JPH01301502A - Production of ceramic microsphere - Google Patents
Production of ceramic microsphereInfo
- Publication number
- JPH01301502A JPH01301502A JP31712388A JP31712388A JPH01301502A JP H01301502 A JPH01301502 A JP H01301502A JP 31712388 A JP31712388 A JP 31712388A JP 31712388 A JP31712388 A JP 31712388A JP H01301502 A JPH01301502 A JP H01301502A
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- metal compound
- aqueous solution
- soluble metal
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 239000004005 microsphere Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 35
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
- C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は水溶性金属化合物の水溶液に油を混合し超音波
振動により生成した油中水型エマルジョンを加熱するこ
とにより、水分と油分を除去してセラミックマイクロ球
を製造する方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention removes water and oil by mixing oil with an aqueous solution of a water-soluble metal compound and heating a water-in-oil emulsion generated by ultrasonic vibration. The present invention relates to a method for manufacturing ceramic microspheres.
［従来の技術］
この種のセラミックマイクロ球の製造方法として、本出
願人はセラミック微粉体を水に分散させた懸濁液をこの
懸濁液とほぼ同じ比重であって水と混合せずかつセラミ
ック微粉体と反応しない高沸点液体中に小滴状で分散さ
せた後、セラミックマイクロ球を得る方法を特許出願し
く特開昭６ｌ−２６３６２８） 、更にセラミック微粉
体をアルコール溶液中に分散させた懸濁液又はゾルを流
動パラフィン中に小滴状に分散させた後、アルコールを
蒸発させてセラミックマイクロ球を得る方法を特許出願
した（特開昭６２−２６２７３４）。[Prior Art] As a method for producing this type of ceramic microspheres, the applicant has developed a method for producing a suspension of fine ceramic powder dispersed in water, which has approximately the same specific gravity as this suspension and which is not mixed with water. A patent application has been filed for a method for obtaining ceramic microspheres by dispersing them in the form of small droplets in a high-boiling liquid that does not react with the ceramic fine powder (Japanese Patent Application Laid-Open No. 61-263628), and the ceramic fine powder was further dispersed in an alcohol solution. A patent application was filed for a method for obtaining ceramic microspheres by dispersing a suspension or sol in liquid paraffin in the form of small droplets and then evaporating the alcohol (Japanese Patent Laid-Open No. 62-262734).
［発明が解決しようとする課題］
上記従来の製造方法は、均一な粒径を有する真球のセラ
ミックマイクロ球が得られる優れた方法であるが、オリ
フィスを通してセラミック微粉体の懸濁液を高沸点液体
中に小滴状に分散させるため、得られるセラミックマイ
クロ球の平均粒径はオリフィス径に依存し、数μｍから
数１０μｍの比較的大きなものしかつくることができな
い。[Problems to be Solved by the Invention] The conventional manufacturing method described above is an excellent method for obtaining truly spherical ceramic microspheres having a uniform particle size. Since the ceramic microspheres are dispersed in the form of small droplets in a liquid, the average particle size of the resulting ceramic microspheres depends on the orifice diameter, and only relatively large particles ranging from several μm to several tens of μm can be produced.
また上記従来の製造方法は、懸濁液を調製するために使
用するセラミック微粉体の粒径が常に目的とするセラミ
ックマイクロ球の粒径よりも遥かに小さな粒径であるこ
とが必要であり、そのためアルコキシド加水分解法のよ
うな特別の製法によりつくられた微細なセラミック微粉
体を用いなければならない不具合があった。Furthermore, in the conventional manufacturing method described above, it is necessary that the particle size of the ceramic fine powder used to prepare the suspension is always much smaller than the particle size of the target ceramic microspheres. Therefore, there was a problem in that fine ceramic powder produced by a special manufacturing method such as an alkoxide hydrolysis method had to be used.
本発明の目的は、出発原料として微細なセラミック微粉
体を必要とすることなく、粒度分布幅の狭い、サブミク
ロンオーダの平均粒径を有するセラミックマイクロ球が
得られるセラミックマイクロ球の製造方法を提供するこ
とにある。An object of the present invention is to provide a method for producing ceramic microspheres that does not require fine ceramic powder as a starting material, and can produce ceramic microspheres with a narrow particle size distribution and an average particle size on the submicron order. It's about doing.
