CN103570027B - A kind of SiO 2/ ZrO 2/ Al 2o 3the preparation method of compound nano-hollow sphere - Google Patents
A kind of SiO 2/ ZrO 2/ Al 2o 3the preparation method of compound nano-hollow sphere Download PDFInfo
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- CN103570027B CN103570027B CN201310548419.6A CN201310548419A CN103570027B CN 103570027 B CN103570027 B CN 103570027B CN 201310548419 A CN201310548419 A CN 201310548419A CN 103570027 B CN103570027 B CN 103570027B
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Abstract
The present invention discloses a kind of SiO
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere, employing high molecular polymer is template, by different organic precursor alternating deposits, then is prepared from through calcining, its density≤0.2g/cm
3, ultimate compression strength>=500MPa, size is 100 ~ 500nm; The SiO that the present invention utilizes the silicon source of low cost, zirconium source and aluminium source to prepare
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere, its size and even particle size distribution, good dispersity and intensity is high; This technical process is simultaneously simple, and preparation cycle is short, less energy consumption, and cost is low, is conducive to suitability for industrialized production and large-scale application.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of SiO
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere material.
Background technology
Nano-scale hollow microballoon because its density is little, the performance such as large, the thermostability of specific surface area and good and remarkable quantum size effect, small-size effect and the macro quanta tunnel effect of Surface Permeability is subject to more and more paying close attention to and studying.Meanwhile, nano-scale hollow microballoon at high temperature has high-strength, the performance such as high-ductility, high stability and has potential application in fields such as electronic package material, polymer composite, stupalith, rubber, plastics, coating, paint, seal gums.
At present, the main method of preparation nano-scale hollow micro-sphere material has: (1) removes template: it is by controlling the precipitation of presoma on nuclear membrane plate surface or reaction, form surface coated core/shell structure, finally heating or chemical reaction remove nuclear membrane plate, form the tiny balloon of Nano/micron yardstick." polymer material science and engineering " (2010, the first phase, 137-139 page) Wu's tor seminar of Nanjing University utilizes poly-(vinylbenzene-4-vinylpridine altogether) particle template successfully to synthesize the hollow SiO of nanoscale
2microballoon.(2) microemulsion method: utilize the presoma of target product to generate corresponding oxyhydroxide or hydrous oxide at drop surface hydrolysis, form stable colloidal particle through polycondensation and be coated on emulsion droplet surface, form the nucleocapsid structure of emulsion/gel, by adding water and acetone and other organic solvents, separated product and microemulsion, tensio-active agent is removed in calcining and organic solvent can to the nano-scale hollow ball with mesopore orbit.U.S.'s " Langmuir " (Langmuir, the 16th volume, 8285-8290 page in 2000) Mckelvey group adopts this method to synthesize diameter 120nm, the hollow sphere polymer of the thick 10nm of shell.(3) spray reaction: with water, ethanol or other solvents by target presoma wiring solution-forming, by spraying plant by solution atomization, atomized liquid forms drop through nozzle and enters in reactor, the solvent on drop surface evaporates rapidly, the chemical reactions such as solute generation thermolysis or burning, precipitation forms hollow ball structure.U.S.'s " advanced material " (Advancedmaterials, calendar year 2001, the 13rd volume, 1620-1624 page) the Tartaj group standby SiO of diameter at 50-250nm of this legal system
2/ Fe
2o
3composite hollow ball, the people such as U.S.'s " chemical material " (Chemistrymaterials, the 10th volume, 3780-3782 page in 1998) Sasaki adopt to use the same method and successfully synthesize the TiO of 50nm
2hollow ball.
Through extensively retrieval, SiO
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere is not yet published and relevant report.Compound hollow microsphere material not only has outside the various characteristics of single tiny balloon, also there is compound and synergistic function, " modern chemical industry " (2009,29th volume, 6th phase, 37-41 page) white wave seminar adopts yeast biological template to synthesize Ti-W-Si compound hollow microballoon, because the method preparation cost is high, product balling ratio is low, and under shell parcel not exclusively causes ternary system, nano level composite hollow microballoon rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of Microsphere Size and even particle size distribution, good dispersity and the high SiO of intensity
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere preparation method, the density≤0.2g/cm of hollow ball
3, ultimate compression strength>=500MPa, size is 100 ~ 500nm, and the method technical process is simple, and preparation cycle is short, less energy consumption, and cost is low, is conducive to suitability for industrialized production and large-scale application.
