CN101913612A - Method for preparing micron-sized monodisperse silica microspheres - Google Patents
Method for preparing micron-sized monodisperse silica microspheres Download PDFInfo
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- CN101913612A CN101913612A CN 201010270523 CN201010270523A CN101913612A CN 101913612 A CN101913612 A CN 101913612A CN 201010270523 CN201010270523 CN 201010270523 CN 201010270523 A CN201010270523 A CN 201010270523A CN 101913612 A CN101913612 A CN 101913612A
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Abstract
The invention provides a method for preparing micron-sized monodisperse silica microspheres, which comprises the following steps of: mixing monodisperse SiO2 seeds, NH3-H2O and low-carbon alcohol to prepare seed liquid; adding solution of NH3/H2O/low-carbon alcohol to react with tetraethoxysilane (TEOS)/solution of low-carbon alcohol to make SiO2 generated by hydrolyzing the TEOS grow on the external surface of the SiO2 seeds, and performing mechanical stirring and ultrasonic treatment during reaction; stopping feeding after the SiO2 microspheres grow into microspheres with required particle size and continuing to react until the TEOS is completely hydrolyzed; and centrifuging and washing reaction liquid to obtain the monodisperse micron SiO2 microspheres after the reaction is finished. The invention also provides the micron-sized monodisperse silica microspheres prepared by the method. The average particle size of the SiO2 microspheres is 2 to 20mu m and the specific gravity is 1.7 to 2.0; and the SiO2 microspheres are imporous or nearly imporous.
Description
Technical field
The invention relates to a kind of preparation method of micron-sized monodisperse silica microspheres, particularly about the preparation method of median size greater than the monodisperse silica microspheres of 2 μ m.
Background technology
Since the synthetic monodisperse silica (SiO of people such as nineteen sixty-eight Stober
2) since the microballoon, people are to single SiO that disperses
2The research of microballoon application facet increases gradually.Because single SiO that disperses
2Microballoon has characteristics such as the shape homogeneity is good, controllable size, and because SiO
2Be a kind of non-metallic material of nontoxic, pollution-free, stable in properties, aspects such as its self-assembly at ceramic, pigment, catalyzer, chromatograph packing material, photonic crystal, liquid-crystal display liner and granulometry thing all have a wide range of applications.At present, people can prepare the monodisperse silica microspheres less than 2.5 μ m on certain scale.
CN101492164A has reported a kind of dispersed nano SiO
2The preparation method of microballoon wherein is to utilize seed multistep growth method, by selecting the ratio of ethanol, ammoniacal liquor and water suitable in seed preparation and the process of growth, make the particle diameter deviation less than 3%, silicon dioxide microsphere with high circularity and monodispersity.Compare with traditional technology, this building-up process has increased by two important links: the first, changed the number density of seed, and after seed generates, the number density of the silicon-dioxide seed that will be used to grow will be original 1/10th; The second, change the solution environmental that seed generates and grows, generate at seed and selected different H respectively with growth phase
2O and NH
3H
2The concentration of O.It is single SiO of dispersion of 100～325nm that this method has finally been synthesized particle diameter
2Microballoon.
CN1608985A has reported the single high-specific surface area SiO that disperses of a kind of preparation
2The method of micropore microballoon, this method adopts alkylamine as template and catalyzer, promote compound of silicate class being that solvent and water are in the system of disperse phase with the alcohols,, prepare single SiO of dispersion of particle diameter 500～1500nm by the self assembling process of two stage hydrolytie polycondensation and template
2The micropore microballoon.
Because the forming process of monodisperse system is comparatively responsive to condition, and be subjected to the restriction of multiple complicated factor, this gives the big particle diameter of preparation monodispersed SiO
2Microballoon has caused certain difficulty.Domestic and international research personnel have done a lot of work to this.People such as K.Nozawa prepare single SiO of dispersion that maximum particle diameter is 2 μ m by the control feed rate
2Microballoon (K.Nozawa., H.Gailhanou., L. Raison., et al.[J] .Langmuir, 2005,21:1516～1523).People such as Dong Peng are on the basis of Stober method, and utilizing the continuous growth method to prepare maximum particle diameter is single SiO of dispersion of 2.5 μ m
2Microballoon (Dong Peng .[J]. natural science progress, 2000,10 (3): 201～207).