また本発明の別の目的は、油中水型エマルジョンを生成
するための超音波の周波数を変えることにより所望の平
均粒径のセラミックマイクロ球を作り出せるセラミック
マイクロ球の製造方法を提供することにある。Another object of the present invention is to provide a method for producing ceramic microspheres that can produce ceramic microspheres with a desired average particle size by changing the frequency of ultrasonic waves for producing a water-in-oil emulsion. .
［課題を解決するための手段］
上記目的を達成するために、本発明のセラミックマイク
ロ球の製造方法は、水溶性金属化合物が溶解した水溶液
にこの水溶液に不溶で水より高沸点の油を混合し、この
混合液に超音波振動を与えて油中水型エマルジョンを生
成し、このエマルジョンを水の沸点未満の温度で加熱し
、前記水溶性金属化合物が溶解する液滴の水分を萬発さ
せて油相に球形の水溶性金属化合物を分散させた後、こ
の分散液を前記水溶性金属化合物が分解し金属酸化物と
なる温度以上でこの金属酸化物の粒成長開始温度未満の
温度範囲で加熱して油を蒸発又は分解して除去し、金属
酸化物のマイクロ球を得る方法である。[Means for Solving the Problems] In order to achieve the above object, the method for manufacturing ceramic microspheres of the present invention includes mixing an aqueous solution in which a water-soluble metal compound is dissolved with an oil that is insoluble in this aqueous solution and has a higher boiling point than water. Then, ultrasonic vibration is applied to this mixed liquid to generate a water-in-oil emulsion, and this emulsion is heated at a temperature below the boiling point of water to devour the water in the droplets in which the water-soluble metal compound is dissolved. After dispersing a spherical water-soluble metal compound in an oil phase, the dispersion is heated in a temperature range above the temperature at which the water-soluble metal compound decomposes to form a metal oxide and below the temperature at which grain growth of the metal oxide starts. In this method, the oil is removed by evaporation or decomposition by heating to obtain metal oxide microspheres.
本発明の出発原料は目的とするセラミックスを構成する
水溶性金属化合物である。この水溶性金属化合物を所定
の組成比で２０〜５０℃の水に溶解して水溶液を調製す
る。The starting material of the present invention is a water-soluble metal compound constituting the desired ceramic. An aqueous solution is prepared by dissolving this water-soluble metal compound in water at a temperature of 20 to 50°C at a predetermined composition ratio.
この水溶液に油を混合して油中水型エマルジョンを生成
する。油は上記水溶液に不溶でありかつ水より高沸点の
ものであれば、特に限定されず、毒性及び価格の点から
パラフィン油が望ましい。Oil is mixed with this aqueous solution to produce a water-in-oil emulsion. The oil is not particularly limited as long as it is insoluble in the aqueous solution and has a boiling point higher than water, and paraffin oil is preferred from the viewpoint of toxicity and cost.
またエマルジョンを生成する際にはエマルジョンを長時
間安定に存在させるために乳化剤を使用した方がよい。Furthermore, when producing an emulsion, it is better to use an emulsifier in order to keep the emulsion stable for a long time.
この乳化剤はイオン系乳化剤、非イオン系乳化剤等いず
れの乳化剤でもよい。上記水溶液１００重量部に対して
油は３５〜１００重量部また乳化剤は１〜６重量部混合
する。This emulsifier may be any emulsifier such as an ionic emulsifier or a nonionic emulsifier. 35 to 100 parts by weight of oil and 1 to 6 parts by weight of emulsifier are mixed with 100 parts by weight of the above aqueous solution.
