JPS6197134A - Powder of zirconia agglomerated particle and preparation thereof - Google Patents
Powder of zirconia agglomerated particle and preparation thereofInfo
- Publication number
- JPS6197134A JPS6197134A JP59216767A JP21676784A JPS6197134A JP S6197134 A JPS6197134 A JP S6197134A JP 59216767 A JP59216767 A JP 59216767A JP 21676784 A JP21676784 A JP 21676784A JP S6197134 A JPS6197134 A JP S6197134A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- zirconia
- agglomerated
- aggregated
- powder
- 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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Abstract
Description
【発明の詳細な説明】
本発明は結晶子径が１００Ａ以下の結晶質１次粒子から
成り、特別の微溝造を持ち、ファインセラミックスとし
て最も重要な０３〜３μｍの範囲の且つ比較的狭い部分
にある。はぼ球状をしたジルコニア系凝集粒子粉末、お
よびこれに関連したジルコニア系凝集粒子および凝集粒
子粉末の製造方法に係るものである。ここにジルコニア
系とはジルコニアを主成分とする固溶体や化合物を含め
る意である。Detailed Description of the Invention The present invention consists of crystalline primary particles with a crystallite diameter of 100A or less, has a special microgroove structure, and has a relatively narrow portion in the range of 03 to 3μm, which is the most important for fine ceramics. It is in. The present invention relates to a spherical zirconia-based agglomerated particle powder, and a method for producing the zirconia-based agglomerated particle and agglomerated particle powder related thereto. Here, the term zirconia-based includes solid solutions and compounds containing zirconia as a main component.
最近ファインセラミックスの高性能化とともに。With the recent improvement in the performance of fine ceramics.
使用原料は超微粒子化の傾向にあり、ジルコニア系セラ
ミックス、特に強靭性セラミックスとして注目されてい
る半安定化ジルコニアセラミックスなども超微粒子原料
が次第に重要性を増し、サブミクロンの微粒子、或は５
００人程変身下の超微粒子が使用され始めている。There is a trend toward ultrafine raw materials, and ultrafine raw materials are gradually becoming more important for zirconia ceramics, especially semi-stabilized zirconia ceramics, which are attracting attention as strong ceramics.
About 00 people have begun to use ultrafine particles under the transformation.
しかしながら、微粒子、特に５００Ａ程度以下の超微粒
子は少くとも次の２点において、セラミック製造上重要
な障害を伴うものである。その一つは粉末製造上の問題
であり、他は粉末から成形体を得る際の問題である。However, fine particles, especially ultrafine particles of about 500A or less, pose important obstacles in the production of ceramics in at least the following two points. One of them is a problem in powder production, and the other is a problem in obtaining a molded body from powder.
すなわち一般に５００Ａ以下の超微粒子は、粉末調製の
ための乾燥仮焼の段階で水の作用などにより強固な粒子
間の結合を生じて不規則塊状となり。That is, in general, ultrafine particles of 500A or less form irregular lumps due to strong bonding between particles due to the action of water during the drying and calcining stage for powder preparation.
粉砕しても再び均一粒径の粉末になり難く、超微粒子の
特性の殆んどすべてを失うことである。通常乾燥の前に
水分を高価なアルコール等で置換するか、凍結乾燥によ
るかして強固不規則な凝集化を防ぐ必要があり、繁雑で
且つ不経済なものであった。Even after pulverization, it is difficult to re-form powder with a uniform particle size, and almost all of the characteristics of ultrafine particles are lost. Usually, before drying, it is necessary to replace water with expensive alcohol or the like or freeze-dry to prevent strong and irregular agglomeration, which is complicated and uneconomical.
