JPS6355119A - Production of alumina zirconia based fine powder - Google Patents
Production of alumina zirconia based fine powderInfo
- Publication number
- JPS6355119A JPS6355119A JP19806486A JP19806486A JPS6355119A JP S6355119 A JPS6355119 A JP S6355119A JP 19806486 A JP19806486 A JP 19806486A JP 19806486 A JP19806486 A JP 19806486A JP S6355119 A JPS6355119 A JP S6355119A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- solution
- fine powder
- precipitate
- salt
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- -1 aluminum ion Chemical class 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RQFMCJMUOOBOCQ-UHFFFAOYSA-N OO.[Zr] Chemical compound OO.[Zr] RQFMCJMUOOBOCQ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は構造用セラミックス林料の原料として用いられ
るアルミナジルコニア系微粉末の製法に関する。ジルコ
ニア粒子を分散させてなる高強度かつ高靭性のセラミッ
クスは分散強化セラミックフェア系微粉末が望まれてい
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing alumina-zirconia fine powder used as a raw material for structural ceramic materials. For high-strength and high-toughness ceramics made by dispersing zirconia particles, dispersion-strengthened ceramic fair-based fine powders are desired.
〈従来技術と問題点〉
アルミナジルコニア系微粉末の製法にはアルミナ〔Ａ）
２０３〕粉末とジルコニア（Ｚｒ０２）粉末もしくはＺ
ｒ０２にＣ！ａ、Ｍｇ及びＹなどの６価以上の原子価を
有する金属元素（安定化剤という）の少なくとも１２１
を含有する粉末をボールミル等の一般の混合方法により
混合する方法が一般的である（文献例： Ｎ、０１ａｕ
ｓｓ＋ｅｎ：Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ａｍｅｒ
ｉｃａｎＣｅｒａｍｉｃ ８ｏｃｉｅｔｙ、第５９巻、
４９〜５１頁、１９７６年）。<Conventional technology and problems> Alumina [A] is used in the production method of alumina-zirconia fine powder.
203] Powder and zirconia (Zr02) powder or Z
C on r02! At least 121 of a metal element having a valence of 6 or more (referred to as a stabilizer) such as a, Mg and Y
A common method is to mix powder containing N, 01au using a general mixing method such as a ball mill
ss+en: Journal of The Amer
icanCeramic 8ociety, Volume 59,
49-51, 1976).
しかしながら、この方法ではジルコニア粉末をアルミナ
中に均一に分散することが困難であり、機械的特性の優
れたアルミナジルコニア系セラミックス焼結体が得にく
い欠点があった。However, this method has the disadvantage that it is difficult to uniformly disperse zirconia powder in alumina, making it difficult to obtain an alumina-zirconia ceramic sintered body with excellent mechanical properties.
また、アルミニウムの塩とジルコニウムの塩トを含む酸
性水溶液あるいはさらにこれに安定化剤の塩を添加した
酸性水溶液とアンモニア、水酸化ナトリウムなどのアル
カリあるいは炭酸アンモニウム、シュウ酸塩などの塩と
を反応させて沈殿を形成させる方法すなわち共沈法が知
られている（なお、文献は見当らない）。この方法によ
れば溶液状態から沈殿を生成させるためにジルコニアが
かなり均一に分散させることができる。しかしながら、
この方法においては生成したジルコニウムの沈殿粒子（
たとえば水酸化ジルコニウム沈殿粒子〕同志が凝集粒子
を形成しやすく微細なジルコニア粒子を分散したアルミ
ナジルコニア系微粉末が得られにくい欠点があった。In addition, an acidic aqueous solution containing an aluminum salt and a zirconium salt, or an acidic aqueous solution to which a stabilizer salt is added, is reacted with an alkali such as ammonia or sodium hydroxide, or a salt such as ammonium carbonate or oxalate. A method is known in which a precipitate is formed by causing a precipitate to form, that is, a coprecipitation method (no literature has been found). According to this method, zirconia can be dispersed fairly uniformly to form a precipitate from a solution state. however,
In this method, the produced zirconium precipitate particles (
For example, zirconium hydroxide precipitated particles] comrades tend to form agglomerated particles, making it difficult to obtain alumina-zirconia fine powder in which fine zirconia particles are dispersed.
本発明は粒子の均一性に優れ、かつ、分散性のよいアル
ミナジルコニア系微粉末の↓遣方法を提供することを目
的とする。An object of the present invention is to provide a method for dispensing alumina-zirconia fine powder with excellent particle uniformity and good dispersibility.
