CN111848206A - Preparation method of monodisperse micron-sized hollow ceramic microspheres - Google Patents
Preparation method of monodisperse micron-sized hollow ceramic microspheres Download PDFInfo
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- CN111848206A CN111848206A CN202010697760.8A CN202010697760A CN111848206A CN 111848206 A CN111848206 A CN 111848206A CN 202010697760 A CN202010697760 A CN 202010697760A CN 111848206 A CN111848206 A CN 111848206A
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- polysiloxane
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- 239000004005 microsphere Substances 0.000 title claims abstract description 107
- 239000000919 ceramic Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 45
- -1 polysiloxane Polymers 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000002612 dispersion medium Substances 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 230000004580 weight loss Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
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- 239000002296 pyrolytic carbon Substances 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000002468 ceramisation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- OGFYGJDCQZJOFN-UHFFFAOYSA-N [O].[Si].[Si] Chemical group [O].[Si].[Si] OGFYGJDCQZJOFN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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Abstract
The invention belongs to the technical field of ceramic microsphere preparation, and particularly relates to a preparation method of monodisperse micron-sized hollow ceramic microspheres, which comprises the steps of taking siloxane monomers as reaction monomers and deionized water as reaction dispersion media, utilizing a basic catalyst to catalyze the reaction to carry out polymerization reaction on the monomers, obtaining polysiloxane microsphere powder through the reaction, and sintering the polysiloxane microsphere powder at high temperature to ceramic the polysiloxane microsphere powder to obtain the monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 microns; the method has the advantages of simple steps, easily controlled reaction conditions and high production efficiency, and can realize large-scale batch production.
Description
Technical Field
The invention belongs to the technical field of ceramic microsphere preparation, and particularly relates to a preparation method of monodisperse micron-sized hollow ceramic microspheres.
Background
The ceramic spherical particles have the advantages of high specific surface area, low density, heat resistance, corrosion resistance, high strength and the like, and have wide application prospects in the fields of heat insulation, high-temperature coatings, optical products, light structural materials and the like. In recent years, the conversion technology of polymer precursors has been greatly developed to prepare ceramic materials. By utilizing the characteristics of easy molding and processing of precursor polymer and the like, the ceramic material with complex shape, such as ceramic fiber, ceramic film, foamed ceramic, nano complex phase ceramic and the like, which is difficult to obtain by the traditional ceramic preparation process can be obtained. Common precursor polymers comprise polycarbosilane, polysilazane, polysiloxane and the like, wherein the polysiloxane has the characteristics of simple synthesis process, low price and the like, is widely used for preparing high-temperature structural materials with excellent performance, such as porous ceramics, ceramic matrix composite materials and the like, and is one of the best raw materials for preparing high-performance ceramic materials at low cost at present.
The polysiloxane is an organic silicon polymer containing a silicon-oxygen-silicon structure, organic functional groups or branched chains are connected to silicon atoms, the glass transition temperature is low (Tg is-127 ℃), and the polysiloxane has the characteristics of excellent flexibility, high and low temperature resistance, radiation resistance, oxidation resistance, physiological inertia and the like, becomes a high polymer material with unique structure and performance, and the silicon-containing material also has the characteristics of physiological inertia, no toxicity and no smell, and can make contribution to clean production. Currently, the most commonly used method for preparing polysiloxane microspheres is the hydrolytic polycondensation process invented by Stober in 1968. The hydrolysis polycondensation method is mainly a polysiloxane microsphere prepared by taking tetraethoxysilane as a monomer and ammonia water as a catalyst in a water/ethanol mixed solution, but a large amount of unreacted silanol is remained on the surface of the polysiloxane microsphere prepared by the method, particle agglomeration is easily caused in the later product drying process, and the particle size distribution of the polysiloxane microsphere prepared by the method is generally wide.
Patent CN110154201A provides a method for preparing ceramic microspheres by a ceramic microsphere and suspension photocuring method, which comprises: step S1, preparing ceramic slurry containing a light curing agent; step S2, discontinuously dropping the ceramic slurry into a suspending agent with viscosity higher than that of the ceramic slurry, and gradually sinking the droplets of the ceramic slurry in the suspending agent to be converted into spherical droplets; step S3, ultraviolet rays irradiate the spherical liquid drops in the suspending agent to excite the light curing agent in the spherical liquid drops to be cured, and then the spherical state of the spherical liquid drops is preserved to form a ceramic microsphere blank; step S4, separating the ceramic microsphere blank from the suspending agent, drying the separated ceramic microsphere blank, and removing organic components by degumming to obtain a ceramic microsphere precursor; step S5, sintering the ceramic microsphere precursor at high temperature to obtain ceramic microspheres; the method has high cost and complicated step control, and is not beneficial to realizing green production.
