JPH06293564A - Method for producing zirconia powder containing solid solution of stabilizer - Google Patents
Method for producing zirconia powder containing solid solution of stabilizerInfo
- Publication number
- JPH06293564A JPH06293564A JP5104986A JP10498693A JPH06293564A JP H06293564 A JPH06293564 A JP H06293564A JP 5104986 A JP5104986 A JP 5104986A JP 10498693 A JP10498693 A JP 10498693A JP H06293564 A JPH06293564 A JP H06293564A
- Authority
- JP
- Japan
- Prior art keywords
- stabilizer
- zirconium hydroxide
- slurry
- metal ions
- hydroxide
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
(57)【要約】
【目的】 本発明は安定化剤を固溶したジルコニア粉の
製造方法に係り、特に安定化剤を固溶した焼結性の良好
なジルコニア粉の低コストの工業的製造方法を提供す
る。
【構成】 水酸化ジルコニウムを水に解砕してスラリー
化し、このスラリーを撹拌しながらイットリウム等のジ
ルコニア安定化剤の水可溶性塩の一種以上を含む水溶液
を添加混合して安定化剤金属イオンの大部分を水酸化ジ
ルコニウムに吸着させ、このスラリーをアンモニア水等
で中和することにより、安定化剤金属イオンを水酸化ジ
ルコニウム中に沈殿させ、未吸着の金属イオンの残部も
水酸化物として水酸化ジルコニウム表面に沈殿させ、得
られた水酸化ジルコニウムの混合沈殿物を濾過した後、
仮焼する工程をとる。(57) [Summary] [Object] The present invention relates to a method for producing a zirconia powder in which a stabilizer is dissolved, and particularly to a low-cost industrial production of a zirconia powder in which a stabilizer is dissolved and which has good sinterability. Provide a way. [Structure] Zirconium hydroxide is crushed into water to form a slurry, and an aqueous solution containing at least one water-soluble salt of a zirconia stabilizer such as yttrium is added and mixed while stirring the slurry to form a stabilizer metal ion. Most of the metal ions are adsorbed on zirconium hydroxide, and the slurry metal ions are precipitated in zirconium hydroxide by neutralizing this slurry with aqueous ammonia, etc., and the rest of the unadsorbed metal ions are also converted to hydroxide. After precipitation on the zirconium oxide surface and filtering the resulting mixed precipitate of zirconium hydroxide,
Take the step of calcination.
Description
【０００１】[0001]
【産業上の利用分野】本発明は安定化剤を固溶したジル
コニア粉の製造方法に係り、特に結晶粒が微細で焼結性
の良好なジルコニア粉を安価に製造でき、かつ製造履歴
の異なる水酸化ジルコニウムを原料として選択すること
により、粉体特性の異なるジルコニア粉を造り分けるこ
ともできる製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a zirconia powder containing a stabilizer as a solid solution. In particular, it is possible to inexpensively produce a zirconia powder having fine crystal grains and good sinterability, and having a different production history. The present invention relates to a manufacturing method in which zirconium hydroxide having different powder characteristics can be produced separately by selecting zirconium hydroxide as a raw material.
【０００２】[0002]
【従来の技術】従来、安定化剤を固溶したジルコニア粉
の製造方法として、次の２方法等が知られている。すな
わち、 ジルコニウム可溶性塩と安定化剤の可溶性塩とを含む
水溶液をアンモニア水等で中和して共沈させ、この沈殿
を濾過水洗した後、乾燥仮焼する方法。 ジルコニウム可溶性塩と安定化剤の可溶性塩とを含む
水溶液を加水分解させて得た水酸化物を乾燥、仮焼する
方法。 ところが、上記従来方法には次のような欠点がある。す
なわち、の方法は安定化剤とジルコニウムの沈殿のＰ
Ｈが異なるため水酸化ジルコニウムに安定化剤が均質に
分解させることが困難で、均質な組成及び結晶子を有す
る安定化剤を固溶したジルコニアが得られない。また、
の方法ではオ−トクレ−ブ内で高温高圧下に長時間処
理するという工程を必須としており、これらの高価な製
造設備並びに該設備の運転費用の面で経済性にかける。2. Description of the Related Art Conventionally, the following two methods have been known as a method for producing a zirconia powder containing a stabilizer as a solid solution. That is, a method in which an aqueous solution containing a zirconium-soluble salt and a stabilizer-soluble salt is neutralized with ammonia water or the like to coprecipitate, the precipitate is filtered, washed with water, and then dried and calcined. A method of drying and calcining a hydroxide obtained by hydrolyzing an aqueous solution containing a zirconium-soluble salt and a stabilizer-soluble salt. However, the above conventional method has the following drawbacks. That is, the method of P is used for stabilizing and zirconium precipitation.
