JPS61111919A - Production of zirconium oxide fine powder - Google Patents
Production of zirconium oxide fine powderInfo
- Publication number
- JPS61111919A JPS61111919A JP23335284A JP23335284A JPS61111919A JP S61111919 A JPS61111919 A JP S61111919A JP 23335284 A JP23335284 A JP 23335284A JP 23335284 A JP23335284 A JP 23335284A JP S61111919 A JPS61111919 A JP S61111919A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium
- water
- zirconium oxide
- zirconium salt
- 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.)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
本発明は、酸化ジルコニウム微粉末の製造方法【関する
。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] The present invention relates to a method for producing fine zirconium oxide powder.
従来酸化ジルコニウム微粉末の製造方法は。 What is the conventional manufacturing method of zirconium oxide fine powder?
ＺｒＯ２濃度換算で５０〜１ｏ ａ ｔ／ｌのジルコニ
ウム塩水溶液中へアルカリ添加し、中和洗浄、濾過を行
っていた。An alkali was added to an aqueous solution of zirconium salt at a concentration of 50 to 1 oat/l in terms of ZrO2 concentration, and neutralization washing and filtration were performed.
さらＫＷ過ケーキを仮焼後、破砕し、酸化ジルコニウム
を得ていた。After calcining the KW filter cake, it was crushed to obtain zirconium oxide.
しかしながら、上記方法ではゲル状になり易く、従って
濾過性が悪＜、濾過洗浄に長時間を要する欠点を有して
いた。However, the above method has disadvantages in that it tends to become gel-like, resulting in poor filterability and requiring a long time for filtration and cleaning.
また、このため洗浄も不十分になり易く、仮焼時におけ
る凝集をもたらし１粒子が粗大化し好ましいものが得ら
れなかった。In addition, cleaning tends to be insufficient for this reason, resulting in agglomeration during calcination, resulting in coarse particles, making it impossible to obtain a desirable product.
さらに破砕等の工程が必然的に必要となり。Furthermore, processes such as crushing are inevitably required.
これによる不純物の混入の問題を生じるなど種々の問題
を生じていた。This has caused various problems such as the problem of contamination with impurities.
本発明者等は、上記欠点を排除すべく鋭意検討した結果
、水溶性ジルコニウム塩とアルカリ水を、ジルコニウム
塩の濃度としてＺｒＯ，換算３００〜４５０ ？／ｌで
反応させ微粉末を得ることを発明した。As a result of intensive studies to eliminate the above-mentioned drawbacks, the inventors of the present invention determined that water-soluble zirconium salt and alkaline water had a concentration of zirconium salt of 300 to 450 in terms of ZrO. He invented a method to obtain a fine powder by reacting at 1/l.
また具体的実施態様として。Also as a specific embodiment.
水溶性ジルコニウム塩をアルカリ水の中へ添加し９反応
させる方法。A method in which a water-soluble zirconium salt is added to alkaline water and reacted.
水溶性ジルコニウム塩に対し、アルカリ濃度を［１５モ
ル以上の過剰で反応させる方法。A method in which a water-soluble zirconium salt is reacted with an alkali concentration in excess of 15 moles or more.
ジルコニウム塩がオキシ塩化ジルコニウム。Zirconium salt is zirconium oxychloride.
硝酸ジルコニウム、硫酸ジルコニウム塩のいずれか一種
以上である方法。A method using one or more of zirconium nitrate and zirconium sulfate.
反応波濾過した後、アルコール洗浄する方法。A method of washing with alcohol after reaction wave filtration.
反応後、洗浄、濾過し、仮焼する際、仮焼の昇温速度を
５０〜ｂ
アルコールが、Ｃ８〜Ｃ，アルコールでアル方法。After the reaction, washing, filtration, and calcining, the heating rate of calcining is set at 50 to 50% alcohol.
反応時に、安定化剤であるカルシウム、マグネシウム、
イツトリウムの塩のうち一種以上を含む方法。During the reaction, stabilizers such as calcium, magnesium,
A method containing one or more of the salts of yztrium.
を発明した。invented.
以下本発明について詳細に説明する。The present invention will be explained in detail below.
本発明で用いるジルコニウムは水溶性ジルコニウム塩で
あり、オキシ塩化ジルコニウム、硝酸ジルコニウム、硫
酸ジルコニウムのいずれか一種以上であることが好まし
い。The zirconium used in the present invention is a water-soluble zirconium salt, and is preferably one or more of zirconium oxychloride, zirconium nitrate, and zirconium sulfate.