Patent CN106631112A provides a method for preparing hollow ceramic microspheres, which comprises providing metal spheres or metal oxide spheres as cores; depositing a pyrolytic carbon layer on the core in a high temperature fluidized bed chemical vapor deposition device; depositing a silicon carbide layer and/or a boron carbide layer and/or a zirconium carbide layer on the pyrolytic carbon layer to form solid ceramic particles; opening holes on the solid ceramic particles by using laser drilling equipment to obtain open-hole microspheres, wherein the holes at least penetrate through the silicon carbide layer and/or the boron carbide layer and/or the zirconium carbide layer; carrying out high-temperature oxidation heat treatment on the open-pore microspheres, and removing the pyrolytic carbon layer to form pyrolytic carbon layer-free microspheres; vacuum dipping the non-pyrolytic carbon layer microspheres, and removing cores to form the hollow ceramic microspheres. The ceramic microspheres prepared by the method have the advantages of complex process, low efficiency and incapability of realizing controllable particle size.
At present, ceramic microspheres can be produced by an emulsification-chemical crosslinking method, an emulsification-solvent evaporation method, a sol-gel method, a spray drying method and other methods, but the methods have the defects of high cost, complicated steps, high requirements on reaction condition control and the like, or have the poor performance conditions of low strength, poor sphericity, uneven particle size distribution, uncontrollable size, large relative density and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of monodisperse micron-sized hollow ceramic microspheres.
The method is realized by the following technical scheme:
a preparation method of monodisperse micron-sized hollow ceramic microspheres takes siloxane monomers as reaction monomers and deionized water as a reaction dispersion medium, utilizes a basic catalyst to catalyze the reaction to carry out polymerization reaction on the monomers, obtains polysiloxane microsphere powder through the reaction, and then sinters the polysiloxane microsphere powder at high temperature to ceramic the polysiloxane microsphere powder to prepare the monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 mu m.
A preparation method of monodisperse micron-sized hollow ceramic microspheres comprises the following steps:
1) adding siloxane monomers into deionized water for hydrolysis, then adding a basic catalyst for polymerization reaction to obtain a monodisperse micron-sized hollow polysiloxane microsphere solution, filtering the microsphere solution, washing, drying in an oven, and crushing by using a crusher to obtain polysiloxane microsphere powder;
2) and placing the polysiloxane microsphere powder in a high-temperature furnace, continuously heating to the temperature of 900-1500 ℃, and carrying out heat preservation sintering for more than 1h to obtain the ceramic microsphere.
Preferably, the siloxane monomer is one or a combination of methyl trimethoxy silane, Y-hydrophobic propyl trimethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, aminopropyl trimethoxy silane and epoxy trimethoxy silane.
Preferably, the particle size of the polysiloxane microsphere powder is 1-6 μm,
the hydrolysis process conditions are as follows: the mass ratio of the siloxane monomer to the deionized water is (1-80): 100, the time is 5-60 min; preferably, (10-50): 100, 20-40 min.
The polymerization reaction has the following process conditions: the mass ratio of the alkaline catalyst to the deionized water is (0.01-1): 100, the time is 1-60 min; preferably (0.02-1): 100, 5-40 min.
Preferably, the alkaline catalyst is any one or a combination of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the mass concentration of the ammonia water is 5% -10%.
The drying process comprises the following process conditions: the temperature is 100-; preferably 120-150 ℃.
The working parameters of the pulverizer are as follows: the rotation rate is 3000 and 7000 rpm; preferably 4000-.
The temperature is raised, and the process conditions are as follows: the speed is 1-20 ℃/min.
Preferably, the step 2) is continuously heated to 1000-1450 ℃.
Under the alkaline condition, the siloxane monomer is subjected to polycondensation reaction to form colloid at first, then a layer of shell is formed on the surface of the colloid, more and more siloxane monomers are gathered in the shell and subjected to polycondensation along with the extension of the reaction time, the shell is thickened continuously, but the interior of the shell is not filled, and further the hollow microspheres are realized. The siloxane monomer can be completely condensed by taking water as a solvent, the occurrence of a non-condensation part is avoided, and the existence of the monomer which does not participate in the reaction is avoided by controlling the dosage of the siloxane monomer, the deionized water and the alkaline catalyst.
The drying and crushing process is favorable for improving the activity of the polysiloxane microsphere powder in the ceramic process, is favorable for improving the crystalline state conversion efficiency, reduces the calcination temperature, realizes the process of converting organic to inorganic at the calcination temperature of 1500 ℃ below 900 plus one year in 1h, further reduces the calcination energy consumption, and further realizes the formation of the ceramic microsphere with smooth surface, good sphericity and complete spherical morphology at the calcination temperature of 1500 ℃ below 900 plus one year.