Since the H is different, it is difficult to uniformly decompose the stabilizer into zirconium hydroxide, and it is impossible to obtain zirconia in which the stabilizer having a uniform composition and crystallite is solid-dissolved. Also,
In the method (1), a step of treating at high temperature and high pressure in an autoclave for a long time is indispensable, which is economical in terms of these expensive production equipment and the operating cost of the equipment.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、上記
従来法の欠点を排除して、安定化剤を均一に固溶した均
質な組成および結晶子を有する焼結性の良好なジルコニ
ア粉を安価に製造する効果的な方法を提供することにあ
る。DISCLOSURE OF THE INVENTION The object of the present invention is to eliminate the above-mentioned drawbacks of the conventional method and to provide a zirconia powder having a uniform composition and a crystallite in which a stabilizer is uniformly dissolved, and having a good sinterability. The object is to provide an effective method for manufacturing the resin at low cost.
【０００４】[0004]
【課題を解決するための手段】本発明の上記目的は、次
の２発明によって、何れも満足して達成できることを見
出した。該２発明のそれぞれ要旨とするところは次の如
くである。すなわち、 （１）水酸化ジルコニウムを水に解砕してスラリー化す
る段階と、前記スラリーを撹拌しながらイツトリウム、
カルシウム、セリウム、アルミニウム等の通常用いられ
ているジルコニア安定化剤の水可溶性塩の一種以上を含
む水溶液を添加して混合することにより前記安定化剤金
属イオンの大部分を水酸化ジルコニウムに吸着させる段
階と、前記処理したスラリーをアンモニア水等で中和す
ることにより前記吸着した安定化剤金属イオンを水酸化
ジルコニウム中に沈殿させる段階と、前記安定化剤金属
イオンの未吸着の残部を水酸化物として水酸化ジルコニ
ウム表面に沈殿させる段階と、得られた水酸化ジルコニ
ウムの混合沈殿物を水溶液と分離した後仮焼する段階
と、を有して成ることを特徴とする安定化剤を固溶した
ジルコニア粉の製造方法。 （２）水酸化ジルコニウムを水に解砕してスラリー化す
る段階と、前記スラリーを撹拌しながらイツトリウム、
カルシウム、マグネシウム、セリウム、アルミニウム等
の通常用いられているジルコニア安定化剤の水可溶性塩
の一種以上を含む水溶液を添加して混合することにより
前記安定化剤金属イオンの大部分を水酸化ジルコニウム
に吸着させる段階と、前記処理したスラリーを加熱昇温
して添加安定化剤金属イオンの吸着量を増加させた後に
アンモニア水等で中和することにより吸着した安定化剤
金属イオンを水酸化ジルコニウム中に沈殿させる段階
と、前記安定化剤金属イオンの未吸着の残部を水酸化物
として水酸化ジルコニウム表面に沈殿させる段階と、得
られた水酸化ジルコニウムの混合沈殿物を水溶液と分離
した後仮焼する段階と、を有してなることを特徴とする
安定化剤を固溶したジルコニア粉の製造方法。It has been found that the above objects of the present invention can be satisfactorily achieved by the following two inventions. The gist of each of the two inventions is as follows. That is, (1) a step of crushing zirconium hydroxide into water to form a slurry, and yttrium while stirring the slurry,
Most of the stabilizer metal ions are adsorbed on zirconium hydroxide by adding and mixing an aqueous solution containing one or more water-soluble salts of commonly used zirconia stabilizers such as calcium, cerium and aluminum. A step of precipitating the adsorbed stabilizer metal ions in zirconium hydroxide by neutralizing the treated slurry with aqueous ammonia and the like, and hydroxylating the unadsorbed remainder of the stabilizer metal ions. As a product, a step of precipitating on the surface of zirconium hydroxide, and a step of separating the obtained mixed precipitate of zirconium hydroxide from the aqueous solution and then calcining the solution, to form a solid solution of a stabilizer. Of producing the zirconia powder. (2) Disintegrating zirconium hydroxide into water to form a slurry, and stirring the slurry with yttrium,