本発明の特徴ある点の１つはエマルジョンを超音波振動
により生成する。エマルジョンの生成を超音波振動以外
の攪拌式ホモジナイザ、圧力式ホモジナイザ等の手段で
行った場合には、液滴の径は部分的にサブミクロンのオ
ーダとなるが、平均的にサブミクロンのオーダとならず
、しかもその液滴径の分布幅は広いため、最終的に得ら
れるセラミックマイクロ球の平均粒径が大きくかつ不揃
いとなる。このため超音波振動以外の方法は本発明に適
しない。この超音波の周波数は１０ｋＨｚ〜１００ｋＨ
ｚの範囲が好ましい。超音波は一般的に可聴域より上の
周波数、すなわち２０ｋＨｚ以上の音波であるが、本発
明では１０ｋＨｚの周波数においても液滴の平均径をサ
ブミクロンのオーダにすることができるので、周波数が
１０ｋＨｚ以上で２０ｋＨｚ未満の音波についても、超
音波の用語を用いる。周波数を高めて強い超音波にする
と、本発明の最終生成物であるセラミックマイクロ球の
平均粒径がより一層細かくなり、反対に周波数を低くし
て弱い超音波にすると、平均粒径が大きくなる。このこ
とから超音波の周波数を適宜選定すれば、平均粒径を所
望の値に設定することができる。One of the characteristics of the present invention is that the emulsion is generated by ultrasonic vibration. When the emulsion is generated using a means other than ultrasonic vibration, such as a stirring homogenizer or a pressure homogenizer, the diameter of the droplets is partially on the order of submicrons, but on average it is on the order of submicrons. Moreover, since the distribution width of the droplet size is wide, the average particle size of the ceramic microspheres finally obtained is large and irregular. Therefore, methods other than ultrasonic vibration are not suitable for the present invention. The frequency of this ultrasonic wave is 10kHz to 100kHz
A range of z is preferred. Ultrasonic waves generally have a frequency above the audible range, that is, a sound wave of 20 kHz or more, but in the present invention, even at a frequency of 10 kHz, the average diameter of droplets can be made to the order of submicrons. In the above, the term ultrasonic wave is also used for sound waves of less than 20 kHz. If the frequency is increased to make the ultrasound stronger, the average particle size of the ceramic microspheres, which is the final product of the present invention, will become finer. Conversely, if the frequency is lowered to make the ultrasound weaker, the average particle size will become larger. . From this, by appropriately selecting the frequency of the ultrasonic waves, the average particle size can be set to a desired value.
生成したエマルジョンを加熱して水溶性金属化合物が溶
解する液滴の水分を蒸発させるときの加熱温度は、高温
の方が迅速に液滴の水分を除去できるが、１００℃を越
えると水の沸騰が起きエマルジョンが壊れるので、１０
０℃未満、望ましくは７０〜９５℃がよい。When heating the generated emulsion to evaporate the water in the droplets in which the water-soluble metal compound is dissolved, the higher the heating temperature, the faster the water in the droplets can be removed, but if the temperature exceeds 100°C, the water will boil. occurs and the emulsion breaks, so 10
The temperature is preferably less than 0°C, preferably 70 to 95°C.
更に油を蒸発又は分解するとともに水溶性金属化合物を
熱分解するときの加熱温度は、水溶性金属化合物が分解
し金属酸化物となる温度以上でこの金属酸化物の粒成長
開始温度未満の温度であることが必要である。Furthermore, the heating temperature when evaporating or decomposing the oil and thermally decomposing the water-soluble metal compound is at least the temperature at which the water-soluble metal compound decomposes into a metal oxide and lower than the temperature at which grain growth of this metal oxide starts. It is necessary that there be.
［作 用］
水溶性金属化合物が溶解した水溶液に油を混合し、必要
により乳化剤を加えて超音波振動を与えると、超音波に
よる強力なキャビテーション効果が混合液全体に均一に
加わり、前記水溶液がサブミクロンのオーダの液滴にま
で細分割されて油相に分散する。ここで超音波の周波数
を適宜選定すれば、マイクロ球の所望の平均粒径を決め
ることができる。[Function] When oil is mixed with an aqueous solution in which a water-soluble metal compound is dissolved, an emulsifier is added if necessary, and ultrasonic vibration is applied, a strong cavitation effect due to ultrasonic waves is uniformly applied to the entire mixed solution, and the aqueous solution is It is finely divided into droplets on the order of submicrons and dispersed in the oil phase. By appropriately selecting the frequency of the ultrasonic waves, a desired average particle size of the microspheres can be determined.
このエマルジョンを加熱して水溶性金属化合物が溶解す
る液滴の水分を蒸発させると、液滴が濃縮され、油相に
サブミクロンのオーダの球形の水溶性金属化合物が分散
する。When this emulsion is heated to evaporate the water in the droplets in which the water-soluble metal compound is dissolved, the droplets are concentrated and the spherical water-soluble metal compound on the order of submicrons is dispersed in the oil phase.