According to the invention, the calcination temperature is selected to be 900-1500 ℃, so that the polysiloxane microspheres can be cracked in 1h to generate the transformation from the amorphous state to the crystalline state, and finally the SiC crystalline phase and the silicon dioxide crystalline phase are generated.
Considering that the chain length, the carbon number, the capability of forming hydrogen bonds with water and the difference of formed network structures of different functional group siloxanes can influence the orderliness and the compact stacking degree of molecular chains in the microspheres, the polysiloxane microspheres with better heat resistance and stability can be obtained by selecting one or a combination of methyl trimethoxy silane, Y-hydrophobic propyl trimethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, aminopropyl trimethoxy silane and epoxy trimethoxy silane as monomers; the inventor selects a German NETZSCH TG 209F1 thermal analyzer to perform thermogravimetric analysis, and the conditions are as follows: under the atmosphere of nitrogen (40ml/min), the test range is from normal temperature to 800 ℃, the heating rate is 20 ℃/min, polysiloxane microspheres prepared from different monomers begin to lose weight at about 400 ℃, and the microspheres prepared from epoxy trimethoxy silane, phenyl trimethoxy silane, aminopropyl trimethoxy silane, methyl trimethoxy silane and vinyl trimethoxy silane do not show an obvious weight reduction trend along with the temperature rise, and the weight loss rate is as follows: epoxy trimethoxy silane < phenyl trimethoxy silane < aminopropyl trimethoxy silane < methyl trimethoxy silane < vinyl trimethoxy silane < Y-mercaptopropyl trimethoxy silane. Wherein, a thermogravimetric analysis chart of the polysiloxane microsphere prepared by the methyltrimethoxysilane shows that the weight reduction trend is obvious after 400 ℃, and the weight loss rate at 800 ℃ is only 11.73 percent compared with the weight ratio before the heat weight loss test.
The temperature range of the first thermal weight loss is approximately 400-550 ℃ within the test temperature range of room temperature-800 ℃, wherein the temperature with the maximum decomposition rate is 518.52 ℃, and the thermal weight loss mass percentage is about 4.835%; the temperature range of the second thermal weight loss is approximately 550-750 ℃, wherein the temperature with the maximum decomposition rate is 568.42 ℃, and the thermal weight loss mass percentage is about 6.888%; the sample residue at 800 ℃ is about 88.27%.
Has the advantages that:
the method has the advantages of simple steps, easily controlled reaction conditions and high reaction efficiency, and realizes large-scale batch production.
The ceramic microspheres prepared by the method have the advantages of small relative density, uniform particle size distribution, high strength, stable physical and chemical properties, corrosion resistance, acid and alkali resistance, high temperature resistance, high pressure resistance and excellent self-cleaning effect.
Drawings
FIG. 1 is a scanning electron micrograph of hollow silicone microspheres from example 1;
FIG. 2 is a scanning electron micrograph of the ceramic microspheres of example 1 after ceramization of the hollow polysiloxane microspheres;
FIG. 3 is a scanning electron micrograph of hollow silicone microspheres according to example 2;
FIG. 4 is a scanning electron micrograph of the ceramic microspheres of example 2 after ceramization of the hollow polysiloxane microspheres;
FIG. 5 is a scanning electron micrograph of hollow silicone microspheres from example 3;
FIG. 6 is a scanning electron micrograph of the ceramic microspheres of example 3 after ceramization of the hollow polysiloxane microspheres;
FIG. 7 is a thermogravimetric analysis of the polysiloxane microspheres prepared in example 1.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A preparation method of monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 mu m comprises the following steps:
1) taking 0.3g of sodium hydroxide as an alkaline catalyst to prepare 20g of sodium hydroxide solution to obtain alkaline catalyst solution;
2) adding 20g of methyltrimethoxysilane monomer into 180mL of deionized water for hydrolysis for 15min, then adding a prepared basic catalyst solution for polymerization reaction for 3min to obtain a monodisperse micron-sized hollow polysiloxane microsphere solution, filtering and washing the microsphere solution, drying the microsphere solution at 100 ℃ for 10h, and then crushing the microsphere solution by a crusher at the rotating speed of 4500 rpm to obtain polysiloxane microsphere powder, wherein the average particle size is 2.6 microns, the apparent density is 0.41g/mL, and the true density is 1.32 g/mL;
3) Placing the polysiloxane microsphere powder in a high temperature furnace, heating to 1300 ℃ at the speed of 3 ℃/min, and then sintering at 1300 ℃ for 1.2h under the condition of heat preservation to obtain the ceramic microsphere, wherein the average grain diameter of the ceramic microsphere is 1.8 microns, the apparent density is 0.25g/ml, and the true density is 0.85 g/ml.