Present synthetic method be used to prepare greater particle size particularly particle diameter greater than single SiO of dispersion of 2 μ m
2During microballoon, SiO takes place easily
2Microballoon sedimentation bonding phenomenon, SiO
2Microballoon has comparatively serious bonding in process of growth, be difficult to successfully single SiO of dispersion of synthetic greater particle size
2Microballoon.
Summary of the invention
The objective of the invention is at the problems of the prior art, provide a kind of can prepare greater particle size particularly particle diameter greater than the technology of preparing of the monodisperse silica microspheres of 2 μ m.
Another object of the present invention is to provide a kind of monodisperse silica microspheres with greater particle size.
On the one hand, the invention provides a kind of preparation method of monodisperse silica microspheres, it mainly comprises step: will singly disperse SiO
2Microballoon seed, NH
3-H
2O and low-carbon alcohol mixing are made into seed liquor, add NH then
3/ H
2O/ low-carbon alcohol solution and tetraethoxy (TEOS)/low-carbon alcohol solution reacts, the SiO that the TEOS hydrolysis is generated
2At SiO
2Grow on the microballoon seed outside surface, and in reaction, carry out mechanical stirring and supersound process;
Treat SiO
2After microballoon grows to required particle diameter, stop to feed in raw material, and continue reaction up to the TEOS complete hydrolysis;
Reaction will contain SiO after finishing
2The centrifugal washing of the reaction solution of microballoon obtains single micron SiO that disperses
2Microballoon.The proportion of this microballoon is more typically between 1.75～1.95 1.7～2.0 usually, can directly use, and also can pass through to re-use after high-temperature roasting (500～1100 ℃) improves its physical strength and chemical stability.Through after the high-temperature roasting, the proportion of microballoon is usually between 1.90～2.25.
It is single SiO of dispersion of 1 micron to tens of microns that the preparation method of monodisperse silica microspheres of the present invention is particularly suitable for preparing median size
2Microballoon more is particularly suitable for preparing the micron-sized monodisperse silica microspheres that median size is 2～20 μ m.Certainly, method of the present invention equally also can be used for the single SiO of dispersion less than 2 μ m
2Synthesizing of microballoon is although particle diameter is less than single SiO that disperses of 2 μ m
2The synthetic mechanical stirring that only needs of microballoon just can.
According to specific embodiments of the present invention, single SiO that disperses described in the method for the present invention
2Seed is that particle diameter is less than the single SiO of dispersion of target
2Single SiO that disperses of microspherulite diameter
2Microballoon.Described single SiO that disperses
2Seed can be synthetic according to the method preparation of prior art, also can be synthetic according to method preparation of the present invention.
According to specific embodiments of the present invention, among the preparation method of monodisperse silica microspheres of the present invention, described temperature of reaction is the temperature of liquid phase for keeping reaction system, and preferred temperature of reaction is 5～45 ℃; Low-carbon alcohol of the present invention can be ethanol or methyl alcohol or their mixture; NH in the described reaction system
3Concentration is 0.5～4M, and the concentration of water is 2～20M; Described NH
3/ H
2The adding mode of O/ low-carbon alcohol solution and TEOS/ low-carbon alcohol solution can be for add or add in batches continuously.According to preferred specific embodiments of the present invention, SiO in the reaction system of the present invention
2The number density of microballoon seed should greater than
(individual/ml), less than
(individual/ml), seed particle diameter d
pUnit be μ m.
In the method for the present invention, described supersound process and mechanical stirring must be for carrying out simultaneously.According to preferred version of the present invention, described supersound process condition: the ultrasonic power of unit reaction solution volume is preferably 10～200W/L more than or equal to 10W/L, and ultrasonic frequency is 10～100KHz.Ultrasonic power is too small can not to prevent that then seed is bonding.Described machinery stirs companion's intensity for making SiO
2The physical strength that microballoon suspends in reaction solution, that is, mechanical stirring intensity is can stop SiO
2Microballoon is deposited in reaction solution bottom and is advisable, and those skilled in the art can determine concrete stirring intensity easily according to the size of what and selected mechanical stirring device of reaction solution after reading the present invention.