Most of the stabilizer metal ions are converted into zirconium hydroxide by adding and mixing an aqueous solution containing one or more water-soluble salts of commonly used zirconia stabilizers such as calcium, magnesium, cerium and aluminum. In the zirconium hydroxide stage, the adsorbed stabilizer metal ions are adsorbed by neutralizing the adsorbed stabilizer metal ions by heating and heating the treated slurry to increase the adsorbed amount of the stabilizer metal ions. And a step of precipitating the unadsorbed residual metal ions of the stabilizer on the surface of the zirconium hydroxide as hydroxide, and the resulting mixed precipitate of zirconium hydroxide is separated from the aqueous solution and then calcined. The method for producing a zirconia powder containing a stabilizer as a solid solution, which comprises:
【０００５】本発明を詳細に説明する。まず水溶性ジル
コニウム化合物、例えばオキシ塩化ジルコニウム等の水
溶液又は塩基性硫酸ジルコニウム沈殿を含むスラリーを
アンモニア水等のアルカリ溶液で中和することにより得
られた水酸化ジルコニウム沈殿を濾過、水洗し、これを
繰り返して不純物の少ない水酸化ジルコニウムを得る。
次に該水酸化ジルコニウムを適量の水に解砕してスラリ
ー状にする。このときの添加する水の量は水酸化ジルコ
ニウムがスラリー化するに足る十分な量であれば良い。
撹拌混合しているスラリー中にＺｒＯ2１モル当たり必
要量の安定化剤、例えばＹ2Ｏ3の場合には塩化イットリ
ウム、硝酸イットリウム等の水溶性イットリウム化合物
の必要量を添加する。水酸化ジルコニウムはイオン交換
能力があるので添加した３価のイットリウム等の安定化
剤金属イオンの大部分が水酸化ジルコニウムに吸着固定
される。このように安定化剤金属イオンを水酸化ジルコ
ニウムに分子レベルで均質に固定化させることが本発明
の特徴の一つである。添加量が４モル％以下であると安
定化剤を一度に添加しても吸着率は高く保たれるが、８
モル％程度の高い添加率の場合には一度に添加すると吸
着率が低下するので２度に分割して操作する。すなわ
ち、４モル％分を添加して吸着させた後にアンモニア水
で中和し濾過して、濾過ケークを再びスラリー化して残
りの４モル％分を添加して同じ操作で吸着させると、吸
着率は最初の４モル％分と同様に高くなる。これをアン
モニア水で中和して濾過、水洗を行い仮焼する。The present invention will be described in detail. First, a zirconium hydroxide precipitate obtained by neutralizing a water-soluble zirconium compound, for example, an aqueous solution such as zirconium oxychloride or a slurry containing a basic zirconium sulfate precipitate with an alkaline solution such as ammonia water is filtered and washed with water. Repeatedly, zirconium hydroxide containing few impurities is obtained.
Next, the zirconium hydroxide is crushed into an appropriate amount of water to form a slurry. The amount of water added at this time may be an amount sufficient to make zirconium hydroxide into a slurry.
ZrO 2 1 mole per required amount of the stabilizing agent in the slurry being stirred and mixed, for example in the case of Y 2 O 3 is the addition of the necessary amount of the water-soluble yttrium compound such as yttrium chloride, yttrium nitrate. Since zirconium hydroxide has an ion exchange ability, most of the added stabilizer metal ions such as trivalent yttrium are adsorbed and fixed on zirconium hydroxide. Thus, one of the features of the present invention is to uniformly immobilize the stabilizer metal ion on zirconium hydroxide at the molecular level. If the addition amount is 4 mol% or less, the adsorption rate is kept high even if the stabilizer is added all at once.