この水溶性金属化合物が分散した油液を加熱して油を蒸
発又は分解するとともに水溶性金属化合物を熱分解させ
れば、サブミクロンのオーダの金属酸化物のマイクロ球
が得られる。By heating the oil liquid in which the water-soluble metal compound is dispersed to evaporate or decompose the oil and thermally decompose the water-soluble metal compound, submicron-order metal oxide microspheres can be obtained.
［発明の効果］
以上述べたように、本発明の製造方法は、超音波振動に
よりサブミクロンのオーダの水溶性金属化合物の液滴が
油相に分散するエマルジョンを生成した後、このエマル
ジョンを加熱して水と油を順次除去してセラミックマイ
クロ球を製造するので、従来のように出発原料として微
細なセラミック微粉体を用いずに、真球に近い粉体粒子
が得られる。[Effects of the Invention] As described above, the manufacturing method of the present invention involves generating an emulsion in which submicron-order water-soluble metal compound droplets are dispersed in an oil phase by ultrasonic vibration, and then heating this emulsion. Since ceramic microspheres are manufactured by sequentially removing water and oil, powder particles that are close to perfect spheres can be obtained without using fine ceramic powder as a starting material as in the past.
特に乳化が超音波振動により行われ、かつ油の蒸発・分
解温度が金属酸化物の粒成長開始温度未満であるため、
得られた粒子は互いに本質的に点接触するだけで凝集せ
ず、サブミクロンのオーダの平均粒径を有し、かつ粒度
分布幅の狭いセラミックマイクロ球となる。In particular, emulsification is carried out by ultrasonic vibration, and the evaporation and decomposition temperature of the oil is below the grain growth starting temperature of the metal oxide.
The obtained particles essentially only make point contact with each other and do not aggregate, resulting in ceramic microspheres having an average particle size on the order of submicrons and a narrow particle size distribution.
更に超音波の周波数を適宜選定すれば、マイクロ球の平
均粒径を所望の値にすることができる。Furthermore, by appropriately selecting the frequency of the ultrasonic waves, the average particle diameter of the microspheres can be set to a desired value.
［実施例］ 次に本発明の実施例を比較例とともに説明する。[Example] Next, examples of the present invention will be described together with comparative examples.
〈実施例１〉
Ｚｒ０（ＮＯｓ）＊ ・２Ｈ＊０１０ｇを４０℃の水２
５ｇに溶解して水溶液を調製した。この水溶液をパラフ
ィン油５０ｇと乳化剤としてポリ・オキシエチレン・ノ
ニルフェニル・エーテルＩｇを加えた後、超音波発生機
（Ｂｒａｎｓｏｎ社製Ｂ−３０社製上り１５秒間超音波
振動を与えて油中水型エマルジョンを生成した。この時
の超音波の周波数は３０ｋＨｚであった。このエマルジ
ョンを乾燥器に入れ、大気圧下８０℃の温度で８時間乾
燥し、水を蒸発させて除去した。エマルジョンはＺｒＯ
，粒子が分散する懸濁液となった。この懸濁液を大気圧
下７００℃の温度で３時間焼成し油を分解して除去し、
ＺｒＯ，球を得た。走査型電子顕微鏡によりこのＺｒＯ
，球の粒径を測定したところ、平均粒径が０．１μ晴で
粒度分布幅が±０．０２μｍの極めて微細でバラツキの
少ないＺｒＯ２の単分散セラミックマイクロ球であった
。<Example 1> Zr0(NOs)*・2H*010g was added to 40°C water 2
5 g to prepare an aqueous solution. After adding 50 g of paraffin oil and polyoxyethylene nonylphenyl ether Ig as an emulsifier to this aqueous solution, ultrasonic vibration was applied for 15 seconds using an ultrasonic generator (manufactured by Branson B-30). An emulsion was produced.The frequency of the ultrasonic wave at this time was 30kHz.This emulsion was placed in a dryer and dried at a temperature of 80°C under atmospheric pressure for 8 hours to evaporate and remove water.The emulsion was made of ZrO
, resulting in a suspension in which the particles were dispersed. This suspension was calcined at a temperature of 700°C under atmospheric pressure for 3 hours to decompose and remove the oil.
ZrO, spheres were obtained. Using a scanning electron microscope, this ZrO
When the particle size of the spheres was measured, they were found to be extremely fine and uniform ZrO2 monodisperse ceramic microspheres with an average particle size of 0.1 μm and a particle size distribution width of ±0.02 μm.