Use method of the present invention, can adopt one step growth to obtain single SiO of dispersion of required particle diameter
2Microballoon also can carry out single SiO of dispersion that the multistep growth obtains required particle diameter
2Microballoon.Use method of the present invention, generally, one step growth can make the microspherulite diameter growth reach about 3 microns.On the other hand, the present invention also provides a kind of micron order list to disperse SiO
2Microballoon, it prepares according to the method described in the present invention.Disperse SiO according to micron order list provided by the present invention
2Microballoon, its median size are 2～20 μ m, between the proportion 1.7～2.0 (after the high-temperature roasting, the proportion of microballoon is usually between 1.90～2.25), are atresia or atresia SiO almost
2Microballoon.
Key of the present invention is dexterously the dissemination of supersound process and mechanical agitation are organically combined.At the single SiO of dispersion that utilizes traditional mechanical stirring method preparation greater than 2 μ m
2In the time of microballoon, because SiO
2Microspherulite diameter is big, SiO
2Microballoon can be because action of centrifugal force to the reactor wall enrichment, causes SiO in whipping process
2Microballoon bonds in process of growth seriously.The contriver finds in experiment, at single the disperse SiO of preparation greater than 2 μ m
2During microballoon,, do not adopt mechanical stirring simultaneously, because SiO if only adopt supersound process
2Microspherulite diameter is big, SiO
2Microballoon can be deposited to reactor bottom, can cause SiO equally
2Microballoon bonds in process of growth seriously, and the SiO that generates
2Microballoon size heterogeneity, bigger SiO
2Microsphere surface is adhering to a plurality of less SiO
2Microballoon.And adopting method of the present invention, supersound process and mechanical stirring act on simultaneously in reaction process, then can address this problem well, obtain single SiO of dispersion of required particle diameter
2Microballoon.
Description of drawings
The single SiO that disperses of synthetic 0.497 μ m among Fig. 1 embodiment 1
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 0.927 μ m among Fig. 2 embodiment 2
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 2.014 μ m among Fig. 3 embodiment 3
2The SEM photo of microballoon.
Synthetic among Fig. 4 embodiment 4～3 μ m SiO
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 2.67 μ m among Fig. 5 embodiment 5
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 4.88 μ m among Fig. 6 embodiment 6
2The SEM photo of microballoon.
Synthetic among Fig. 7 embodiment 7～5 μ m SiO
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 6.72 μ m among Fig. 8 embodiment 8
2The SEM photo of microballoon.
Synthetic among Fig. 9 embodiment 9～7 μ m SiO
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 8.68 μ m among Figure 10 embodiment 10
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 10.1 μ m among Figure 11 embodiment 11
2The SEM photo of microballoon.
The single SiO that disperses of synthetic 10.1 μ m among Figure 12 embodiment 11
2The optical microscope photograph of microballoon.
Embodiment
Below introduce realization of the present invention and the beneficial effect that had in detail by specific embodiment, understand novelty essence of the present invention place better to help the reader, but but do not constitute qualification the present invention's practical range.
The single SiO that disperses of embodiment 1, about 0.5 μ m
2The preparation of microballoon seed
Add 300mL ethanol, 344mL methyl alcohol, 6mL water and 150mL massfraction respectively and be 25% ammoniacal liquor in the 2000mL there-necked flask, the temperature of there-necked flask is controlled at 25 ℃.Under whipped state, 50mL TEOS and 150mL alcoholic acid mixing solutions are added above solution and stirring reaction 1h rapidly then.Add 40mL TEOS and 40mL alcoholic acid mixing solutions subsequently, restir reaction 2h takes out reaction solution, and centrifugal washing obtains～the single SiO of dispersion of 0.5 μ m
2The microballoon seed.
Fig. 1 is scanning electron microscope (SEM) photo of this sample, synthetic SiO
2Microspherulite diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 0.497 μ m, and the size distribution standard deviation is 4.5%.SiO
2The proportion of microballoon is～1.80.
The single SiO that disperses of embodiment 2, about 1 μ m
2The preparation of microballoon seed
Add 504mL methyl alcohol in the 2000mL there-necked flask respectively, 130mL water and 40mL massfraction are 25% ammoniacal liquor.The median size of getting preparation among the 6.25g embodiment 1 then is about single SiO of dispersion of 0.5 μ m
2The microballoon seed adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 6.6 * 10
10Individual/mol), and the control reacting liquid temperature is at 30 ℃.Then at mechanical stirring and supersound process (power: 50W/L; Frequency: 40KHz) under the state, drip 61mL ammoniacal liquor (solubility of ammoniacal liquor is 25 heavy % among the embodiment)/mixing solutions of 35mL water/104mL methyl alcohol and mixing solutions of 163mL TEOS/37mL methyl alcohol, the dropping time is 3 hours.Drip and finish back continuation reaction 3 hours, centrifugal then washing separates, and obtains～the single SiO of dispersion of 1 μ m
2Microballoon.This 8iO
2The SEM photo of microballoon seed is seen Fig. 2, synthetic SiO
2Microspherulite diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 0.927 μ m, and the size distribution standard deviation is 3.5%.SiO
2The proportion of microballoon is 1.82.