く問題点を解決するための手段〉
本発明者らは先に、水酸化ジルコニウムはアルカリ中で
過酸化水素と錯体を形成して溶解し、このアルカリ水溶
液を加熱処理すると、配位子の過酸化水素を徐々に分解
−説離し、分散性のよいＺｒＯ２超微粒子が生成すると
の知見を得て出願したが（特願昭６０−１１１１７９号
及び％願昭６０−２６７２７７号）、本発明者らはこの
方法をアルミナジルコニア系微粉末の製造法に応用する
ことを考え、種々研究を重ねた結果、アルミニウムは両
性金属であり、アルカリ中でイオンとなり溶解すること
を見出し、この発明を完成するに至った。Means for Solving the Problems> The present inventors first discovered that zirconium hydroxide forms a complex with hydrogen peroxide and dissolves in an alkali, and when this alkaline aqueous solution is heat-treated, the ligands are superimposed. The present inventors filed an application based on the knowledge that hydrogen oxide can be gradually decomposed and dissociated to produce ZrO2 ultrafine particles with good dispersibility (Japanese Patent Application No. 111179/1982 and % Application No. 267277/1982). thought of applying this method to the production of alumina-zirconia fine powder, and after conducting various researches, discovered that aluminum is an amphoteric metal and dissolves as ions in an alkali. It's arrived.
すなわち、本発明はジルコニウム塩及びアルミニウム塩
の混合水漬液をアルカリ性にして、過酸化水素を加える
ことにより、ジルコニウムイオンの過酸化水素錯体とア
ルミニウムイオンとの混合液とし、つぎに、前記混合液
を温度８０〜２００℃で加熱したのち、水溶液の−を４
〜１０の範囲とすることによって沈殿を生成させ、該沈
殿を分離することを特徴とするアルミナジルコニア系微
粉末の製法である。That is, in the present invention, a mixed solution of a zirconium salt and an aluminum salt is made alkaline and hydrogen peroxide is added to obtain a mixed solution of a hydrogen peroxide complex of zirconium ions and aluminum ions. After heating at a temperature of 80 to 200℃, the - of the aqueous solution is reduced to 4.
This is a method for producing alumina-zirconia-based fine powder, which is characterized in that a precipitate is generated by adjusting the range of 10 to 10, and the precipitate is separated.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においてジルコニウム塩及びアルミニウム塩の塩
とは塩酸塩、硝酸塩、硫酸塩、酢酸塩などである。これ
らの金属成分濃度は特別な制限はないが、実用上０．１
〜１．０モル／ノ程度が適切である。In the present invention, zirconium salts and aluminum salts include hydrochloride, nitrate, sulfate, acetate, and the like. There is no particular limit to the concentration of these metal components, but in practice it is 0.1
~1.0 mol/no is appropriate.
アルカリ剤としては、ジルコニウムイオンの過酸化水素
錯体が溶解し始める水素イオン濃度ｐ）１１２以上を容
易に達成できるもので、しかも、加熱処理を施すに際し
揮発性でないものが望ましい。通常は水酸化す） ＩＪ
ウムまたは水酸化カリウムが適している。なお、この場
合において、アルカリ濃度を高めてたとえば−＞１３．
５にすルト、ジルコニウムイオンの過酸化水素錯体の分
解、脱離速度が著しく遅くなるので分散性にすぐれた微
粉末を農造することができる。しかも、溶質によるモル
沸点上昇効果も大きくとれるので、次の処理である過酸
化水素錯体の熱処理温度を高くすることができ、分散性
をさらに向上させることができる。従って、本発明にお
いては、アルカリ濃度を高めることは好ましいことであ
る。The alkaline agent is desirably one that can easily achieve a hydrogen ion concentration p) of 112 or higher at which the hydrogen peroxide complex of zirconium ions begins to dissolve, and that is not volatile during heat treatment. Usually hydroxylated) IJ
um or potassium hydroxide are suitable. In this case, the alkali concentration is increased to, for example, ->13.
Since the rate of decomposition and desorption of the hydrogen peroxide complex of zirconium ions is significantly slowed down, fine powder with excellent dispersibility can be produced. Moreover, since the effect of raising the molar boiling point by the solute can be greatly increased, the temperature of the subsequent heat treatment of the hydrogen peroxide complex can be increased, and the dispersibility can be further improved. Therefore, in the present invention, it is preferable to increase the alkali concentration.
