CN101113219A - Preparation method of monodisperse polystyrene/zirconium dioxide core-shell colloid composite spherical particles - Google Patents
Preparation method of monodisperse polystyrene/zirconium dioxide core-shell colloid composite spherical particles Download PDFInfo
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- CN101113219A CN101113219A CNA2006100889887A CN200610088988A CN101113219A CN 101113219 A CN101113219 A CN 101113219A CN A2006100889887 A CNA2006100889887 A CN A2006100889887A CN 200610088988 A CN200610088988 A CN 200610088988A CN 101113219 A CN101113219 A CN 101113219A
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- monodisperse polystyrene
- zirconium dioxide
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 50
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 50
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000084 colloidal system Substances 0.000 title claims description 14
- 239000012798 spherical particle Substances 0.000 title abstract 7
- 239000002245 particle Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 49
- 239000003292 glue Substances 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- -1 zirconium alkoxide Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000011246 composite particle Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of preparation and application of submicron-sized composite materials, and particularly relates to a preparation method of monodisperse core-shell composite spherical particles with several-to dozens of nanometers of zirconium dioxide coated on monodisperse polystyrene colloidal spherical particles (the particle diameter is 80-3000 nanometers), and a corresponding spherical zirconium dioxide hollow sphere obtained by removing template particles through high-temperature calcination. The preparation method is simple, the obtained core-shell spherical particles have good dispersibility, the coating layer is uniform, and the thickness of the coating layer can be controlled by reaction conditions. In addition, core-shell spherical particles with different sizes can be obtained by changing the size of the polystyrene particles as templates. The core-shell spherical particles can remove template particles through high-temperature calcination, so that more uniform zirconium dioxide hollow spherical particles are obtained.
Description
Technical field
The invention belongs to the preparation and the applied technical field of submicron-scale matrix material, particularly relate at monodisperse polystyrene colloid ball particle (particle diameter is 80～3000 nanometers) and go up the single preparation method who disperses the nucleocapsid composite ball particle who coats zirconium dioxide, and obtain corresponding spheric zirconium dioxide hollow ball by high-temperature calcination removal template particles.
Background technology
Zirconium dioxide (ZrO
2) as a kind of high function fine inorganic material, be important pottery, semi-conductor and catalytic material, because it has special performances such as good weathering resistance, chemical resistance, higher chemical stability, thermostability, nontoxicity, photosensitivity, so be widely used in fields such as chemical industry, electronics, biology, coating, transmitter, dielectric materials, plastics, printing ink, papermaking, chemical fibre, rubber, for example:
(1) the molten boiling point height of zirconium dioxide, erosion resistance is strong, can resist the erosion of acid and neutral melt, so be used as refractory materials;
(2) the zirconium dioxide surface has weak acid, weak base double function characteristic, both can be used as catalyzer and also can be used as support of the catalyst and use;
(3) zirconium dioxide has physical strength preferably, can also be as the catalyst structure auxiliary agent;
(4) zirconium dioxide is that the ceramic chemical stability of raw material is good, the hardness height, high temperature resistant, and have good conductivity, be widely used in making aspects such as piezoelectric element, ceramic condenser, gas sensor, solid electrolyte fuel cell, ceramic combustion engine engine.
Zirconium dioxide sub-micron ball particulate monodispersity has very big influence to it in many application, yet the single relatively difficulty of zirconia balls particulate material of disperseing that directly prepares submicron-scale, people such as Widoniak (" European Journal of Inorganic Chemistry " 2005,15,3149) once report adopts the single zirconium dioxide ball particle that disperses of zirconium hydrolysis of alkoxide preparation, but the too fast easily independent nucleation of zirconium hydrolysis of alkoxide, make particle monodispersity variation, the particles dispersed degree is greater than 10%.
When on template particles, coating inorganic materials shell such as zirconium dioxide, adopt the method for zirconium alkoxide precursor hydrolysis can obtain the purity high product, but because the hydrolysis of zirconium alkoxide precursor is very fast, exist coating layer second-rate, shell thickness is difficult to shortcomings such as control (" Inorganic Chemistry Communications " 2003,6,942).
Summary of the invention
One of purpose of the present invention provides the preparation method of monodisperse polystyrene/zirconia core-shell glue composite ball particle.
Two of purpose of the present invention provides the monodisperse polystyrene/zirconia core-shell glue composite ball particle that coats the zirconium dioxide layer on the surface of monodisperse polystyrene colloid ball particle; This zirconium dioxide shell thickness can be realized controlled by changing processing condition.
Three of purpose of the present invention provides by high-temperature calcination monodisperse polystyrene/zirconia core-shell glue composite ball particle, obtains corresponding spheric zirconium dioxide hollow ball to remove template particles.