When the addition rate is as high as about mol%, the adsorption rate decreases when added at once, so the operation is divided into two steps. That is, when 4 mol% was added and adsorbed, the mixture was neutralized with ammonia water, filtered, the filter cake was slurried again, and the remaining 4 mol% was added and adsorbed by the same operation. Is as high as the first 4 mol%. This is neutralized with aqueous ammonia, filtered, washed with water and calcined.
【０００６】吸着はイオン交換反応であるからイオン濃
度が高い方が吸着率は高い。従つて水酸化ジルコニウム
のスラリー濃度は高いほど金属イオンの吸着率が高くな
り好ましい。また金属イオンの添加後にスラリーを加熱
昇温することも金属イオンの吸着率向上に効果がある。
これは、温度により反応平衡が移動して結合する金属イ
オンが増加することによるものと考えられる。このよう
にして大部分の安定化剤金属イオンを水酸化ジルコニウ
ムに結合させた後に、水酸化ジルコニウムに結合してい
ない安定化剤金属イオンはアンモニア水等のアルカリ溶
液で中和して水酸化物沈殿となし、水酸化ジルコニウム
沈殿の表面に共沈させる。撹拌混合しているスラリー中
で沈殿を生成するため安定化剤金属イオンの水酸化物は
分子レベルの接触には至らないが、ほぼ均一に水酸化ジ
ルコニウム表面に吸着される。Since adsorption is an ion exchange reaction, the higher the ion concentration, the higher the adsorption rate. Therefore, the higher the slurry concentration of zirconium hydroxide, the higher the adsorption rate of metal ions, which is preferable. Further, heating the temperature of the slurry after the addition of the metal ions is also effective in improving the adsorption rate of the metal ions.
It is considered that this is because the reaction equilibrium moves depending on the temperature and the number of bound metal ions increases. After binding most of the stabilizer metal ions to zirconium hydroxide in this way, the stabilizer metal ions not bound to zirconium hydroxide are neutralized with an alkaline solution such as aqueous ammonia to form hydroxides. Without precipitation, coprecipitate on the surface of the zirconium hydroxide precipitate. The hydroxide of the stabilizer metal ion does not come into contact at the molecular level because a precipitate is generated in the slurry being stirred and mixed, but it is almost uniformly adsorbed on the zirconium hydroxide surface.
【０００７】安定化剤を吸着、共沈した水酸化ジルコニ
ウムは濾過、水洗により陰イオンを十分に除去した後仮
焼して安定化剤固溶のジルコニアを得るのであるが、分
子レベルで安定化剤金属イオンを結合した水酸化ジルコ
ニウムは、極めて低温の仮焼で容易に金属イオンを固溶
することができる。すなわち、６００℃〜１０００℃の
温度で仮焼することにより安定化剤を固溶させたジルコ
ニア仮焼粉とした後に、これを粉砕して粒度を整え微粒
の安定化剤固溶ジルコニア粉とすることができる。この
方法では仮焼温度が低いため結晶粒子の成長が少なく、
これを焼成する場合には１４００℃程度の低温で真比重
に近い密度に焼結することができる。かくの如く本発明
方法によると、極めて操作が容易で、しかも長時間の反
応操作を必要とせずに安定化剤を固溶したジルコニア粉
を製造することができ、しかも安定化剤の大部分は分子
レベルで水酸化ジルコニウムと接触しているため仮焼時
の反応が容易で、低温度で固溶させることができるので
結晶子のグレインサイズの小さな焼結性の良好な原料ジ
ルコニア粉を製造することができる。上記本発明の方法
によつて得られたジルコニア粉は、ジルコニウム源とな
る水酸化ジルコニウムを仮焼したときの粉体特性を受け
継ぎ、これに極めて類似した粉体特性を有する安定化剤
固溶ジルコニアになる。従つて目的に応じた水酸化ジル
コニウムを選ぶことにより粉体特性の異なる安定化剤固
溶ジルコニア粉の作り分けを行うこともできる。Zirconium hydroxide on which a stabilizer is adsorbed and coprecipitated is filtered and washed with water to sufficiently remove anions, and then calcined to obtain zirconia in the form of a solid solution of the stabilizer, which is stabilized at the molecular level. Zirconium hydroxide bonded with the agent metal ion can easily form a solid solution with the metal ion by calcination at an extremely low temperature. That is, after calcining at a temperature of 600 ° C. to 1000 ° C., a zirconia calcined powder in which a stabilizer is solid-dissolved is formed, and then the zirconia calcined powder is pulverized to adjust the particle size to obtain a fine stabilizer-dissolved zirconia powder. be able to. In this method, since the calcination temperature is low, the growth of crystal grains is small,