欠点の他の一つは、セラミック原料粉末は微粒子になる
と、たとえ強固不規則な凝集化を防ぐことができたとし
てもなお著しく成形田無なことである。すなわち微粒子
は均一な密充填が困魚となり、焼成収縮率は増大し、変
形や亀裂が発生し易くなり、焼成後の寸法精度が悪くな
るなどである。Another drawback is that when the ceramic raw material powder becomes fine particles, even if strong and irregular agglomeration can be prevented, it is still extremely difficult to shape. In other words, it is difficult to pack the fine particles evenly and tightly, the firing shrinkage rate increases, deformation and cracks are more likely to occur, and the dimensional accuracy after firing deteriorates.
この成形における均一密充填性を改善する工業的手段は
噴霧乾燥による造粒技術であるが、前述したように水使
用は微粒子の特性を損うため、仮焼などで凝集化した後
でこれを造粒することとなり。The industrial means to improve the uniform close packing properties in this molding is granulation technology using spray drying, but as mentioned above, the use of water impairs the characteristics of the fine particles, so it is necessary to use water after agglomeration by calcination etc. It will be granulated.
この場合構成する凝集粒子は超微粒子の特性を失いかつ
不均一なもので、結局成形体内部組織に不均一性を導入
することとなる。In this case, the constituting agglomerated particles lose the characteristics of ultrafine particles and are non-uniform, resulting in non-uniformity being introduced into the internal structure of the compact.
本発明は活性なジルコニア系超微粒子を、均一な０．３
〜３μｍの範囲でほぼ球状の凝集粒子として液中に生成
させるもので、上記の欠点をすべて除去するものであり
、水による噴霧乾燥処理を行っても微粒子性を失わず、
また噴霧乾燥を必ずしも必要としない球状をしたファイ
ンセラミックス用のジルコニア系微粒子粉末を与えるも
のである。The present invention uses active zirconia-based ultrafine particles with a uniform 0.3
It is produced as approximately spherical agglomerated particles in the range of ~3 μm, which eliminates all of the above drawbacks, and does not lose its fine particle nature even when spray-dried with water.
Further, it provides a spherical zirconia-based fine particle powder for use in fine ceramics that does not necessarily require spray drying.
本発明者は詳細な研究によって、ジルコニウム塩水溶液
の９０〜２５０℃の加熱加水分解によって生成する懸濁
粒子は結晶子径１００Ａ以下の単斜ジルコニア微結晶（
ハフニウム等不純物の固溶体を含む）の双晶的な凝集２
次粒子であり、その２次粒子径は３０〜３０００ Ａの
範囲にあることを見出した。Through detailed research, the present inventor has discovered that suspended particles produced by heating hydrolysis of a zirconium salt aqueous solution at 90 to 250°C are monoclinic zirconia microcrystals (with a crystallite diameter of 100A or less).
(including solid solutions of impurities such as hafnium) twinned agglomeration 2
It was found that the secondary particles are secondary particles, and the secondary particle diameter is in the range of 30 to 3000 A.
しかし如何に条件を変えてもこの凝集粒子は３０００Å
以上には殆んど成長しなかった。従来このような３００
０ Ａ以上の凝集粒子から成る粉末は従って全く得られ
ていなかったし、その特徴についても全く問題にされて
いなかった。本発明はこのような３０００ Ａ以上の大
きさの凝集粒子粉末を容易に製造し実用化させるもので
ある。However, no matter how the conditions are changed, these aggregated particles remain at 3000 Å.
It didn't grow much beyond that. Conventionally, 300 like this
Therefore, no powder consisting of agglomerated particles of 0 A or more has been obtained, and its characteristics have not been questioned at all. The present invention aims to easily produce and put into practical use such agglomerated particle powder having a size of 3000 A or more.