水溶性ジルコニウム塩は、アルカリ水と反応させる。The water-soluble zirconium salt is reacted with alkaline water.
アルカリ水と水溶性ジルコニウム塩と反応させる場合に
は、 ＺｒＯ２換算で３００−４５０ ’ｆ／ｌの濃
度で反応させる。ＺｒＯ□濃度が高いと第１図に示すご
とぐ濾過性が良く、その後処理が容易なため微細なＺｒ
Ｏ□を得ることが容易なためである。ただ４５０ ｆ／
Ｌ以上になるとゲル状態がひど（なり１反応し難くなる
。When alkaline water is reacted with a water-soluble zirconium salt, the reaction is carried out at a concentration of 300-450 f/l in terms of ZrO2. If the ZrO
This is because it is easy to obtain O□. Just 450 f/
If it exceeds L, the gel state becomes severe (it becomes difficult to react).
水溶性ジルコニウムとアルカリ水との反応は。What is the reaction between water-soluble zirconium and alkaline water?
水溶性ジルコニウム塩とアルカリ水と同時に反応槽に入
れるか、好ましくはアルカリ水中に水溶性ジルコニウム
塩とを反応させる。The water-soluble zirconium salt and alkaline water are put into a reaction tank at the same time, or preferably the water-soluble zirconium salt is reacted in alkaline water.
この方法により、より濾過性の良いＺｒＯ２粉を得るこ
とができる。By this method, ZrO2 powder with better filterability can be obtained.
マタ、アルカリ水の濃度は、水溶性ジルコニウム塩に対
し、０．５モル以上の過剰で反応させることが好ましい
。The concentration of alkaline water is preferably 0.5 mole or more in excess of the water-soluble zirconium salt.
即ち、水溶性ジルコニウム塩の濃度をよシ高く、アルカ
リ水の濃度をよシ濃い状態で一時に反応を生ぜしめるこ
とが一番好ましい反応なのである。That is, the most preferable reaction is to carry out the reaction at a high concentration of water-soluble zirconium salt and high concentration of alkaline water at the same time.
アルカリ水は、 ＮＨ，ＯＨ水、 ＮａＯＨ水、ＫＯ
Ｈ水等が用いられるが、アルカリ金属を嫌う用途の場合
はＮＨ４ＯＨ水が好ましい。Alkaline water is NH, OH water, NaOH water, KO
H water or the like is used, but NH4OH water is preferable for applications that dislike alkali metals.
また、構造材等として用いる場合あるいはその他機能材
と用いる場合に、安定剤又は準安定剤を必要とする場合
は、イツトリウム、マグネシウム、イツトリウムの壇の
うち、いずれが一種以上を含ませる。この添加は、水溶
性ジルコニウム塩とアルカリ水との反応時に添加するこ
とが好ましい。よシ微細なＺｒＯ，粉を得ることができ
るためである。In addition, if a stabilizer or metastabilizer is required when used as a structural material or with other functional materials, one or more of yttrium, magnesium, and yttrium base is included. This addition is preferably carried out during the reaction of the water-soluble zirconium salt and alkaline water. This is because very fine ZrO powder can be obtained.
水溶性ジルコニウム塩とアルカリ水との反応温度は、２
０〜４０℃の範囲で行うことが好ましい。The reaction temperature between water-soluble zirconium salt and alkaline water is 2
It is preferable to carry out in the range of 0-40 degreeC.
反応は１〜３時間程度攪拌し、熟成させる。The reaction is stirred and aged for about 1 to 3 hours.
生成した水酸化ジルコニウムは、蒸留水を添加し５〜２
０分攪拌し、１０〜３０分静置し上澄液を排出し、濾過
し洗浄を行う。この洗浄は６〜１０回行われる。該洗浄
後好ましくはアルコール洗浄する。二次凝集を防止する
ためである。これは第２図に示すとと〈濾過ケーキ中の
ＺｒＯ□濃度が高いことから、好ましいことが容易に把
握できる。The generated zirconium hydroxide is mixed with distilled water for 5 to 2 hours.
Stir for 0 minutes, leave to stand for 10 to 30 minutes, drain the supernatant, filter and wash. This washing is performed 6 to 10 times. After this washing, it is preferable to wash with alcohol. This is to prevent secondary aggregation. This is easily understood from the fact that the ZrO□ concentration in the filter cake is high as shown in FIG. 2.
この場合のアルコールは、０２〜Ｃｓアルコールである
。このアルコールの中で好ましくは、イソプロピルアル
コールである。The alcohol in this case is 02-Cs alcohol. Among these alcohols, isopropyl alcohol is preferred.