The single SiO that disperses of embodiment 3, about 2 μ m
2The preparation of microballoon seed
Add 844mL ethanol in the 2000mL there-necked flask respectively, 6mL water and 150mL massfraction are 25% ammoniacal liquor.Get the single SiO of dispersion of 1 μ m of preparation among the 12.5g embodiment 2 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 1.36 * 10
10Individual/mol), and the control reacting liquid temperature is at 30 ℃.Under the mechanical stirring state, drip 125mL ammoniacal liquor/70mL water/121mL alcoholic acid mixing solutions and 325mL TEOS/175mL alcoholic acid mixing solutions then, reinforced process is 3h.Reaction 2h is continued in the reinforced back of finishing, and centrifugation then obtains～the single SiO of dispersion of 2 μ m
2Microballoon.This SiO
2The SEM photo of microballoon seed is seen Fig. 3, synthetic SiO
2Microspherulite diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 2.014 μ m, and the size distribution standard deviation is 2.0%.The proportion of microballoon is 1.84.
The single SiO that disperses of embodiment 4, about 3 μ m
2One of preparation of microballoon
Add 400mL ethanol in the 2000mL there-necked flask respectively, 444mL methyl alcohol, 6g water and 150mL massfraction are 25% ammoniacal liquor.Get the single SiO of dispersion of about 2 μ m of preparation among the 28g embodiment 3 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 2.98 * 10
9Individual/mol), and controlled temperature is at 30 ℃.(no supersound process) drips 125mL ammoniacal liquor/65mL water/110mL alcoholic acid mixing solutions and 300mL TEOS/200mL alcoholic acid mixing solutions under the mechanical stirring state then, and reinforced process is 3h.Reaction 2h is continued in the reinforced back of finishing, and centrifugal then washing obtains SiO
2Microballoon.Observe discovery by SEM, the synthetic SiO that obtains
2Microballoon bonds mutually.The SEM photo of sample is seen Fig. 4.
The single SiO that disperses of embodiment 5, about 3 μ m
2Two of the preparation of microballoon
Reactor size, reagent dosage, feed way and temperature of reaction etc. are identical with embodiment 4, and difference is in the mechanical stirring reaction process, simultaneously reaction solution is carried out supersound process (power: 100W/L; Frequency: 60KHz).Reaction 2 hours is continued in the reinforced back of finishing, and centrifugal then washing separates, and obtains the SiO of median size for～3 μ m
2Microballoon.Synthetic SiO
2Microballoon SEM photo is seen Fig. 5, and the sample particle diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 2.67 μ m, and the size distribution standard deviation is 2.0%.SiO
2The proportion of microballoon is 1.84.
The single SiO that disperses of embodiment 6, about 5 μ m
2One of preparation of microballoon
Add 772mL methyl alcohol in the 2000mL there-necked flask respectively, 78mL water and 150mL massfraction are 25% ammoniacal liquor.Get the single SiO of dispersion of about 3 μ m of preparation among the 20g embodiment 4 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 9.12 * 10
8Individual/mol), and controlled temperature is at 30 ℃.Reaction solution is carried out mechanical stirring and supersound process (power: 50W/L; Frequency: 40KHz).Preparation 400mL ammonia-water-ethanol mixing solutions (wherein containing 237mL 25 heavy % ammoniacal liquor and 163mL ethanol) and 400mL TEOS-alcoholic acid mixing solutions (containing 250mL TEOS, 150mL ethanol).Successively add 60mL ammonia-water-ethanol solution and 60mL TEOS-alcoholic acid solution, and add once, add up to these two kinds of solution every half an hour with graduated cylinder.In the charging reaction process, all the time reaction solution is carried out supersound process and mechanical stirring.Reaction 1.5h is continued in the reinforced back of finishing, and centrifugal then washing separates, and obtains～the single SiO of dispersion of 5 μ m
2Microballoon.Synthetic SiO
2Microballoon SEM photo is seen Fig. 6, and the sample particle diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 4.88 μ m, and the size distribution standard deviation is 1.5%.SiO
2The proportion of microballoon is 1.85.