すなわち、ジルコニウム塩水溶液を加熱加水分解して得
られる約１００ＯＡ以上の結晶質ジルコニア系凝集粒子
にジルコニウム塩を加えた混合懸濁水溶液のＰＨを１以
下の強酸性とし、凝集粒子を浮遊状態に保ちながら９０
〜２５０℃の温度で加熱加水分解を行い、懸濁粒子を種
結晶としてこれを３０００λ以上に成長させることを特
徴とするものである。That is, a mixed suspended aqueous solution in which a zirconium salt is added to crystalline zirconia-based aggregated particles of about 100 OA or more obtained by heating and hydrolyzing an aqueous zirconium salt solution is made to have a strongly acidic pH of 1 or less, and the aggregated particles are kept in a suspended state. While 90
It is characterized by performing thermal hydrolysis at a temperature of ~250°C and growing the suspended particles to a size of 3000λ or more using them as seed crystals.
本発明者の実験によれば、ジルコニウム塩の加熱加水分
解の温度は９０’Ｃ以下では成長に時間がかかり過ぎ、
２５０℃以上では１次粒子が大きくなって反応活性を失
うとともに２次凝集粒子相互に接合が生じ始めるので適
当でない。また１０００ Ａ以上の凝集粒子は小さい程
その重量当り成長表面積が大きくなり且つ液中に浮遊し
て成長し易いが自身は３０００λ以上には成長せず、沈
降し易い比較的粗大な凝集粒子の成長を妨げることが判
明した。According to the inventor's experiments, if the heating hydrolysis temperature of zirconium salt is below 90'C, it takes too long for growth.
A temperature of 250° C. or higher is not suitable because the primary particles become large and lose their reaction activity, and the secondary agglomerated particles begin to bond with each other. In addition, the smaller the aggregated particles of 1000 A or more, the larger the growth surface area per weight, and the easier they are to float in the liquid and grow, but they themselves do not grow to over 3000λ, and the growth of relatively coarse aggregated particles that tend to settle. It was found that it hinders.
またＰＨｌ以下の強酸性では孤立微粒子が発生し燈いこ
とも見出された。上記の発明はこれらの実験結果を応用
したものである。It has also been found that in strong acidity below PHL, isolated fine particles are generated and light is emitted. The above invention is an application of these experimental results.
なおさらに実験を繰返し１本発明者は、ＰＨが一層低く
なり、塩酸濃度で１．５Ｎ以上となるとジルコニア系懸
濁粒子は相互に凝集して沈降し始めること、この凝集は
ＰＨが高い場合と異って孤立した０、５〜３μｍ程度の
ほぼ球状の比較的弱い凝集粒子となること、および、さ
らにこの一時的な沈降性凝集粒子は＠濁状態でもしくは
これにジルコニウム塩を加えた懸濁状態で９０℃〜２５
０“′Ｃに加熱処理すれば強固安定な凝集粒子となるこ
となどを見出した。恐らく凝集状態での再結晶あるいは
凝集粒子表面での成長によると考えられる。After repeated experiments, the inventor discovered that when the pH becomes lower and the hydrochloric acid concentration exceeds 1.5N, the zirconia-based suspended particles begin to coagulate and settle, and that this aggregation occurs when the pH is high. Differently, isolated, approximately spherical, relatively weak agglomerated particles of about 0.5 to 3 μm are formed, and furthermore, these temporary sedimentary agglomerated particles are formed in a turbid state or in a suspension with a zirconium salt added thereto. 90℃~25℃
It has been found that heat treatment at 0"'C results in strong and stable aggregated particles. This is probably due to recrystallization in an aggregated state or growth on the surface of the aggregated particles.
本発明の一部は以上の発見に基づくものであり。A part of the present invention is based on the above discovery.
結晶質ジルコニア系微粒子ゾルに＠濁粒子が相互に凝集
して沈降を起すに十分な量の酸を加え、生成する一時的
な沈降性凝集粒子を９０〜２５０℃の温度で必要時間加
熱処理を行い、これを安定な形状の２次凝集粒子に変え
ることを特徴とする方法である。A sufficient amount of acid is added to the crystalline zirconia-based fine particle sol to cause the turbid particles to coagulate with each other and cause sedimentation, and the temporary sedimentary agglomerated particles that are formed are heated at a temperature of 90 to 250°C for the necessary time. This method is characterized by converting the secondary agglomerated particles into stable-shaped secondary agglomerated particles.