アルコール洗浄後濾過し、仮焼を行う。After washing with alcohol, it is filtered and calcined.
仮焼の昇温速度は５０〜ｂ ことが好ましい。二次凝集を極力避けるためである。Temperature increase rate for calcination is 50~b It is preferable. This is to avoid secondary aggregation as much as possible.
仮焼温度は７００〜９００℃である。仮焼保持時間は２
〜６時間である。The calcination temperature is 700 to 900°C. Calcination holding time is 2
~6 hours.
以上の内容を実施することにより、以下の効果が得られ
る。By implementing the above contents, the following effects can be obtained.
（１） 極めて濾過性の良い水酸化ジルコニウムが得
られるため、活性の高い超微粉末のＺｒＯ，を得ること
ができる。(1) Since zirconium hydroxide with extremely good filterability is obtained, highly active ultrafine powder ZrO can be obtained.
ＺｒＯ２粉の粒子径が１００〜２２０又の微粉が得られ
る。A fine powder of ZrO2 powder having a particle size of 100 to 220 is obtained.
また比表面積は２０〜５０ ｒｄ／ｌのものが得られる
。Further, a specific surface area of 20 to 50 rd/l can be obtained.
細孔容積は（Ｌ２００ｃｒｊｆ 〜α２６０ｃｃ／ｙ
（７）ものが得られる。The pore volume is (L200crjf ~ α260cc/y
(7) You can get something.
（２） また得られるＺｒＯ，粉は微粉であり、かつ
活性の高いＺｒＯ２粉が得られる。(2) In addition, the ZrO powder obtained is a fine powder and highly active ZrO2 powder can be obtained.
（３） さらに構造材等に用いる場合は、極めて高い
強度をもたらす。(3) Furthermore, when used for structural materials, etc., it provides extremely high strength.
（４） 濾過性が２０〜４０倍であるため生産性が高
い。(4) Productivity is high because the filterability is 20 to 40 times higher.
実施例１
蒸留水１６５ｍｊにオキシ塩化ジルコニウム（Ｚｒ０Ｃ
２，・８Ｈ２０） ３２５ ｔを加えて溶解させた水溶
液（３５ｏｉ）をアンモニア水（ＮＨ８２９ｗｔ４）
２００−の中へ添加し、温度３０℃で２時間攪拌熟成す
る。そのスラリーの中へ７５０−の蒸留水を添加後１０
分間攪拌、２０分間静置して上澄液を排出、この操作を
くり返し行い洗浄を行った後、プフナーロートで濾過、
取シ出したケーキをイソプロピルアルコール９００ｒＲ
１で再度洗浄濾過し、ケーキを取シ出し石英ボー１４入
れ１００℃／ｈｒで昇温、７００℃で４時間加熱焙焼を
行い、酸化ジルコニウムで１１Ｏｆを得た。Example 1 Zirconium oxychloride (Zr0C) was added to 165 mj of distilled water.
2,・8H20) Add and dissolve the aqueous solution (35 oi) of 325 t into ammonia water (NH829wt4).
200- and aged with stirring at a temperature of 30°C for 2 hours. After adding 750 - of distilled water into the slurry, 10
Stir for 20 minutes, let stand for 20 minutes, drain the supernatant, repeat this process for washing, and then filter with a Puchner funnel.
Pour the removed cake into isopropyl alcohol 900rR.
The cake was washed and filtered again in Step 1, and the cake was taken out and placed in a quartz bowl 14 at a rate of 100° C./hr. The mixture was heated and roasted at 700° C. for 4 hours to obtain 11Of with zirconium oxide.
得られた粉体のＸ線回折線の半価幅（１１１）面による
５ｈｅｒｒｅｒの式を用いた粒子径は１７０Ａであシ、
電子顕微鏡での結果は２００Ａであった（第３図）。こ
れら粉体の比表面積は２７ｉ／７細孔容積ＣＬ２２８Ｃ
Ｃ／ｆであった。The particle diameter using the 5herrer formula based on the half width (111) plane of the X-ray diffraction line of the obtained powder was 170A,
The result of electron microscopy was 200A (Fig. 3). The specific surface area of these powders is 27i/7 pore volume CL228C
It was C/f.