過酸化水素としては、濃度が約３０チの過酸化水素水を
用いるのが望ましく、その添加量は、水溶性ジルコニウ
ムイオンの過酸化水素錯体を形成するために溶液中のジ
ルコニウム量の当モル以上とするのがよい。アルカリ剤
と過酸化水素の添加順序は分割添加などどのような方法
であってもよい。反応温度は、通常、常温で行われる。As hydrogen peroxide, it is preferable to use a hydrogen peroxide solution with a concentration of about 30%, and the amount added is equal to or more than the equivalent mole of zirconium in the solution in order to form a hydrogen peroxide complex of water-soluble zirconium ions. It is better to The alkaline agent and hydrogen peroxide may be added in any order, such as by adding them in portions. The reaction temperature is usually room temperature.
以上のようにして得られたジルコニウムの過酸化水素錯
体とアルミニウムイオンを含む溶液を加熱処理し、つい
で酸の添加あるいはイオン交換樹脂処理により−を４〜
１０として沈殿生成を行なう。酸は、塩酸、硝酸、炭酸
、面識、シュウ酸などでよい。加熱処理温度としては、
８０〜２００°Ｃ１好ましくは９０〜１４０°ｃである
。８０℃未満では、粉末の析出に長大な時間を要し経済
的にも実際的でなく、一方、２００°Ｃをこえると反応
時間は短縮されるが、生成する粉末が粗大で粒度が不均
一となるので好ましくない。The solution containing the zirconium hydrogen peroxide complex and aluminum ions obtained as described above is heat-treated, and then the -
Step 10: Precipitate formation. The acid may be hydrochloric acid, nitric acid, carbonic acid, citric acid, oxalic acid, or the like. The heat treatment temperature is
The temperature is 80 to 200°C, preferably 90 to 140°C. If the temperature is less than 80°C, it will take a long time for the powder to precipitate, making it economically impractical. On the other hand, if the temperature exceeds 200°C, the reaction time will be shortened, but the resulting powder will be coarse and the particle size will be uneven. This is not desirable.
上記反応中は、反応の均一性を高め、得られる粉末の均
一化を図るために充分な攪拌を行なうことが望ましい。During the above reaction, it is desirable to perform sufficient stirring in order to improve the uniformity of the reaction and to make the resulting powder uniform.
得られた沈殿は濾過、遠心分離法などにより分離し、充
分に洗浄後、乾燥することによってアルミナジルコニア
系微粉末が得られる。The obtained precipitate is separated by filtration, centrifugation, etc., thoroughly washed, and then dried to obtain alumina-zirconia fine powder.
洗浄は沈澱物中のｃｉ−やＮＯゴなどの不純物を除去す
るため充分に行なうことが望ましく、また不純物除去後
、エタノールやアセトンなどで洗浄することによって沈
澱粒子同志の凝集を防ぐことも有効である。It is desirable to wash thoroughly to remove impurities such as ci- and NO in the precipitate, and it is also effective to prevent the precipitated particles from agglomerating together by washing with ethanol, acetone, etc. after removing the impurities. be.
乾燥は通常の加熱乾燥、真空乾燥の他、噴霧乾燥方法、
振動流動乾燥法、ドラムドライヤー乾燥法、フィルムエ
バポレーター乾燥法などの方法がある。Drying can be done by regular heat drying, vacuum drying, spray drying,
Methods include vibration fluidized drying, drum dryer drying, and film evaporator drying.
粉末同志の凝集を防ぐことは微粉末を得る際に重要であ
るので乾燥後にボールミル、振動ボールミル、ジェット
ミルなどによる解砕を行なうことは有効である。Since it is important to prevent powders from agglomerating together when obtaining a fine powder, it is effective to crush the powder using a ball mill, vibrating ball mill, jet mill, etc. after drying.
このようにして得られるアルミナジルコニア系微粉末の
粒子特性をとくに高めるために、上記乾燥後の粉末また
は解砕後の粉末を仮焼し、仮焼後の解砕を行なうことが
好ましい。In order to particularly improve the particle characteristics of the alumina-zirconia fine powder obtained in this manner, it is preferable to calcinate the dried powder or crushed powder, and then crush the calcined powder.