For achieving the above object, the present invention takes following technical scheme: a kind of SiO
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere, it is characterized in that, be prepared from by following steps, (1) taking high molecule polymer template joins in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute after interpolation cetyl trimethyl tertiary amine, forms suspension and is also incubated in the water-bath of 60-90 DEG C; (2) taking Zircosol ZN is dissolved in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute, forms suspension and is incubated in the water-bath of 60-90 DEG C; (3) taking aluminum isopropylate is dissolved in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute, forms suspension and is incubated in the water-bath of 60-90 DEG C; (4) above-mentioned first two suspension is mixed, under agitation, the suspension of alternate dropwise addition aluminum isopropylate and tetraethoxy in 2-4 hour, add ammoniacal liquor regulates pH value to 8-12 simultaneously, continue to stir 3-6 hour, adopt dehydrated alcohol and secondary deionized water to wash respectively to neutrality, 50-60 DEG C obtained SiO after vacuum-drying 6-10 hour
2/ ZrO
2/ Al
2o
3composite Nano solid sphere; (5) by SiO
2/ ZrO
2/ Al
2o
3composite Nano solid sphere is placed in retort furnace under nitrogen protection, is warming up to 600 DEG C with the temperature rise rate of 5 DEG C/min, within calcining at constant temperature 6-8 hour, makes SiO
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere; Made SiO
2/ ZrO
2/ Al
2o
3density≤the 0.2g/cm of compound nano-hollow sphere
3, ultimate compression strength>=500MPa, size is 100 ~ 500nm;
The mass ratio of described high molecule polymer template, cetyl trimethyl tertiary amine, Zircosol ZN, aluminum isopropylate and tetraethoxy is 1:(0.1-0.5): (0.5-10): (0.5-10): (1-20), in the mixing solutions of ethylene glycol and water, the volume ratio of ethylene glycol and water is 1:(1-10).
Described high molecule polymer template is the one in polystyrene, urethane, polyacrylic acid ester microsphere, and particle diameter is 50-200n.
Beneficial effect: the SiO that the present invention utilizes the silicon source of low cost, zirconium source and aluminium source to prepare
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere, this Microsphere Size and even particle size distribution, good dispersity and intensity is high; This technical process is simultaneously simple, and preparation cycle is short, less energy consumption, and cost is low, is conducive to suitability for industrialized production and large-scale application.
Embodiment
The invention provides a kind of SiO
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere, the density≤0.2g/cm of made hollow ball
3, ultimate compression strength>=500MPa, size is 100 ~ 500nm.
Embodiment one:
Taking 1g particle diameter is that the polystyrene microsphere of 50nm joins in the mixing solutions of 50ml ethylene glycol and water, adds 0.1g cetyl trimethyl tertiary amine, ultrasonic disperse 15 minutes simultaneously, forms suspension and is also incubated in the water-bath of 60 DEG C.Taking 0.5g Zircosol ZN is dissolved in the mixing solutions of 100ml ethylene glycol and water, ultrasonic disperse 15 minutes, forms suspension and is incubated in the water-bath of 60 DEG C.Taking 0.5g aluminum isopropylate is dissolved in the mixing solutions of 50ml ethylene glycol and water, ultrasonic disperse 15 minutes, forms suspension and is incubated in the water-bath of 60 DEG C.Above-mentioned first two suspension is poured in there-necked flask together, under certain stirring velocity, the suspension of alternate dropwise addition aluminum isopropylate and 1g tetraethoxy in 2 hours, add ammoniacal liquor regulates pH value to 8 simultaneously, continue stirring 3 hours, adopt dehydrated alcohol and secondary deionized water to wash respectively to neutrality, 50 DEG C of vacuum-dryings obtained SiO after 6 hours
2/ ZrO
2/ Al
2o
3composite Nano solid sphere; Wherein the ratio of ethylene glycol and water is 1:1.By obtained SiO
2/ ZrO
2/ Al
2o
3composite Nano solid sphere is placed in retort furnace under nitrogen protection, is warming up to 600 DEG C with the temperature rise rate of 5 DEG C/min, calcining at constant temperature 6 hours, and obtained size is 100-200nm, and density is 0.1g/cm
3, ultimate compression strength is the SiO of 550MPa
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere.