Example 2
A preparation method of monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 mu m comprises the following steps:
1) taking 0.15g of potassium hydroxide as an alkaline catalyst to prepare 30g of potassium hydroxide solution to obtain alkaline catalyst solution;
2) adding 40g of phenyltrimethoxysilane monomer into 300mL of deionized water for hydrolysis for 20min, then adding a prepared basic catalyst solution for polymerization reaction for 8min to obtain a monodisperse micron-sized hollow polysiloxane microsphere solution, filtering and washing the microsphere solution, drying the microsphere solution at 150 ℃ for 18h, and then crushing the microsphere solution by a crusher at a rotating speed of 5500 revolutions per minute to obtain polysiloxane microsphere powder, wherein the average particle size is 3.05 microns, the apparent density is 0.43g/mL, and the true density is 1.34 g/mL;
3, placing the polysiloxane microsphere powder in a high-temperature furnace, heating to 1200 ℃ at the speed of 5 ℃/mi, and then carrying out heat preservation sintering for 2 hours to obtain ceramic microspheres, wherein the average particle size of the ceramic microspheres is 2.5 microns, the apparent density is 0.29g/ml, and the true density is 0.82 g/ml;
Example 3
A preparation method of monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 mu m comprises the following steps:
1) 60g of vinyl trimethoxy silane and 5g of aminopropyl trimethoxy silane are mixed and then added into 220mL of deionized water for hydrolysis for 30min, then 30g of ammonia water solution (the mass fraction is 5%) is added for polymerization reaction for 16min to obtain monodisperse micron-sized hollow polysiloxane microsphere solution, the microsphere solution is filtered and washed, after being dried for 20h at the temperature of 115 ℃, the microsphere solution is crushed by a crusher at the rotating speed of 5000 r/min to obtain polysiloxane microsphere powder, the average particle size is 6.3 microns, the apparent density is 0.49g/mL, and the true density is 1.31 g/mL;
2) placing the polysiloxane microsphere powder in a high temperature furnace, heating to 1350 ℃ at the speed of 3.5 ℃/min, and then carrying out heat preservation sintering for 1.5h to obtain the ceramic microsphere, wherein the average grain diameter of the ceramic microsphere is 4.5 microns, the apparent density is 0.22g/ml, and the true density is 0.83 g/ml.
Claims (9)
1. A preparation method of monodisperse micron-sized hollow ceramic microspheres is characterized in that siloxane monomers are used as reaction monomers, deionized water is used as a reaction dispersion medium, the monomers are subjected to polymerization reaction under the catalysis of a basic catalyst to obtain polysiloxane microsphere powder, and the polysiloxane microsphere powder is sintered at high temperature to be ceramic so as to prepare the monodisperse micron-sized hollow ceramic microspheres with the particle size of 1-6 microns.
2. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1, comprising the steps of:
1) adding siloxane monomers into deionized water for hydrolysis, then adding a basic catalyst for polymerization reaction to obtain a monodisperse micron-sized hollow polysiloxane microsphere solution, filtering the microsphere solution, washing, drying in an oven, and crushing by using a crusher to obtain polysiloxane microsphere powder;
2) and placing the polysiloxane microsphere powder in a high-temperature furnace, continuously heating to the temperature of 900-1500 ℃, and carrying out heat preservation sintering for more than 1h to obtain the ceramic microsphere.
3. The method for preparing monodisperse micron-sized hollow ceramic microspheres as claimed in claim 1 or 2, wherein the siloxane monomer is one or more of methyltrimethoxysilane, Y-mercaptopropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, aminopropyltrimethoxysilane and epoxytrimethoxysilane.
4. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1 or 2, wherein the polysiloxane microsphere powder has a particle size of 1-6 μm.
5. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1 or 2, wherein the hydrolysis is performed under the following process conditions: the mass ratio of the siloxane monomer to the deionized water is (1-80): 100, the hydrolysis time is 5-60 min.
6. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1 or 2, wherein the polymerization reaction is carried out under the following process conditions: the mass ratio of the alkaline catalyst to the deionized water is (0.01-1): 100, and the polymerization time is 1-60 min.
7. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1 or 2, wherein the basic catalyst is one or a combination of sodium hydroxide, potassium hydroxide and ammonia water.
8. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 2, wherein the drying process comprises the following process conditions: the temperature is 100 ℃ and 150 ℃, and the time is 10-24 h.
9. The method for preparing monodisperse micron-sized hollow ceramic microspheres according to claim 1, wherein the temperature is raised under the following process conditions: the speed is 1-20 ℃/min.
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