) | 1983-10-11 |
Family
ID=12973616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57054544A Pending JPS58172233A (en) | 1982-03-31 | 1982-03-31 | Manufacture of spherical fine zirconia particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58172233A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60176921A (en) * | 1984-02-22 | 1985-09-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of zirconia fine powder |
| WO1986005170A1 (en) * | 1985-03-05 | 1986-09-12 | Idemitsu Kosan Company Limited | Super-fine spherical particles of metal oxide and process for their preparation |
| US4719091A (en) * | 1986-07-01 | 1988-01-12 | Corning Glass Works | Preparation of mono-sized zirconia powders by forced hydrolysis |
| GB2204573B (en) * | 1987-03-31 | 1991-03-27 | Shinagawa Refractories Co | Spinning solution for producing zirconia fibers. |
| ES2190300A1 (en) * | 2000-02-04 | 2003-07-16 | Consejo Superior Investigacion | Production of stable tetragonal structure zirconium oxide powders comprises polycondensation of sol to form gel based on zirconyl chloride and ammonia |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55132626A (en) * | 1979-04-02 | 1980-10-15 | Takeda Chem Ind Ltd | Preparation of spherical particle |
| JPS56145118A (en) * | 1980-04-11 | 1981-11-11 | Agency Of Ind Science & Technol | Preparation of finely divided particles of zirconium oxide |
-
1982
- 1982-03-31 JP JP57054544A patent/JPS58172233A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55132626A (en) * | 1979-04-02 | 1980-10-15 | Takeda Chem Ind Ltd | Preparation of spherical particle |
| JPS56145118A (en) * | 1980-04-11 | 1981-11-11 | Agency Of Ind Science & Technol | Preparation of finely divided particles of zirconium oxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60176921A (en) * | 1984-02-22 | 1985-09-11 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of zirconia fine powder |
| JPH044978B2 (en) * | 1984-02-22 | 1992-01-30 | ||
| WO1986005170A1 (en) * | 1985-03-05 | 1986-09-12 | Idemitsu Kosan Company Limited | Super-fine spherical particles of metal oxide and process for their preparation |
| US4842832A (en) * | 1985-03-05 | 1989-06-27 | Idemitsu Kosan Company Limited | Ultra-fine spherical particles of metal oxide and a method for the preparation thereof |
| US4719091A (en) * | 1986-07-01 | 1988-01-12 | Corning Glass Works | Preparation of mono-sized zirconia powders by forced hydrolysis |
| GB2204573B (en) * | 1987-03-31 | 1991-03-27 | Shinagawa Refractories Co | Spinning solution for producing zirconia fibers. |
| ES2190300A1 (en) * | 2000-02-04 | 2003-07-16 | Consejo Superior Investigacion | Production of stable tetragonal structure zirconium oxide powders comprises polycondensation of sol to form gel based on zirconyl chloride and ammonia |
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