The single SiO that disperses of embodiment 7, about 5 μ m
2Two of the preparation of microballoon
Reactor size, reagent dosage, feed way and temperature of reaction etc. are identical with embodiment 6, and difference is only sample to be carried out supersound process (power: 50W/L; Frequency: 40KHz).Discovery is SiO in reaction process
2Seed can sink to reactor bottom.Reaction 2h is continued in the reinforced back of finishing, and centrifugal then washing obtains SiO
2Microballoon.Synthetic SiO
2Sample SEM photo is seen Fig. 7.Observe discovery by SEM, the synthetic SiO that obtains
2Microballoon bonds seriously mutually.
The single SiO that disperses of embodiment 8, about 7 μ m
2One of preparation of microballoon
In the 2000mL there-necked flask, add 530mL ethanol and 170mL massfraction respectively and be 25% ammoniacal liquor.Get the single SiO of dispersion of about 5 μ m of preparation among the 36g embodiment 6 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 3.84 * 10
8Individual/mol), and controlled temperature is at 15 ℃.Reaction solution is carried out supersound process (power: 20W/L; Frequency: 60KHz) and mechanical stirring.Drip the mixing solutions and the 180mLTEOS/220mL alcoholic acid mixing solutions of 125mL ammoniacal liquor/98mL water/177mL methyl alcohol, reinforced process is 1.5h.In the charging reaction process, all the time reaction solution is carried out supersound process and mechanical stirring.Reaction 1.5h is continued in the reinforced back of finishing, and centrifugal then washing separates, and obtains～the single SiO of dispersion of 7 μ m
2Microballoon.Synthetic SiO
2Microballoon SEM photo is seen Fig. 8, and the sample particle diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 6.72 μ m, and the size distribution standard deviation is 1.3%.SiO
2The proportion of microballoon is 1.88.
The single SiO that disperses of embodiment 9, about 7 μ m
2Two of the preparation of microballoon
Conditions such as reactor size, reagent dosage, feed way and temperature of reaction are identical with embodiment 8, and difference is only sample to be carried out mechanical stirring.We find SiO in reaction process
2Seed can be deposited on the wall of reactor.Reaction 2h is continued in the reinforced back of finishing, and centrifugal then washing obtains SiO
2Microballoon.Synthetic SiO
2Sample SEM photo is seen Fig. 9.Observe discovery by SEM, the synthetic SiO that obtains
2Microballoon bonds seriously mutually.
The single SiO that disperses of embodiment 10, about 9 μ m
2The preparation of microballoon
In the 2000mL there-necked flask, add 460mL ethanol and 40mL massfraction respectively and be 25% ammoniacal liquor.Get the single SiO of dispersion of about 7 μ m of preparation among the 47g embodiment 8 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 2.69 * 10
8Individual/mol), and controlled temperature is at 40 ℃.Reaction solution is carried out supersound process (power: 150W/L; Frequency: 60KHz) and mechanical stirring.Drip 125mL ammoniacal liquor/98mL water/177mL alcoholic acid mixing solutions and 180mLTEOS/220mL alcoholic acid mixing solutions, reinforced process is 5h.In the charging reaction process, all the time reaction solution is carried out supersound process and mechanical stirring.Reaction 4h is continued in the reinforced back of finishing, and centrifugal then washing separates, and obtains～the single SiO of dispersion of 9 μ m
2Microballoon.Synthetic SiO
2Microballoon SEM photo is seen Figure 10, and the sample particle diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 8.68 μ m, and the size distribution standard deviation is 1.3%.SiO
2The proportion of microballoon is 1.90.