When this is fired, it can be sintered at a low temperature of about 1400 ° C. to a density close to the true specific gravity. As described above, according to the method of the present invention, it is possible to produce a zirconia powder having a stabilizer dissolved therein, which is extremely easy to operate and does not require a long-time reaction operation, and most of the stabilizer is Since it is in contact with zirconium hydroxide at the molecular level, the reaction during calcination is easy, and since it can be solid-solved at low temperature, it produces a zirconia powder with a small crystallite grain size and good sinterability. be able to. The zirconia powder obtained by the method of the present invention inherits the powder characteristics when zirconium hydroxide serving as a zirconium source is calcined, and has a powder property very similar to that of the stabilizer solid solution zirconia. become. Therefore, by selecting zirconium hydroxide according to the purpose, it is possible to separately prepare stabilizer-dissolved zirconia powder having different powder characteristics.
【０００８】[0008]
【実施例１】原料水酸化ジルコニウムの一種を水に解砕
してスラリーとした。スラリー中のＺrＯ2量は４１．６
ｇ、スラリーは全容量が１リットルになるようにした。
スラリーを撹拌しながらＹ2Ｏ3として３モル％に相当す
る２．３６ｇを含むＹＣ１3溶液を加えた。３０分後に
上澄み液の３価のイットリウム濃度を分析して水酸化ジ
ルコニウムに結合しているＹの総添加量に対する比率を
計算すると７８％であつた。撹拌を続けながらアンモニ
ア水５０ｍｌ添加して３０分撹拌継続後に濾過、洗浄を
繰り返して過剰のアンモニア分、塩化物を除去した後に
得られた水酸化ジルコニウムを８００℃で２時間仮焼し
た。得られた粉末の粉体特性はＤ50・１．２μｍ、嵩密
度０．２ｇ／ｃｍ3、タッブ密度０．４ｇ／ｃｍ3、比表
面積・３２ｍ2／ｇ、Ｘ線回折して正方晶系のｄ＝２．
９６（１１１）、単斜晶系ｄ＝３．１６（１１１）、ｄ
＝２．８４（１１１）とから正方晶率を計算すると８９
％であつた。Ｘ線回折結果を第１図に示す。なお正方晶
率＝正方晶系ピーク高さ／単斜晶系ピーク高さ（d2.84.
+d3.16）＋正方晶系ピーク高さとして計算した。また、
Ｄ50はマイクロトラックにより測定した平均粒径（μ
ｍ）を指す。Example 1 One kind of raw material zirconium hydroxide was crushed into water to obtain a slurry. The amount of ZrO 2 in the slurry is 41.6
g, the total volume of the slurry was 1 liter.
While stirring the slurry, a YC1 3 solution containing 2.36 g corresponding to 3 mol% as Y 2 O 3 was added. After 30 minutes, the concentration of trivalent yttrium in the supernatant was analyzed and the ratio to the total amount of Y bound to zirconium hydroxide was calculated to be 78%. While continuing stirring, 50 ml of ammonia water was added, and after stirring was continued for 30 minutes, filtration and washing were repeated to remove excess ammonia content and chloride, and zirconium hydroxide obtained was calcined at 800 ° C. for 2 hours. The powder properties of the obtained powder are D 50 1.2 μm, bulk density 0.2 g / cm 3 , tab density 0.4 g / cm 3 , specific surface area 32 m 2 / g, tetragonal system by X-ray diffraction D = 2.