本発明方法により得られる以上の凝集粒子は。The above agglomerated particles obtained by the method of the present invention are as follows.
すべて水系の懸濁液の状態として生成し、すべて１００
八以下の結晶質の１次超微粒子から構成され。All are produced as aqueous suspensions, and all are 100%
It is composed of crystalline primary ultrafine particles of 8 or less.
且つ３０００ Ａ以上の孤立化したほぼ球状をした凝集
粒子として得られる点に著しい特徴がある。これは沈降
法又は遠心法によれば粒径の分級が容易であり２通常の
加熱乾燥でその特性を失わず、乾燥後容易にほぐれて孤
立した凝集粒子からなる粉末を与える。これはまさに水
中での微小造粒法と６いえるもので、このような０．３
〜３μｍの微小範囲での造粒は従来全く行れておらず、
特ｌこ特許請求の範囲０）に記載されたジルコニア系凝
集粒子粉末は従来全く得られていないものである。これ
らの凝集を＃御された凝集粒子粉末は後述するように極
めて工業的価値の高いものである。It is also remarkable in that it is obtained as isolated, almost spherical agglomerated particles of 3000 A or more. It is easy to classify the particle size by sedimentation or centrifugation, does not lose its properties by ordinary heat drying, and is easily loosened after drying to give a powder consisting of isolated agglomerated particles. This can be truly called a microgranulation method in water6, and this 0.3
Until now, granulation in the microscopic range of ~3 μm has not been carried out at all,
Particularly, the zirconia-based agglomerated particle powder described in claim 0) has not been obtained at all heretofore. The agglomerated particle powder whose aggregation is controlled has extremely high industrial value, as will be described later.
さらに本発明方法により得られろ凝集粒子の特徴として
、仮焼処理の容易さがある。すなわち沈降法等によって
所望の大きさに分級された上記のような凝集粒子は単独
で、または他の金属化合物を混合し、 １０００℃以
下の増白な温度で熱処理または仮焼することにより、そ
の１次粒子の大きさ。Furthermore, the agglomerated particles obtained by the method of the present invention are characterized by ease of calcining treatment. In other words, the above-mentioned agglomerated particles classified into a desired size by a sedimentation method or the like can be treated alone or mixed with other metal compounds, and then heat-treated or calcined at a whitening temperature of 1000°C or less. Size of primary particles.
結晶形、化学組成、凝集状態などを変化させろことがで
きる。１ｏ００’ｃ以下での仮焼では通常起る凝集粒子
間の接合は内部と較べて相対的に弱いので容易にほぐれ
２ｍ集粒子の形状や粒径の均一性。It is possible to change the crystal shape, chemical composition, agglomeration state, etc. During calcination at temperatures below 1o00'c, the bonds between aggregated particles that normally occur are relatively weak compared to the inside, so they are easily loosened, resulting in uniformity in shape and size of 2m aggregated particles.
孤立性などは殆んど損れない。There is almost no loss of isolation.
以上によって９本発明方法は、最終的に、３ミクロン以
下０．３ミクロンまで（３００００λ〜３０００λ）の
任意の粒径と分布を持つ、はぼ球状をした孤立粒子か・
ら成る理想的なセラミック用粉末を与えるものであり、
しかもこの粉末粒子は０．０５ミクロン（５００Ａ）以
下の１次超微粒子から成る凝集２次粒子であって極めて
活性であり反応性、焼結性に優れ、さらに目的に応じて
仮焼、固相反応などにより化学組成、１次粒子の大きさ
と凝集状態等の内部微組織を適宜調節可能であるなど２
粒子自体も極めて侵れた特性を持つものである。According to the above, the method of the present invention can finally produce isolated particles having a spherical shape and having an arbitrary particle size and distribution of 3 microns or less and up to 0.3 microns (30,000λ to 3,000λ).