実施例２
蒸留水１６５−にオキシ塩化ジルコニウム（ＺｒＯＯｔ
、−８Ｈ，Ｏ） ３２５ ｔ 、塩化イツトリウム（Ｙ
Ｃｌ３・６Ｈ＊Ｏ） １ ＆ １ ｔを加えて溶解させ
た水溶液３７０−を、アンモニア水（ＮＨ３２８ｗｔ４
） ２１０−の中へ添加し、温度３０℃で２時間攪拌熟
成する。Example 2 Zirconium oxychloride (ZrOOt) in distilled water 165-
, -8H,O) 325 t, yttrium chloride (Y
Cl3.6H*O) 1 & 1 t was added and dissolved in an aqueous solution 370-, and aqueous ammonia (NH328wt4
210-, and stirred and aged at a temperature of 30°C for 2 hours.
熟成後、そのスラリーの中へ７５０−の蒸留水を添加後
１０分間攪拌、２０分間靜置し上澄液を排出、この操作
をくり返し行い洗浄を行った後、プフナーロートで濾過
、取り出されたケーキはイソプロピルアルコール９００
−で洗浄ヂ過後ケーキを取り出し石英ボートに入れｉｏ
。After ripening, 750-g distilled water was added to the slurry, stirred for 10 minutes, left to stand for 20 minutes, and the supernatant liquid was drained. After repeating this operation and washing, the cake was filtered with a Puchner funnel and removed. is isopropyl alcohol 900
After washing with −, take out the cake and put it in a quartz boat.
.
ｃ／ｈｒで昇温、７００℃で４時間加熱焙焼を行い、準
安定化ジルコニア１２２ｆを得た。得られた粉体のＸ線
回折線の半価幅（１１１）面より。The temperature was raised at a rate of c/hr, and heating and roasting was performed at 700° C. for 4 hours to obtain meta-stabilized zirconia 122f. From the half width (111) plane of the X-ray diffraction line of the obtained powder.
５ｈｅｒｒｅｒの式を用いた粒子径は１２０Ａであり。The particle size using the 5herrer formula is 120A.
電子顕微鏡での結果は１５０Ａであった（第４図）。こ
れら粉体の比表面積は４４ ｒｄ／ｌ 、細孔容積ｃＬ
２４６ｃｃ／ｒであった。The result of electron microscopy was 150A (Fig. 4). The specific surface area of these powders is 44 rd/l, and the pore volume is cL.
It was 246cc/r.
実施例３
硝酸ジルコニウム（ＺｒＯ（Ｎｏ、）１・２Ｈ２ｏｌ
２４０ ｔを蒸留水２２５−を加えて溶解させた水溶液
をアンモニア水（ＮＨ，２９ｗｔ係）２００−の中へ添
加。Example 3 Zirconium nitrate (ZrO(No,)1.2H2ol
An aqueous solution in which 240 t was dissolved by adding 225 liters of distilled water was added to 200 liters of ammonia water (NH, 29 wt).
温度３０℃で２時間攪拌する。熟成が終了後これらスラ
１１−の中へ７５０−蒸留水を添加、１０分間攪拌、２
０分間靜装して上澄み液を排出する。この操作をくり返
し８回行い洗浄を行った後、ブフナーロートで濾過、取
）出したケーキはイソプロピルアルコール７０〇−洗浄
濾過し取り出したケーキを石英ボートに入れ１００℃／
ｈｒで昇温し７００℃で４時間焙焼を行い、酸化ジルコ
ニウム１０８ｆを得た。Stir for 2 hours at a temperature of 30°C. After completion of ripening, add 750-distilled water into these slurries 11-, stir for 10 minutes, 2
Incubate for 0 minutes and drain the supernatant. This operation was repeated 8 times, and after washing, the cake was filtered with a Buchner funnel.The removed cake was washed and filtered with isopropyl alcohol 700, and the removed cake was placed in a quartz boat at 100°C.
The temperature was raised at 700° C. for 4 hours, and zirconium oxide 108f was obtained.
得られた粉体はＸ線回折線の半価幅（１１１面）による
５ｈｓｒｒθｒの式を用いた粒子径１７０Ａ。The obtained powder had a particle diameter of 170A using the formula 5hsrrθr based on the half width of the X-ray diffraction line (111 planes).
電子顕微鏡の結果２００Ａ、また比表面積は２５ ｄ／
ｆ 、細孔容ｇｃｔｚ３ｓｃｃ／ｐであった。The result of electron microscopy is 200A, and the specific surface area is 25 d/
f, pore volume gctz3scc/p.
第１図はＺｒＯ，濃度と濾過時間の関係、第２図はＺｒ
０２ｍ度と中和洗浄ケーキ中のＺｒＯ，含有量の関係、
第３図は実施例１で得られたＺｒＯ２の顕微鏡写真、第
４図は実施例２で得られたＺｒＯ□＋Ｙ２０゜の顕微鏡
写真を示す。Figure 1 shows the relationship between ZrO concentration and filtration time, Figure 2 shows the relationship between ZrO concentration and filtration time.