96 (111), monoclinic system d = 3.16 (111), d
= 2.84 (111) and the tetragonal ratio is calculated to be 89.
It was in%. The X-ray diffraction result is shown in FIG. The tetragonal ratio = tetragonal peak height / monoclinic peak height (d2.84.
+ d3.16) + calculated as tetragonal peak height. Also,
D 50 is the average particle size (μ
m).
【０００９】[0009]
【実施例２】実施例１と同じ方法で水酸化ジルコニウム
スラリーにＹＣｌ3溶液を加えた。該スラリーを撹拌し
ながら加熱して８０℃まで昇温した後、上澄み液の３価
のイットリウム濃度を分析して水酸化ジルコニウムに結
合しているイットリウムの総添加量に対する比率を計算
すると８５％であつた。撹拌を続けながらアンモニア水
５０ｍｌ添加し、以後実施例１と同様に濾過、洗浄を行
い仮焼した。仮焼は６００℃２時間及び８００℃２時間
の２つの条件で行い、得られた粉末をＸ線回折した。Ｘ
線回折結果をそれぞれ第２図および第３図に示す。６０
０℃仮焼の粉は、８００℃仮焼の粉に比べて結晶化が悪
いが単斜晶系はほとんど見られず、イットリアを十分に
固溶していることを示しており、正方晶系率を計算する
といずれも９７％と極めて高い値が得られた。実施例１
と比較してイットリウムイオンの吸着率が高くなつたこ
とにより固溶率も向上したことを示している。８００℃
仮焼の粉末を１．０ｔ／ｃｍ2、１．５ｔ／ｃｍ2、２．
０ｔ／ｃｍ2の圧力で成形し、１３００〜１５００℃で
２時間焼成した後の焼結密度の測定値は表１に示すとお
りであり、極めて焼結性の良好な粉であることを示して
いる。Example 2 A YCl 3 solution was added to a zirconium hydroxide slurry in the same manner as in Example 1. After heating the slurry to 80 ° C. with stirring, the concentration of trivalent yttrium in the supernatant was analyzed to calculate the ratio to the total amount of yttrium bonded to zirconium hydroxide, which was 85%. Atsuta While continuing stirring, 50 ml of ammonia water was added, and thereafter, filtration, washing and calcination were carried out in the same manner as in Example 1. The calcination was performed under two conditions of 600 ° C. for 2 hours and 800 ° C. for 2 hours, and the obtained powder was subjected to X-ray diffraction. X
The line diffraction results are shown in FIGS. 2 and 3, respectively. 60
The 0 ° C. calcined powder has poorer crystallization than the 800 ° C. calcined powder, but almost no monoclinic system is observed, indicating that yttria is sufficiently dissolved as a solid. When the rates were calculated, an extremely high value of 97% was obtained in all cases. Example 1
It is shown that the solid solution rate is also improved due to the higher adsorption rate of yttrium ions as compared with. 800 ° C
The calcinated powder was 1.0 t / cm 2 , 1.5 t / cm 2 , 2.
The measured value of the sintered density after molding at a pressure of 0 t / cm 2 and firing at 1300 to 1500 ° C. for 2 hours is as shown in Table 1, showing that the powder has extremely good sinterability. There is.
【表１】 [Table 1]
【００１０】[0010]
【実施例３】実施例２とは製造履歴の異なる原料水酸化
ジルコニウムを使用して実施例２と同様の操作でイット
リウム固溶のジルコニアを製造した。水酸化ジルコニウ
ムスラリーにＹＣｌ3水溶液を添加し８０℃に加熱した
後イットリウムの吸着率は８９％であり、得られたジル
コニアのＸ線回析結果から正方晶率を計算すると９７％
であつた。粉体特性測定値は平均粒径Ｄ50０．７３μ
ｍ、嵩密度０．４５／ｃｍ3、タツプ密度０．７５ｇ／
ｃｍ3、比表面積３５ｍ2／ｇであつた。Example 3 Yttrium solid solution zirconia was produced in the same manner as in Example 2 by using a raw material zirconium hydroxide having a production history different from that of Example 2. After adding a YCl 3 aqueous solution to the zirconium hydroxide slurry and heating it to 80 ° C., the yttrium adsorption rate was 89%, and when the tetragonal crystal ratio was calculated from the X-ray diffraction results of the obtained zirconia, it was 97%.