Embodiment two
Taking 1g particle diameter is that the polyaminoester microball of 200nm joins in the mixing solutions of 50ml ethylene glycol and water, adds 0.5g cetyl trimethyl tertiary amine, ultrasonic disperse 10 minutes simultaneously, forms suspension and is also incubated in the water-bath of 75 DEG C.Taking 10g Zircosol ZN is dissolved in the mixing solutions of 100ml ethylene glycol and water, ultrasonic disperse 10 minutes, forms suspension and is incubated in the water-bath of 75 DEG C.Taking 10g aluminum isopropylate is dissolved in the mixing solutions of 50ml ethylene glycol and water, ultrasonic disperse 10 minutes, forms suspension and is incubated in the water-bath of 75 DEG C.Above-mentioned first two suspension is poured in there-necked flask together, under certain stirring velocity, the suspension of alternate dropwise addition aluminum isopropylate and 20g tetraethoxy in 3 hours, add ammoniacal liquor regulates pH value to 12 simultaneously, continue stirring 6 hours, adopt dehydrated alcohol and secondary deionized water to wash respectively to neutrality, 55 DEG C of vacuum-dryings obtained SiO after 10 hours
2/ ZrO
2/ Al
2o
3composite Nano solid sphere; Wherein the ratio of ethylene glycol and water is 1:10.Obtained SiO
2/ ZrO
2/ Al
2o
3composite Nano solid sphere is placed in retort furnace under nitrogen protection, is warming up to 600 DEG C with the temperature rise rate of 5 DEG C/min, calcining at constant temperature 8 hours, and obtained size is 300-500nm, and density is 0.2g/cm
3, ultimate compression strength is the SiO of 780MPa
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere.
Embodiment three
Taking 1g particle diameter is that the polyacrylic acid ester microsphere of 150nm joins in the mixing solutions of 50ml ethylene glycol and water, adds 0.3g cetyl trimethyl tertiary amine, ultrasonic disperse 15 minutes simultaneously, forms suspension and is also incubated in the water-bath of 90 DEG C.Taking 6g Zircosol ZN is dissolved in the mixing solutions of 100ml ethylene glycol and water, ultrasonic disperse 15 minutes, forms suspension and is incubated in the water-bath of 90 DEG C.Taking 6g aluminum isopropylate is dissolved in the mixing solutions of 50ml ethylene glycol and water, ultrasonic disperse 15 minutes, forms suspension and is incubated in the water-bath of 90 DEG C.Above-mentioned first two suspension is poured in there-necked flask together, under certain stirring velocity, the suspension of alternate dropwise addition aluminum isopropylate and 12g tetraethoxy in 4 hours, add ammoniacal liquor regulates pH value to 10 simultaneously, continue stirring 5 hours, adopt dehydrated alcohol and secondary deionized water to wash respectively to neutrality, 60 DEG C of vacuum-dryings obtained SiO after 8 hours
2/ ZrO
2/ Al
2o
3composite Nano solid sphere; Wherein the ratio of ethylene glycol and water is 1:5.By obtained SiO
2/ ZrO
2/ Al
2o
3composite Nano solid sphere is placed in retort furnace under nitrogen protection, is warming up to 600 DEG C with the temperature rise rate of 5 DEG C/min, calcining at constant temperature 7 hours, and obtained size is 200-400nm, and density is 0.15g/cm
3, ultimate compression strength is the SiO of 650MPa
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention; Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (2)
1. a SiO