The single SiO that disperses of embodiment 11, about 10 μ m
2The preparation of microballoon
Add 386mL ethanol in the 2000mL there-necked flask respectively, 40g water and 75mL massfraction are 25% ammoniacal liquor.Get the single SiO of dispersion of about 9 μ m of preparation among the 66g embodiment 10 then
2Microballoon adds there-necked flask (reaction system SiO
2The number density of microballoon seed is 1.75 * 10
8Individual/mol), and controlled temperature is at 25 ℃.Drip the mixing solutions and the 140mL TEOS/160mL alcoholic acid mixing solutions of 125mL ammoniacal liquor/90mL water/285mL methyl alcohol, reinforced process is 2h.In the charging reaction process, all the time reaction solution is carried out supersound process (power: 150W/L; Frequency: 60KHz) and mechanical stirring.Reaction 2h is continued in the reinforced back of finishing, and centrifugal then washing separates, and obtains～the single SiO of dispersion of 10 μ m
2Microballoon.Synthetic SiO
2Microballoon SEM photo is seen Figure 11, and optical microscope photograph is seen Figure 12.The sample particle diameter is homogeneous very.Through measuring the SEM photo as can be known, microsphere average grain diameter is 10.1 μ m, and the size distribution standard deviation is 1.5%.SiO
2The proportion of microballoon is 1.92.
Claims (10)
1. the preparation method of a micron-sized monodisperse silica microspheres, the method comprising the steps of:
To singly disperse SiO
2Microballoon seed, NH
3-H
2O and low-carbon alcohol mixing are made into seed liquor, add NH then
3/ H
2O/ low-carbon alcohol solution and TEOS/ low-carbon alcohol solution react, the SiO that the TEOS hydrolysis is generated
2At SiO
2Grow on the microballoon seed outside surface, and in reaction, carry out mechanical stirring and supersound process;
Treat SiO
2After microballoon grows into the microballoon of required particle diameter, stop to feed in raw material, and continue reaction up to the TEOS complete hydrolysis;
Reaction will contain SiO after finishing
2The centrifugal washing of the reaction solution of microballoon obtains the micron order list and disperses SiO
2Microballoon.
2. preparation method according to claim 1, this method are that to be used to prepare median size be single SiO of dispersion of 1 micron to tens of microns
2Microballoon is single SiO of dispersion of 2～20 μ m especially for the preparation median size
2Microballoon.
3. preparation method according to claim 1, wherein, described single SiO that disperses
2The microballoon seed is that particle diameter is less than the single SiO of dispersion of target
2Single SiO that disperses of microspherulite diameter
2Microballoon.
4. preparation method according to claim 1, wherein, described temperature of reaction is the temperature of liquid phase for keeping reaction system, preferred temperature of reaction is 5～45 ℃.
5. preparation method according to claim 1, wherein, described low-carbon alcohol is ethanol or methyl alcohol or their mixture.
6. preparation method according to claim 1, wherein, NH in the described reaction system
3Concentration is 0.5～4M, and the concentration of water is 2～20M; Described NH
3/ H
2The adding mode of O/ low-carbon alcohol solution and TEOS/ low-carbon alcohol solution is to add continuously or add in batches.
7. preparation method according to claim 1, wherein, SiO in the described reaction system
2The number density of microballoon seed greater than
(individual/ml), less than
(individual/ml), seed particle diameter d
pUnit be μ m.
8. preparation method according to claim 1, wherein, described supersound process and mechanical stirring are for carrying out simultaneously; Described supersound process condition: ultrasonic power is 10～200W/L, and ultrasonic frequency is 10～100KHz; Described machinery stirs companion's intensity for making SiO
2The physical strength that microballoon suspends.
9. preparation method according to claim 1 wherein, adopts one step growth to obtain single SiO of dispersion of required particle diameter
2Microballoon, or carry out single SiO of dispersion that the multistep growth obtains required particle diameter
2Microballoon.
10. a micron order list disperses SiO
2Microballoon, it prepares according to each described method of claim 1～9; Preferably, described micron order list disperses SiO
2The median size of microballoon is 2～20 μ m, proportion 1.7～2.0 or after roasting proportion 1.90～2.25, be atresia or atresia SiO almost
2Microballoon.
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| CN115477307A (en) * | 2022-09-21 | 2022-12-16 | 上海工程技术大学 | Preparation method of uniform micron-sized silicon dioxide microspheres |
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| CN107400501A (en) * | 2017-08-31 | 2017-11-28 | 长江存储科技有限责任公司 | A kind of cmp agent, the preparation method of dispersed nano silicon oxide microsphere |
| CN107400501B (en) * | 2017-08-31 | 2019-04-02 | 长江存储科技有限责任公司 | A kind of chemical mechanical grinding agent, dispersed nano silicon oxide microsphere preparation method |
| CN115477307A (en) * | 2022-09-21 | 2022-12-16 | 上海工程技术大学 | Preparation method of uniform micron-sized silicon dioxide microspheres |
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