仮焼温度は４５０℃より低い温度のとき沈澱物中の水分
などの除去が不充分であジ、１２０口０Ｃより高い場合
には粉末同志の焼結などによる凝集が起こり反応性が低
下する難点があり、またエネルギー的にも高温での仮焼
は実際的でない。When the calcination temperature is lower than 450°C, the removal of moisture in the precipitate is insufficient, and when it is higher than 120°C, the powders coagulate due to sintering, resulting in a decrease in reactivity. In addition, calcining at high temperatures is not practical in terms of energy.
従って仮焼温度は４５０〜１２００℃が好ましく６００
〜ｉ ｏｏｏ℃がとくに好ましい。Therefore, the calcination temperature is preferably 450 to 1200°C.
-i ooo°C is particularly preferred.
なお、前記微粉末中に安定化剤すなわち、マグネシウム
、カルシウムまたは３価以上の原子価を肩する金属元素
を配合させると、微粉末の特性がより一層改善され、分
散強化特性が向上する。ここで、６価以上の原子価ｔｉ
する金属元素とは、イツトリウム、セリウム、イッテル
ビウム、スカンジウムなどである。In addition, when a stabilizer, that is, magnesium, calcium, or a metal element having a valence of 3 or more is blended into the fine powder, the characteristics of the fine powder are further improved and the dispersion strengthening characteristics are improved. Here, valence ti of hexavalence or more
The metal elements include yttrium, cerium, ytterbium, scandium, etc.
配合方法は前記安定化剤を塩酸塩、硝酸塩、アルコキシ
ドなどの水浴性化合物として、ジルコニウム塩およびア
ルミニウム塩の溶解時に同時に溶解させる方法が最も好
ましい。The most preferable blending method is to dissolve the stabilizer as a water bathing compound such as a hydrochloride, nitrate, or alkoxide at the same time as the zirconium salt and aluminum salt are dissolved.
これらの成分の添加量は、ジルコニウム金属成分に対し
て２０モルチ以下が好ましい。とくに、マグネシウムと
カルシウムについては６〜１５モル係、イツトリウムな
どは２〜１５モルチが好ましい。The amount of these components added is preferably 20 molti or less relative to the zirconium metal component. In particular, 6 to 15 mol is preferred for magnesium and calcium, and 2 to 15 mol is preferred for yttrium.
〈実施例〉 以下、実施例、比較例をあげてさらに説明する。<Example> Further explanation will be given below with reference to Examples and Comparative Examples.
実施例１
塩化アルミニウム（Ａ）Ｃノ３・６Ｈ２０） ′５９−
５ ｇとオキシ塩化ジルコニウム（ＺｒＯ○）、−８）
Ｉ２０ ） ５．８ｇとを純水２００ｄに溶解し、これ
に濃度０．５そル／ノの水酸化ナトリウム水溶液を加え
、攪拌しながら濃度３１重量％の過酸化水素水５０ｄを
加えた。ついで、濃度８モル／ノの水酸化ナトリウム水
溶ｇ、１２０ ｄを加えて攪拌したところ溶゛液は淡黄
色になった。これを還流下、温度９５ ’Ｃで３時間加
熱し、さらば、濃度５モル／！の塩酸を加えて−を７と
したのち得られた沈殿を充分に水洗ろ過したのち１１０
℃の温度で３時間乾燥後、８００°Ｃで１時間仮焼した
。Example 1 Aluminum chloride (A) C-3/6H20) '59-
5 g and zirconium oxychloride (ZrO○), -8)
I20) 5.8 g was dissolved in 200 d of pure water, to which was added an aqueous sodium hydroxide solution with a concentration of 0.5 solu/no, and while stirring, 50 d of hydrogen peroxide solution with a concentration of 31% by weight was added. Next, 120 g of an aqueous solution of sodium hydroxide having a concentration of 8 mol/min was added and stirred, and the solution turned pale yellow. This was heated under reflux at a temperature of 95'C for 3 hours, and the concentration was 5 mol/! After adding hydrochloric acid to bring the - to 7, the resulting precipitate was thoroughly washed with water and filtered, and the resultant solution was 110
After drying for 3 hours at a temperature of 800°C, it was calcined for 1 hour.