It was. Measured powder characteristics are average particle size D 50 0.73μ
m, bulk density 0.45 / cm 3 , tap density 0.75 g /
It had a cm 3 and a specific surface area of 35 m 2 / g.
【００１１】[0011]
【発明の効果】上記実施例から明らかな如く、本発明に
よる安定剤を固溶したジルコニウム粉の製造方法は次の
如きすぐれた効果を有している。 （イ）本発明方法の操作は極めて容易で、かつ長時間の
反応操作を必要としない。 （ロ）安定化剤の大部分は分子レべルで水酸化ジルコニ
ウムと接触しているため、仮焼時の反応が容易であつて
低温度で固溶させることができる。その結果、仮焼後の
機械的粉砕をほとんど必要としない。 （ハ）結晶粒の小さい焼結性の良好な原料ジルコニア粉
を安価に製造することができる。 （ニ）本発明によるジルコニア粉は、ジルコニウム源と
なる水酸化ジルコニウムを仮焼したときの粉体特性を受
け継ぎ、これと極めて類似した粉体特性を有する安定化
剤を固溶したジルコニア粉となる。 （ホ）その結果、目的に応じて適当な水酸化ジルコニウ
ム原料を選ぶことにより、任意の粉体特性のジルコニア
粉を製造することができる。As is apparent from the above examples, the method for producing a zirconium powder containing the stabilizer as a solid solution according to the present invention has the following excellent effects. (A) The method of the present invention is extremely easy to operate and does not require a long-time reaction operation. (B) Since most of the stabilizer is in contact with zirconium hydroxide at the molecular level, the reaction during calcination is easy and the stabilizer can be solid-dissolved at low temperature. As a result, little mechanical grinding is required after calcination. (C) A raw material zirconia powder having a small crystal grain and good sinterability can be manufactured at low cost. (D) The zirconia powder according to the present invention becomes a zirconia powder in which a stabilizing agent having a powder property extremely similar to that of the powder property when calcining zirconium hydroxide as a zirconium source is inherited . (E) As a result, by selecting an appropriate zirconium hydroxide raw material according to the purpose, a zirconia powder having arbitrary powder characteristics can be produced.
【図１】実施例１における８００℃で２時間仮焼したジ
ルコニア粉のＸ線回折図である。FIG. 1 is an X-ray diffraction diagram of zirconia powder calcined at 800 ° C. for 2 hours in Example 1.
【図２】実施例２における６００℃で２時間仮焼したジ
ルコニア粉のＸ線回折図である。2 is an X-ray diffraction diagram of zirconia powder calcined at 600 ° C. for 2 hours in Example 2. FIG.
【図３】実施例２における８００℃で２時間仮焼したジ
ルコニア粉のＸ線解折図である。FIG. 3 is an X-ray diffraction diagram of zirconia powder calcined at 800 ° C. for 2 hours in Example 2.
Claims (2)
リ−化する段階と、前記スラリ−を撹拌しながらイット
リウム、カルシウム、マグネシウム、セリウム、アルミ
ニウム等の通常用いられているジルコニア安定化剤の水
可溶性塩の一種以上を含む水溶液を添加して混合するこ
とにより前記安定化剤金属イオンの大部分を水酸化ジル
コニウムに吸着させる段階と、前記処理したスラリ−を
アンモニア水等で中和することにより前記吸着した安定
化剤金属イオンを水酸化ジルコニウム中に沈殿させる段
階と、前記安定化剤金属イオンの未吸着の残部を水酸化
物として水酸化ジルコニウム表面に沈殿させる段階と、
得られた水酸化ジルコニウムの混合沈殿物を水溶液と分
離した後仮焼する段階と、有して成ることを特徴とする
安定化剤を固溶したジルコニア粉の製造方法。1. A step of crushing zirconium hydroxide into water to form a slurry, and a method of using a commonly used zirconia stabilizer such as yttrium, calcium, magnesium, cerium and aluminum while stirring the slurry. Adsorbing most of the stabilizer metal ions to zirconium hydroxide by adding and mixing an aqueous solution containing one or more water-soluble salts; and neutralizing the treated slurry with aqueous ammonia or the like. By precipitating the adsorbed stabilizer metal ions in zirconium hydroxide, and precipitating the unadsorbed balance of the stabilizer metal ions on the zirconium hydroxide surface as hydroxide,
A method for producing a zirconia powder containing a stabilizer as a solid solution, which comprises a step of calcination after separating the obtained mixed precipitate of zirconium hydroxide from an aqueous solution.