It provides an ideal ceramic powder consisting of
Moreover, these powder particles are agglomerated secondary particles consisting of primary ultrafine particles of 0.05 microns (500 A) or less, and are extremely active and have excellent reactivity and sinterability. Chemical composition, primary particle size, agglomeration state, and other internal microstructures can be adjusted appropriately through reactions, etc.2
The particles themselves also have extremely aggressive characteristics.
本発明は以上のように比軸的簡単な方法により殆んど完
壁な形の理想的なジルコニア系凝集粒子粉末の工業的製
造を可能とし、ファインセラミックスの工業生産を初め
研磨剤、化粧品、乳濁剤。As described above, the present invention enables industrial production of ideal zirconia-based agglomerated particle powder with almost perfect shape by a relatively simple method, and is suitable for industrial production of fine ceramics, abrasives, cosmetics, etc. Emulsifier.
などの分野においても優れた価値を持つものである。It has excellent value in other fields as well.
実施例１
試薬塩化ジルコニル（ＺｒＯＣｌｚ・８ルＯ）約１０ｇ
を蒸留水約６０ｍ１中に溶解して約０．５ｍｏｌ／ｄの
溶液とし、その約６０ｍ１を密閉容器中で攪拌しつつ１
５０℃に８時間加熱加水分解を行った。得られた＠濁液
はＸ線的に約４０Ａ の単斜超微結晶が配向的に凝集し
た２次粒子であるが、 １００ＯＡ以下の微細凝集粒
子を含むので遠心分離器により約１０００八以上の部分
を分離し、その一部を種結晶として塩化ジルコニル約１
０ｆと混合し約６０肩ｔの懸濁液を作った。溶液中のＺ
ｒに対する秒結晶の割合はＺｒ比で約Ｌ／′８であった
。この懸濁液を再び密閉′８器中で攪拌しつつ１５０℃
に８時間加熱水分解したところ、Ｘ線的な結晶子径は最
初とほぼ同様の約４０較的均−なほぼ球状の凝集粒子で
あった。さらにこの凝集粒子を種結晶として同様の製作
を繰返し。Example 1 Approximately 10 g of reagent zirconyl chloride (ZrOClz・80)
was dissolved in about 60 ml of distilled water to make a solution of about 0.5 mol/d, and about 60 ml of the solution was dissolved in a closed container while stirring.
Hydrolysis was carried out by heating at 50° C. for 8 hours. The obtained @turbidity is X-ray-detected as secondary particles in which monoclinic ultrafine crystals of approximately 40A are aggregated in an oriented manner, but since it contains fine aggregated particles of less than 100OA, it is separated by centrifugation into particles of approximately 1000A or more. Separate the portion and use it as a seed crystal to produce about 1 zirconyl chloride.
A suspension of approximately 60 kg was prepared by mixing with 0f. Z in solution
The ratio of second crystals to r was approximately L/'8 in terms of Zr ratio. This suspension was heated to 150°C while stirring again in a closed vessel.
When the mixture was heated for 8 hours to undergo water decomposition, the X-ray crystallite size was approximately 40, which was approximately the same as the initial size, and the particles were relatively uniform and approximately spherical. The same process was then repeated using these aggregated particles as seed crystals.
４回目で大部分を約１００００人の凝集粒子にまで成長
させることができた。In the fourth attempt, we were able to grow most of the particles to about 10,000 aggregate particles.
実施例２
上記実施例１により得られた単斜ジルコニア凝集粒子懸
濁液から、遠心分離器により約５０００±５００Ａ程度
に相当する部分を分離し、ジルコニアに対し６モル％に
相当する量の硝酸イツトリウムを加えてよ（混合し、
８００’Ｃで１時間仮焼した。Example 2 From the monoclinic zirconia aggregate particle suspension obtained in Example 1 above, a portion corresponding to approximately 5000±500A was separated using a centrifuge, and nitric acid was added in an amount equivalent to 6 mol% based on the zirconia. Add yztrium (mix and
It was calcined at 800'C for 1 hour.