く比較例１〉
超音波発生機の代わりに攪拌式ホモジナイザによりエマ
ルジョンを生成したこと以外は°実施例１と同様にして
Ｚｒ０ｍ球を得た。実施例１と同様にこのＺｒＯ，の粒
径を測定したところ、０．１〜３μｍの粒度分布幅の広
いセラミックマイクロ球であった。Comparative Example 1 Zr0m spheres were obtained in the same manner as in Example 1, except that the emulsion was produced using a stirring homogenizer instead of the ultrasonic generator. When the particle size of this ZrO was measured in the same manner as in Example 1, it was found to be ceramic microspheres with a wide particle size distribution of 0.1 to 3 μm.
〈実施例２〉
ＺｒＯ（Ｎｏｗ）＊ ・２Ｈ！０５．３４ｇとＰｂ（Ｃ
ＨｓＣＯＯ）＊ ・３Ｈｔ０６．７６ｇとを４０℃の水
２５ｇに溶解した水溶液を使用したこと以外は実施例１
と同様にしてＰｂＺｒｏａ球を得た。実施例１と同様に
このＰｂＺｒｏａ球の粒径を測定したところ、実施例１
と同じ０．１±０．０２μｍの極めて微細で粒度分布幅
の狭いＰｂＺｒＯｓの単分散セラミックマイクロ球であ
った。<Example 2> ZrO(Now)* ・2H! 05.34g and Pb(C
Example 1 except that an aqueous solution of 06.76 g of 3Ht and 25 g of 40°C water was used.
PbZroa spheres were obtained in the same manner. When the particle size of this PbZroa sphere was measured in the same manner as in Example 1, it was found that Example 1
The PbZrOs monodisperse ceramic microspheres were extremely fine with the same diameter of 0.1±0.02 μm and had a narrow particle size distribution.
く比較例２〉
超音波発生機の代わりに圧力式ホモジナイザによりエマ
ルジョンを生成したこと以外は実施例２と同様にしてＰ
ｂＺｒｏａ球を得た。実施例１と同様にこのＰｂＺｒＯ
ｓの粒径を測定したところ、比較例１と同じ０．１〜３
μｍの粒度分布幅の広いセラミックマイクロ球であった
。Comparative Example 2 P was carried out in the same manner as in Example 2 except that the emulsion was generated using a pressure homogenizer instead of the ultrasonic generator.
bZroa spheres were obtained. As in Example 1, this PbZrO
When the particle size of s was measured, it was 0.1 to 3, the same as in Comparative Example 1.
They were ceramic microspheres with a wide particle size distribution width of μm.
〈実施例３〉
超音波の周波数を１ＯｋＨｚとした以外は実施例１と同
様にしてＺｒＯ，球を得た。実施例１と同様にこのＺｒ
Ｏ□の粒径を測定したところ、平均粒径が実施例１より
若干大きい０．７μｍで粒度分布幅も実施例１より若干
広い±０．１１μｍのＺｒＯ□の単分散セラミックマイ
クロ球であった。<Example 3> ZrO and spheres were obtained in the same manner as in Example 1 except that the frequency of the ultrasonic waves was 10kHz. As in Example 1, this Zr
When the particle size of O□ was measured, it was found to be monodisperse ceramic microspheres of ZrO□ with an average particle size of 0.7 μm, which is slightly larger than Example 1, and a particle size distribution width of ±0.11 μm, which is slightly wider than Example 1. .
〈実施例４〉
超音波の周波数を１００ｋＨｚとした以外は実施例１と
同様にしてＺｒ０ｗ球を得た。実施例１と同様にこのＺ
ｒＯ□の粒径を測定したところ、平均粒径が実施例１よ
り極めて小さい０．０２μｍで粒度分布幅も実施例１よ
り極めて狭い±０．００３μｍのＺｒＯ２の単分散セラ
ミックマイクロ球であった。<Example 4> A Zr0w sphere was obtained in the same manner as in Example 1 except that the frequency of the ultrasonic wave was 100 kHz. As in Example 1, this Z
When the particle size of rO□ was measured, it was found to be monodisperse ceramic microspheres of ZrO2 with an average particle size of 0.02 μm, which is much smaller than in Example 1, and a particle size distribution width of ±0.003 μm, which is much narrower than in Example 1.