リ−化する段階と、前記スラリ−を撹拌しながらイット
リウム、カルシウム、マグネシウム、セリウム、アルミ
ニウム等の通常用いられているジルコニア安定化剤の水
可溶性塩の一種以上を含む水溶液を添加して混合するこ
とにより前記安定化剤金属イオンの大部分を水酸化ジル
コニウムに吸着させる段階と、前記処理したスラリ−を
加熱昇温して添加安定化剤金属イオンの吸着量を増加さ
せた後にアンモニア水等で中和することにより吸着した
安定化剤金属イオンを水酸化ジルコニウム中に沈殿させ
る段階と、前記安定化剤金属イオンの未吸着の残部を水
酸化物として水酸化ジルコニウム表面に沈殿させる段階
と、得られた水酸化ジルコニウムの混合沈殿物を水溶液
と分離した後仮焼する段階と、有して成ることを特徴と
する安定化剤を固溶したジルコニア粉の製造方法。2. A step of crushing zirconium hydroxide into water to form a slurry, and a commonly used zirconia stabilizer such as yttrium, calcium, magnesium, cerium or aluminum while stirring the slurry. A step of adsorbing most of the stabilizer metal ions to zirconium hydroxide by adding and mixing an aqueous solution containing one or more water-soluble salts, and heating and heating the treated slurry to stabilize the addition. The step of precipitating the adsorbed stabilizer metal ions in the zirconium hydroxide by neutralizing with ammonia water after increasing the adsorbed amount of the agent metal ions, and the remaining unadsorbed part of the stabilizer metal ions The step of precipitating on the surface of zirconium hydroxide as hydroxide, and the resulting mixed precipitate of zirconium hydroxide is separated from the aqueous solution and then calcined A method for producing a zirconia powder in which a stabilizer is formed as a solid solution, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10498693A JP3531678B2 (en) | 1993-04-07 | 1993-04-07 | Method for producing zirconia powder containing solid solution of stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10498693A JP3531678B2 (en) | 1993-04-07 | 1993-04-07 | Method for producing zirconia powder containing solid solution of stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06293564A true JPH06293564A (en) | 1994-10-21 |
| JP3531678B2 JP3531678B2 (en) | 2004-05-31 |
Family
ID=14395420
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10498693A Expired - Fee Related JP3531678B2 (en) | 1993-04-07 | 1993-04-07 | Method for producing zirconia powder containing solid solution of stabilizer |
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| Country | Link |
|---|---|
| JP (1) | JP3531678B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001080919A (en) * | 1999-07-09 | 2001-03-27 | Tosoh Corp | Zirconia fine powder and method for producing the same |
| WO2014196100A1 (en) | 2013-06-04 | 2014-12-11 | 新日本電工株式会社 | Ceria-zirconia mixed oxide and method for producing same |
-
1993
- 1993-04-07 JP JP10498693A patent/JP3531678B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001080919A (en) * | 1999-07-09 | 2001-03-27 | Tosoh Corp | Zirconia fine powder and method for producing the same |
| WO2014196100A1 (en) | 2013-06-04 | 2014-12-11 | 新日本電工株式会社 | Ceria-zirconia mixed oxide and method for producing same |
| JP5706546B1 (en) * | 2013-06-04 | 2015-04-22 | 新日本電工株式会社 | Ceria-zirconia composite oxide and method for producing the same |
| US10010868B2 (en) | 2013-06-04 | 2018-07-03 | Nippon Denko Co., Ltd. | Ceria-zirconia-based composite oxide and method of production of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3531678B2 (en) | 2004-05-31 |
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