仮焼物は軽く凝結したが）Ｌ鉢で容易にほぐれた。Although the calcined product was slightly condensed, it was easily loosened in the L pot.
溶体であり、遊離のＹ２Ｏ２は認められなかった。この
粉末に０．３重量％のセロゾール（ステアリン酸懸濁液
）を潤滑剤として加え、造粒製作をせずにそのまま２
ｔ／ｄの圧力で加圧成形し、 １３５０℃に１時間焼
成したところ理論密度のほぼ９８％に相当する焼結体を
与えた。この場合焼成線収縮率は約１５ ’／’（ｌ
でこの種の易焼結性粉末としては収縮率が極めて小さく
、成形時の充填性が非常に優れていることを示した。It was a solution, and no free Y2O2 was observed. 0.3% by weight of cellosol (stearic acid suspension) was added to this powder as a lubricant, and 2
When the material was press-molded at a pressure of t/d and fired at 1350° C. for 1 hour, a sintered body having approximately 98% of the theoretical density was obtained. In this case, the firing line shrinkage rate is approximately 15'/' (l
It was shown that the shrinkage rate was extremely small for this type of easily sinterable powder, and the filling properties during molding were excellent.
実施例３
試薬塩化ジルコニル約９７ｇ 蒸留水約５００ｘｒｌに
溶解し、これに１：１アンモニア水を十分量加えて水酸
化ジルコニウムの沈澱を作った。これを吸引濾過して得
られる含水状態のケーキに試薬塩化ジルコニル３９ダ
を加え攪拌し流動性スラリーとし、これを９７℃で約４
０時間保持し、Ｘ線的には約３ＯＡ （電子顕微鏡でも
約４ＯＡ）の単斜ジルコニア超微結晶を１次粒子とし、
これが配向的に凝集した約１００ＯＡの２次凝集微粒子
から成るゾルを得た。このゾルに１２Ｎ の塩酸を適下
した所。Example 3 Approximately 97 g of reagent zirconyl chloride was dissolved in approximately 500×rl of distilled water, and a sufficient amount of 1:1 aqueous ammonia was added to form a precipitate of zirconium hydroxide. This is filtered under suction, and the resulting water-containing cake is mixed with the reagent zirconyl chloride (39 dA).
was added and stirred to make a fluid slurry, and this was heated to about 4°C at 97°C.
After holding for 0 hours, monoclinic zirconia ultrafine crystals with an X-ray measurement of approximately 3 OA (electron microscopy approximately 4 OA) were used as primary particles.
A sol consisting of secondary agglomerated fine particles of about 100 OA which were oriented and agglomerated was obtained. 12N hydrochloric acid was added to this sol.
塩酸濃度が約２Ｎ付近になった所で沈降分離が起った。Sedimentation separation occurred when the hydrochloric acid concentration reached approximately 2N.
この沈降物は光学顕＠鏡によれば約１μｍ（１００００
Ａ）の球状凝集粒子であるが、凝集は弱く、そのままで
は乾燥粒子にならない。この沈降物に少量の塩化ジルコ
ニル（Ｚｒ比で１／１０）を加え、密閉容器中で攪拌し
つつ１５０℃に８時間加熱処理したところ、Ｘ線的な結
晶子径は僅かに増加（約３５Ａ）するのみで、その２次
凝集粒子は約１μｍで強固安定となり、乾燥により凝集
粒子間は互に固結しない微粉末を与えた。According to an optical microscope, this sediment is about 1 μm (10,000
A) is a spherical agglomerated particle, but the aggregation is weak and it will not become dry particles as it is. When a small amount of zirconyl chloride (Zr ratio: 1/10) was added to this precipitate and heat treated at 150°C for 8 hours while stirring in a closed container, the X-ray crystallite size increased slightly (approximately 35A). ), the secondary agglomerated particles became strong and stable at about 1 μm, and upon drying, a fine powder was obtained in which the agglomerated particles did not coagulate with each other.