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere, it is characterized in that, be prepared from by following steps, (1) taking high molecule polymer template joins in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute after interpolation cetyl trimethyl tertiary amine, forms suspension and is also incubated in the water-bath of 60-90 DEG C; (2) taking Zircosol ZN is dissolved in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute, forms suspension and is incubated in the water-bath of 60-90 DEG C; (3) taking aluminum isopropylate is dissolved in the mixing solutions of ethylene glycol and water, ultrasonic disperse 10-15 minute, forms suspension and is incubated in the water-bath of 60-90 DEG C; (4) above-mentioned first two suspension is mixed, under agitation, the suspension of alternate dropwise addition aluminum isopropylate and tetraethoxy in 2-4 hour, add ammoniacal liquor regulates pH value to 8-12 simultaneously, continue to stir 3-6 hour, adopt dehydrated alcohol and secondary deionized water to wash respectively to neutrality, 50-60 DEG C obtained SiO after vacuum-drying 6-10 hour
2/ ZrO
2/ Al
2o
3composite Nano solid sphere; (5) by SiO
2/ ZrO
2/ Al
2o
3composite Nano solid sphere is placed in retort furnace under nitrogen protection, is warming up to 600 DEG C with the temperature rise rate of 5 DEG C/min, within calcining at constant temperature 6-8 hour, makes SiO
2/ ZrO
2/ Al
2o
3compound nano-hollow sphere; Made SiO
2/ ZrO
2/ Al
2o
3density≤the 0.2g/cm of compound nano-hollow sphere
3, ultimate compression strength>=500MPa, size is 100 ~ 500nm;
The mass ratio of described high molecule polymer template, cetyl trimethyl tertiary amine, Zircosol ZN, aluminum isopropylate and tetraethoxy is 1:(0.1-0.5): (0.5-10): (0.5-10): (1-20), in the mixing solutions of ethylene glycol and water, the volume ratio of ethylene glycol and water is 1:(1-10).
2. a kind of SiO according to claim 1
2/ ZrO
2/ Al
2o
3the preparation method of compound nano-hollow sphere, is characterized in that, described high molecule polymer template is the one in polystyrene, urethane, polyacrylic acid ester microsphere, and particle diameter is 50-200nm.
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| CN105536807B (en) * | 2015-12-27 | 2018-10-23 | 河南泛锐复合材料研究院有限公司 | A kind of preparation method of bismuth ferrate nano hollow ball |
| CN107511125A (en) * | 2017-09-06 | 2017-12-26 | 南京理工大学 | Load the preparation method of hollow Nano hydrous zirconium oxide(HZO) grade polymer drops |
| CN108585842B (en) * | 2018-05-24 | 2020-09-22 | 宁波海纳机械有限公司 | High-performance engine heat shield and preparation method thereof |
| CN108640151B (en) * | 2018-06-11 | 2020-07-14 | 东南大学 | Aluminum-containing zirconium oxide hollow microsphere and preparation method thereof |
| CN108893765B (en) * | 2018-09-12 | 2019-09-17 | 胜利油田金岛实业有限责任公司 | A kind of overlay coating method of the oil well pump for oil recovery process |
| CN109225169A (en) * | 2018-09-19 | 2019-01-18 | 陕西科技大学 | A kind of preparation method and the photochemical catalyst aoxidizing the agent of zirconium base adsorption photochemical catalysis |
| CN111484053A (en) * | 2020-04-28 | 2020-08-04 | 无锡迈科为生物科技有限公司 | Preparation method of aluminum trioxide microspheres |
| CN116120045B (en) * | 2022-12-30 | 2023-12-08 | 新化县顺达电子陶瓷有限公司 | Ceramic material for light low-heat-conduction 5G signal base station |
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| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN102992334A (en) * | 2011-09-08 | 2013-03-27 | 江南大学 | Hollow nano-grade silica particles and preparation method of heat-insulation paint thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772363A (en) * | 2004-11-11 | 2006-05-17 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
| CN102992334A (en) * | 2011-09-08 | 2013-03-27 | 江南大学 | Hollow nano-grade silica particles and preparation method of heat-insulation paint thereof |
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