一二、′１．−・Ｌ12,'1. -・L
Claims (1)
不溶で水より高沸点の油を混合し、この混合液に超音波
振動を与えて油中水型エマルジョンを生成し、このエマ
ルジョンを水の沸点未満の温度で加熱し、前記水溶性金
属化合物が溶解する液滴の水分を蒸発させて油相に球形
の水溶性金属化合物を分散させた後、この分散液を前記
水溶性金属化合物が分解し金属酸化物となる温度以上で
この金属酸化物の粒成長開始温度未満の温度範囲で加熱
して油を蒸発又は分解して除去し、金属酸化物のマイク
ロ球を得るセラミックマイクロ球の製造方法。 ２）超音波の周波数を１０ｋＨｚ〜１００ｋＨｚの範囲
から選定して所望の平均粒径のマイクロ球を得る請求項
１記載のセラミックマイクロ球の製造方法。 ３）水溶性金属化合物が溶解した水溶液に油とともに乳
化剤を加えて油中水型エマルジョンを生成する請求項１
記載のセラミックマイクロ球の製造方法。[Claims] 1) A water-in-oil emulsion is produced by mixing an aqueous solution in which a water-soluble metal compound is dissolved with an oil that is insoluble in this aqueous solution and has a higher boiling point than water, and applying ultrasonic vibration to this mixture. This emulsion is heated at a temperature below the boiling point of water to evaporate the water in the droplets in which the water-soluble metal compound is dissolved to disperse the spherical water-soluble metal compound in the oil phase. The oil is removed by evaporation or decomposition by heating in a temperature range that is above the temperature at which the water-soluble metal compound decomposes to become a metal oxide and below the temperature at which grain growth of this metal oxide begins, to obtain metal oxide microspheres. Method for manufacturing ceramic microspheres. 2) The method for producing ceramic microspheres according to claim 1, wherein microspheres having a desired average particle size are obtained by selecting the frequency of the ultrasonic waves from a range of 10 kHz to 100 kHz. 3) Claim 1, wherein a water-in-oil emulsion is produced by adding an emulsifier together with oil to an aqueous solution in which a water-soluble metal compound is dissolved.
The method for manufacturing the ceramic microspheres described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31712388A JPH01301502A (en) | 1988-02-18 | 1988-12-15 | Production of ceramic microsphere |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-36239 | 1988-02-18 | ||
| JP3623988 | 1988-02-18 | ||
| JP31712388A JPH01301502A (en) | 1988-02-18 | 1988-12-15 | Production of ceramic microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301502A true JPH01301502A (en) | 1989-12-05 |
| JPH0478562B2 JPH0478562B2 (en) | 1992-12-11 |
Family
ID=26375281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31712388A Granted JPH01301502A (en) | 1988-02-18 | 1988-12-15 | Production of ceramic microsphere |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01301502A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059921A1 (en) * | 1998-05-21 | 1999-11-25 | Sakai Chemical Industries, Ltd. | Method for producing fine spherical particles of carbonate or hydroxide of nickel, cobalt or copper |
| JP2007007625A (en) * | 2005-07-04 | 2007-01-18 | National Institute Of Advanced Industrial & Technology | Liposome-manufacturing device and method by plural ultrasonic irradiation |
-
1988
- 1988-12-15 JP JP31712388A patent/JPH01301502A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059921A1 (en) * | 1998-05-21 | 1999-11-25 | Sakai Chemical Industries, Ltd. | Method for producing fine spherical particles of carbonate or hydroxide of nickel, cobalt or copper |
| US6197273B1 (en) | 1998-05-21 | 2001-03-06 | Sakai Chemical Industry Co., Ltd. | Method for producing fine spherical particles of carbonate or hydroxide of nickel, cobalt or copper |
| JP2007007625A (en) * | 2005-07-04 | 2007-01-18 | National Institute Of Advanced Industrial & Technology | Liposome-manufacturing device and method by plural ultrasonic irradiation |
| JP4543202B2 (en) * | 2005-07-04 | 2010-09-15 | 独立行政法人産業技術総合研究所 | Liposome production apparatus and production method using multiple ultrasonic irradiation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0478562B2 (en) | 1992-12-11 |
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