得られた粉末粒子の反応性、焼結性は実施例２によって
得られた粉末粒子の結果とほぼ同様のものであった。The reactivity and sinterability of the obtained powder particles were almost the same as those of the powder particles obtained in Example 2.
Claims (4)
が配向的に凝集した２次粒子から成り、ほぼ球状で、大
きさが０．３μｍ〜３μｍの範囲の且つ比較的狭い部分
にあることを特徴とするジルコニア系凝集粒子粉末。(1) Consisting of secondary particles in which monoclinic primary ultrafine particles with a crystallite diameter of 100 Å or less are aggregated in an oriented manner, they are approximately spherical and have a size in the range of 0.3 μm to 3 μm and are formed in a relatively narrow part. A zirconia-based agglomerated particle powder characterized by the following.
る約１０００Å以上の単斜ジルコニア系凝集粒子にジル
コニウム塩を加えた混合懸濁水溶液のＰＨを１以下の強
酸性とし、凝集粒子を浮遊状態に保ちながら９０℃〜２
５０℃の温度で加熱加水分解を行い、懸濁粒子を種結晶
としてこれを３０００Å以上に成長させることを特徴と
するジルコニア系凝集粒子の製造方法。(2) A mixed suspension aqueous solution in which a zirconium salt is added to monoclinic zirconia aggregate particles of approximately 1000 Å or more obtained by heating and hydrolyzing an aqueous zirconium salt solution is made to have a strongly acidic pH of 1 or less to bring the aggregate particles into a suspended state. While maintaining 90℃~2
A method for producing zirconia-based aggregated particles, which comprises performing thermal hydrolysis at a temperature of 50° C. and growing suspended particles to a size of 3000 Å or more using seed crystals.
互に凝集して沈降を起すに十分な量の酸を加え、生成す
る一時的な沈降性凝集粒子を９０〜２５０℃の温度で必
要時間加熱処理を行い、これを安定な形状の２次凝集粒
子に変えることを特徴とするジルコニア系凝集粒子の製
造方法。(3) A sufficient amount of acid is added to the crystalline zirconia-based fine particle sol to cause the suspended particles to coagulate with each other and cause sedimentation, and temporary sedimentary agglomerated particles are generated at a temperature of 90 to 250°C. A method for producing zirconia-based aggregated particles, which comprises performing a heat treatment for a period of time to convert the particles into secondary aggregated particles having a stable shape.
る２次凝集粒子を種結晶としてさらに加水分解を続け３
０００Å以上に成長させたジルコニア系凝集粒子、また
は結晶質ジルコニア系微粒子ゾルに酸を加え一時的な沈
降性凝集粒子としこれを安定な形状の２次粒子に変えた
ジルコニア系凝集粒子の何れかを含む白濁液から沈降又
は遠心分離によって大きさが３０００Å以上の任意の粒
径範囲部分を分離し、これを単独で、またはこれに他の
金属化合物を混合し、１０００℃以下の温度で熱処理す
ることを特徴とするジルコニア系凝集粒子粉末の製造方
法。(4) Further hydrolysis is continued using secondary agglomerated particles obtained from heating hydrolysis of a zirconium salt aqueous solution as seed crystals.