得られた粉末全走査型電子顕微鏡（組成分析装置付、以
下、ＳＫＭと略す）で観察したところ、その粉末は粒径
０．２８〜０．３２ μｍ （平均０．３μｍ）で粒径
がそろっていた。また、前記粉末の組成分析結果から、
この粉床中にはｆｆ１０．０５〜０．１ μｍ （平均
０−０８ μｍ ）のＺｒＯ２粒子が含まれたものがあ
り、顕微鏡の視野全体としてはＺｒＯ２は均一に分散し
ていた。When the obtained powder was observed using a total scanning electron microscope (equipped with a composition analyzer, hereinafter abbreviated as SKM), the powder had a uniform particle size of 0.28 to 0.32 μm (average 0.3 μm). was. Furthermore, from the composition analysis results of the powder,
Some of the powder bed contained ZrO2 particles with an ff of 10.05 to 0.1 μm (average 0 to 08 μm), and the ZrO2 was uniformly dispersed throughout the field of view of the microscope.
比較例１
過酸化水素水を添加しなかった外は実施例１と同様にし
て粉末を得た。得られた粉末を実施例１と同様にＳＥＭ
で観察したところ、粉末の径が１〜６μｍ（平均２．８
μｍ）のＡＩ２０３の凝集粒子と、径が２〜５μｒｎ（
平均６．４μｍ）のＺ ｒ Ｏ２の凝集粒子が混在して
おジ、顕微鏡の視野内のＺ ｒ Ｏ２粒子の分布は不均
一であった。Comparative Example 1 A powder was obtained in the same manner as in Example 1 except that hydrogen peroxide solution was not added. The obtained powder was subjected to SEM in the same manner as in Example 1.
When observed, the powder diameter was 1 to 6 μm (average 2.8 μm).
aggregated particles of AI203 with a diameter of 2 to 5 μrn (
The distribution of Z r O2 particles within the field of view of the microscope was non-uniform, with a mixture of agglomerated particles of Z r O2 with an average diameter of 6.4 μm.
実施例２
塩化アルミニウム（Ａ）０１３番６Ｈ２０） ３９−５
Ｌオキシ塩化ジルコニウム（Ｚｒ０Ｏ）２惨３Ｈ２ｏ
） ５−８９および塩化イツトリウム（ＭＯ）３・６
Ｈ２０）０．４５ Ｆ ｅ用いて以下実施例１と同じ操
作で粉末を得た。得られた粉末は程径０．２７〜０．６
３μｍ（平均０．３μｍ）であり、この粉末中には粒径
０．０５〜０．１μｍ（平均０．０８μｍ）のＺｒＯ２
粒子が含まれたものがあり、実施例１と同様に微粉末で
分散性、均一性に優れたものであった。Example 2 Aluminum chloride (A) No. 013 6H20) 39-5
L zirconium oxychloride (Zr0O)2 3H2o
) 5-89 and yttrium chloride (MO) 3.6
H20) A powder was obtained in the same manner as in Example 1 using 0.45 Fe. The obtained powder has a diameter of 0.27 to 0.6
3 μm (average 0.3 μm), and this powder contains ZrO2 with a particle size of 0.05 to 0.1 μm (average 0.08 μm).
Some contained particles, and like Example 1, they were fine powders with excellent dispersibility and uniformity.
実施例３
塩化アルミニウム（Ａ）Ｏノ３−６ａ２ｏ） ３９．５
ｇ、オキシ塩化ジルコニウム（Ｚｒ０Ｏ）２”８Ｈ２
０） ５．８ ｇおよび塩化マグネシウム（ＭｇＣ）２
・６Ｈ２０） ［１，３５９を用いて以下実施例１と同
じ操作で微粉末を得た龍
得られた粉末はぎ径０．２８〜０．３３μｍ（平均０．
３１μｍ）であり、この粉末中には粒径０．０５〜０．
１μｍ（平均０．０８μｍ ）のＺ ｒ ０２粒子が含
まレタものがあり、実施例１と同様に微粉末で分散性、
均一性に優れたものであった。Example 3 Aluminum chloride (A)Ono3-6a2o) 39.5
g, zirconium oxychloride (Zr0O)2”8H2
0) 5.8 g and magnesium chloride (MgC)2
・6H20) [1,359 was used to obtain a fine powder in the same manner as in Example 1.
31 μm), and this powder has a particle size of 0.05 to 0.3 μm.
There is a letter containing Z r 02 particles of 1 μm (average 0.08 μm), and as in Example 1, it is a fine powder and has good dispersibility.
It had excellent uniformity.