Relationship between 02m degree and ZrO content in neutralized washed cake,
FIG. 3 shows a micrograph of ZrO2 obtained in Example 1, and FIG. 4 shows a micrograph of ZrO□+Y20° obtained in Example 2.
Claims (8)
ウム塩の濃度としてＺｒＯ＿２換算３００〜４５０ｇ／
ｌで、反応させ微粉末を得ることを特徴とする酸化ジル
コニウム微粉末の製造方法。(1) Water-soluble zirconium salt and alkaline water, the concentration of zirconium salt is 300 to 450 g/ZrO_2
1. A method for producing fine zirconium oxide powder, characterized in that a fine powder is obtained by reacting in step 1.
、反応させることを特徴とする特許請求の範囲第１項記
載の酸化ジルコニウム微粉末の製造方法。(2) A method for producing fine zirconium oxide powder according to claim 1, characterized in that a water-soluble zirconium salt is added to alkaline water and reacted.
．５モル以上の過剰で反応させることを特徴とする特許
請求の範囲第１項記載の酸化ジルコニウム微粉末の製造
方法。(3) Set the alkali concentration to 0 for water-soluble zirconium salt.
．． 2. The method for producing fine zirconium oxide powder according to claim 1, wherein the reaction is carried out in an excess of 5 moles or more.
ジルコニウム、硫酸ジルコニウム塩のいずれか一種以上
であることを特徴とする特許請求の範囲第１項記載の酸
化ジルコニウム微粉末の製造方法。(4) The method for producing fine zirconium oxide powder according to claim 1, wherein the zirconium salt is one or more of zirconium oxychloride, zirconium nitrate, and zirconium sulfate.
徴とする特許請求の範囲第１項記載の酸化ジルコニウム
微粉末の製造方法。(5) The method for producing fine zirconium oxide powder according to claim 1, which comprises filtering after the reaction and washing with alcohol.
度を５０〜１５０℃／Ｈｒであることを特徴とする特許
請求の範囲第１項記載の酸化ジルコニウム微粉末の製造
方法。(6) Production of zirconium oxide fine powder according to claim 1, characterized in that when washing, filtering, and calcining after the reaction, the heating rate for calcining is 50 to 150°C/Hr. Method.
とを特徴とする特許請求の範囲第５項記載の酸化ジルコ
ニウム微粉末の製造方法。(7) The method for producing fine zirconium oxide powder according to claim 5, wherein the alcohol is a C_2 to C_5 alcohol.
ウム、イットリウムの塩のうち一種以上を含むことを特
徴とする特許請求の範囲第１項記載の酸化ジルコニウム
微粉末の製造方法。(8) The method for producing fine zirconium oxide powder according to claim 1, which comprises containing at least one of calcium, magnesium, and yttrium salts as stabilizers during the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23335284A JPS61111919A (en) | 1984-11-07 | 1984-11-07 | Production of zirconium oxide fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23335284A JPS61111919A (en) | 1984-11-07 | 1984-11-07 | Production of zirconium oxide fine powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61111919A true JPS61111919A (en) | 1986-05-30 |
| JPH0472773B2 JPH0472773B2 (en) | 1992-11-19 |
Family
ID=16953799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23335284A Granted JPS61111919A (en) | 1984-11-07 | 1984-11-07 | Production of zirconium oxide fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61111919A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01188461A (en) * | 1988-01-20 | 1989-07-27 | Noboru Aiko | Al2o3-zro2 ceramic |
| US5318765A (en) * | 1991-03-01 | 1994-06-07 | Degussa Aktiengesellschaft | Monoclinic zirconium dioxide, method of its production and use |
| US6524548B1 (en) | 1994-12-17 | 2003-02-25 | Degussa Ag | Zirconium dioxide powder, method of its production and use |
-
1984
- 1984-11-07 JP JP23335284A patent/JPS61111919A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01188461A (en) * | 1988-01-20 | 1989-07-27 | Noboru Aiko | Al2o3-zro2 ceramic |
| US5318765A (en) * | 1991-03-01 | 1994-06-07 | Degussa Aktiengesellschaft | Monoclinic zirconium dioxide, method of its production and use |
| US6524548B1 (en) | 1994-12-17 | 2003-02-25 | Degussa Ag | Zirconium dioxide powder, method of its production and use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0472773B2 (en) | 1992-11-19 |
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