Either zirconia-based aggregated particles grown to a size of 000 Å or more, or zirconia-based aggregated particles made by adding acid to a crystalline zirconia-based fine particle sol to create temporary sedimentary aggregated particles, which are then changed into stable secondary particles. Separate a particle size range of 3000 Å or more from the white cloudy liquid by sedimentation or centrifugation, and heat-treat this alone or in combination with other metal compounds at a temperature of 1000°C or less. A method for producing a zirconia-based agglomerated particle powder, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59216767A JPS6197134A (en) | 1984-10-16 | 1984-10-16 | Powder of zirconia agglomerated particle and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59216767A JPS6197134A (en) | 1984-10-16 | 1984-10-16 | Powder of zirconia agglomerated particle and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6197134A true JPS6197134A (en) | 1986-05-15 |
| JPH0472772B2 JPH0472772B2 (en) | 1992-11-19 |
Family
ID=16693583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59216767A Granted JPS6197134A (en) | 1984-10-16 | 1984-10-16 | Powder of zirconia agglomerated particle and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6197134A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0194556A2 (en) * | 1985-03-04 | 1986-09-17 | Nissan Chemical Industries Ltd. | Powder of coagulated spherical zirconia particles and process for producing them |
| JPH01153530A (en) * | 1987-10-31 | 1989-06-15 | Degussa Ag | Crystalline zirconium oxide powder, method for its manufacture and method for manufacturing sintered ceramic |
| US5248463A (en) * | 1989-09-29 | 1993-09-28 | Nissan Chemical Industries, Ltd. | Preparation of zirconia sintered body |
| US5318765A (en) * | 1991-03-01 | 1994-06-07 | Degussa Aktiengesellschaft | Monoclinic zirconium dioxide, method of its production and use |
| US5326518A (en) * | 1991-10-08 | 1994-07-05 | Nissan Chemical Industries, Ltd. | Preparation of sintered zirconia body |
| JP2004010418A (en) * | 2002-06-06 | 2004-01-15 | Hosokawa Micron Corp | Method of producing zirconia sol and method of producing zirconia fine powder |
| JPWO2006006277A1 (en) * | 2004-07-09 | 2008-04-24 | 旭化成ケミカルズ株式会社 | Catalyst and process for producing cycloolefin |
| JP2008526669A (en) * | 2004-12-30 | 2008-07-24 | スリーエム イノベイティブ プロパティズ カンパニー | Zirconia particles |
| JP2012236763A (en) * | 2012-07-17 | 2012-12-06 | Sumitomo Osaka Cement Co Ltd | Method for producing particle aggregate |
-
1984
- 1984-10-16 JP JP59216767A patent/JPS6197134A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0194556A2 (en) * | 1985-03-04 | 1986-09-17 | Nissan Chemical Industries Ltd. | Powder of coagulated spherical zirconia particles and process for producing them |
| JPH01153530A (en) * | 1987-10-31 | 1989-06-15 | Degussa Ag | Crystalline zirconium oxide powder, method for its manufacture and method for manufacturing sintered ceramic |
| JPH0574532B2 (en) * | 1987-10-31 | 1993-10-18 | Degussa | |
| US5248463A (en) * | 1989-09-29 | 1993-09-28 | Nissan Chemical Industries, Ltd. | Preparation of zirconia sintered body |
| US5318765A (en) * | 1991-03-01 | 1994-06-07 | Degussa Aktiengesellschaft | Monoclinic zirconium dioxide, method of its production and use |
| US5326518A (en) * | 1991-10-08 | 1994-07-05 | Nissan Chemical Industries, Ltd. | Preparation of sintered zirconia body |
| JP2004010418A (en) * | 2002-06-06 | 2004-01-15 | Hosokawa Micron Corp | Method of producing zirconia sol and method of producing zirconia fine powder |
| JPWO2006006277A1 (en) * | 2004-07-09 | 2008-04-24 | 旭化成ケミカルズ株式会社 | Catalyst and process for producing cycloolefin |
| JP4777891B2 (en) * | 2004-07-09 | 2011-09-21 | 旭化成ケミカルズ株式会社 | Catalyst and process for producing cycloolefin |
| JP2008526669A (en) * | 2004-12-30 | 2008-07-24 | スリーエム イノベイティブ プロパティズ カンパニー | Zirconia particles |
| JP2012236763A (en) * | 2012-07-17 | 2012-12-06 | Sumitomo Osaka Cement Co Ltd | Method for producing particle aggregate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0472772B2 (en) | 1992-11-19 |
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