実施例４
塩化アルミニウム（ｈｉａ）３・６Ｈ２０） ３９．５
Ｌオキシ塩化ジル：Ｉ 二ｆｙ ム（Ｚｒ０Ｏｊ２・
８Ｈ２０） ５−８ ｆ！および炭酸カルシウム０．１
５ｇを用いて以下実施例１と同じ操作で微粉末会得た。Example 4 Aluminum chloride (hia) 3.6H20) 39.5
L oxychloride: I2fymu(Zr0Oj2・
8H20) 5-8 f! and calcium carbonate 0.1
Using 5 g, a fine powder was obtained in the same manner as in Example 1.
得られた粉末は粒径０−２９〜０．３４ μｍ （平均
０．３２ μｍ ）であり、この粉末中には粒径０．０
５〜０．１μｍ（平均０．０８μｍ）のＺ ｒｏ ２粒
子が含まれたものがあり、実施例１と同様に微粉末で分
散性、均一性に優れたものであった。The obtained powder has a particle size of 0-29 to 0.34 μm (average 0.32 μm), and this powder contains particles with a particle size of 0.0 μm.
Some contained Z ro 2 particles of 5 to 0.1 μm (average 0.08 μm), and like Example 1, they were fine powders with excellent dispersibility and uniformity.
〈発明の効果〉
（１１本発明によれば、ジルコニウム塩及びアルミニウ
ム塩の混合水溶液をアルカリ性にして、過酸化水素を加
えることにより、ジルコニウムイオンの過酸化水素錯体
とアルミニウムイオンとの混合液とし、つぎに、加熱処
理をし、ついでアルミニウムイオンをアルカリ性側から
沈殿させることにより、均−性及び分散性に優れたアル
ミナジルコニア系微粉末が得られる。<Effects of the Invention> (11) According to the present invention, a mixed aqueous solution of a zirconium salt and an aluminum salt is made alkaline and hydrogen peroxide is added to form a mixed solution of a hydrogen peroxide complex of zirconium ions and aluminum ions, Next, a heat treatment is performed, and then aluminum ions are precipitated from the alkaline side, thereby obtaining an alumina-zirconia fine powder with excellent uniformity and dispersibility.
（２）本発明の製法は、極めて単純な単位操作から構成
され、同一容器内ですべての操作を行なえばよく大量−
の処理が可能であるため工業的大量生産が容易であり、
その経済的価値は著しく高い。(2) The manufacturing method of the present invention consists of extremely simple unit operations, and all operations can be performed in the same container in large quantities.
It is easy to mass-produce industrially because it is possible to process
Its economic value is significantly high.
Claims (1)
カリ性にして、過酸化水素を加えることにより、ジルコ
ニウムイオンの過酸化水素錯体とアルミニウムイオンと
の混合液とし、つぎに、前記混合液を温度８０〜２００
℃で加熱したのち、水溶液のｐＨを４〜１０の範囲とす
ることによつて沈殿を生成させ、該沈殿を分離すること
を特徴とするアルミナジルコニア系微粉末の製法。A mixed aqueous solution of a zirconium salt and an aluminum salt is made alkaline and hydrogen peroxide is added to obtain a mixed solution of a hydrogen peroxide complex of zirconium ions and aluminum ions, and then the mixed solution is heated to a temperature of 80 to 200 ml.
1. A method for producing alumina-zirconia fine powder, which comprises heating at a temperature of 0.degree. C., adjusting the pH of an aqueous solution to a range of 4 to 10 to form a precipitate, and separating the precipitate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19806486A JPH07100613B2 (en) | 1986-08-26 | 1986-08-26 | Manufacturing method of alumina zirconia-based fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19806486A JPH07100613B2 (en) | 1986-08-26 | 1986-08-26 | Manufacturing method of alumina zirconia-based fine powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6355119A true JPS6355119A (en) | 1988-03-09 |
| JPH07100613B2 JPH07100613B2 (en) | 1995-11-01 |
Family
ID=16384924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19806486A Expired - Lifetime JPH07100613B2 (en) | 1986-08-26 | 1986-08-26 | Manufacturing method of alumina zirconia-based fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07100613B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089247A (en) * | 1988-01-19 | 1992-02-18 | Degussa Aktiengesellschaft | Process for producing zirconium-doped pseudoboehmite |
-
1986
- 1986-08-26 JP JP19806486A patent/JPH07100613B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089247A (en) * | 1988-01-19 | 1992-02-18 | Degussa Aktiengesellschaft | Process for producing zirconium-doped pseudoboehmite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07100613B2 (en) | 1995-11-01 |
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