It is template that the present invention adopts the monodisperse polystyrene colloid ball particle, prepare monodispersed polystyrene/zirconia core-shell glue composite ball particle, the particles dispersed degree of this monodisperse polystyrene/zirconia core-shell glue composite ball particle is less than 3%, and obtains the zirconium dioxide hollow ball of uniform spherical by calcining.By adopting the high template particles of single dispersity, the present invention not only can obtain high-quality composite particles, has also saved raw material simultaneously, has reduced production cost.
The preparation thinking of monodisperse polystyrene/zirconia core-shell glue composite ball particle of the present invention not only can obtain the monodispersed zirconium dioxide inorganic materials of high quality, can remove template particles by the high-temperature calcination method simultaneously, thereby obtain spheric two zirconium dioxide hollow ball, this spheric zirconium dioxide hollow ball will be better mould material, have using value widely at aspects such as microreactor, medicament slow release, high-specific surface area catalytic carrier, ceramic condenser, gas sensor, solid electrolyte fuel cell, ceramic combustion engine engines.
Monodisperse polystyrene/zirconia core-shell glue composite ball particle of the present invention is to be made of monodisperse polystyrene colloid ball particle and zirconium dioxide, and it is to coat the zirconium dioxide layer on the surface of monodisperse polystyrene colloid ball particle; The diameter range of this core-shell glue composite ball particle is 90nm～3200nm, and the zirconium dioxide shell thickness is between 5nm～100nm, preferably between 5nm～70nm.
Described monodisperse polystyrene colloid ball particle diameter is 80nm～3000nm, and the particle size distribution average deviation is less than 5%.
The objective of the invention is to realize by the following method: at ambient temperature, in the mixed solvent system that is dispersed with monodisperse polystyrene colloid ball particle and deionized water, add the mixed solvent that is dispersed with the zirconium alkoxide precursor, the hydrolysis of zirconium alkoxide precursor, form even zirconium dioxide shell on monodisperse polystyrene colloid ball particle surface, this core-shell glue composite ball particle can be got zirconium dioxide hollow sphere particle through high-temperature calcination.
The present invention adopts the preparation method of the monodisperse polystyrene/zirconia core-shell glue composite ball particle of mixed solvent preparation may further comprise the steps:
(1) dehydrated alcohol and polar solvent are mixed, wherein the volume ratio of dehydrated alcohol and polar solvent is 2: 3～9: 1;
(2) with monodisperse polystyrene colloid ball particle ultra-sonic dispersion in the mixed solvent of step (1) gained, wherein the starting point concentration of monodisperse polystyrene colloid ball particle is 0.01～100 grams per liter;
(3) deionized water is joined in the mixture of step (2) gained, stir, wherein the starting point concentration of water is 0.01～5 mol, is preferably 0.1～1.5 mol;
(4) the zirconium alkoxide is dissolved in the mixed solvent of step (1) gained, stirs, its starting point concentration is 1 * 10
-4～5 mol are preferably 5 * 10
-4～1.5 mol;
(5) at ambient temperature, step (4) liquid mixture prepared is joined in step (3) liquid mixture prepared, wherein the volume ratio of the mixed solution of the mixed solution of step (4) and step (3) is 4: 1, magnetic agitation reaction 0.5～10 hour, centrifugation obtains having monodispersed, that coating layer is good monodisperse polystyrene/zirconia core-shell glue composite ball particle;
(6) with gained monodisperse polystyrene in the step (5)/zirconia core-shell glue composite particles further 400～1000 ℃ of following sintering 1～6 hour, obtain spheric zirconium dioxide hollow ball.
The diameter range of described monodisperse polystyrene/zirconia core-shell glue composite particles is 90nm～3200nm, and the zirconium dioxide shell thickness is between 5nm～100nm, and preferred shell thickness is at 5nm～70nm.
The diameter range of described monodisperse polystyrene colloid ball particle is 80nm～3000nm, and preferred diameter is 100nm～3000nm.
Described zirconium alkoxide molecular formula is Zr (OR)
4, wherein R is-C
nH
2n+1, n=2～4.
Described polar solvent is acetone, acetonitrile or methyl alcohol etc.
The diameter range of described spheric zirconium dioxide hollow ball is between 90nm～3000nm, and the zirconium dioxide shell thickness is between 5nm～90nm.
Effect of the present invention and advantage:
Monodisperse polystyrene/zirconia core-shell glue the composite particles that adopts method of the present invention to obtain is the sphere of homogeneous, good dispersity, as shown in Figure 1.
Hydrolysis method energy consumption of the present invention is low, and the employing deionized water is a catalyzer, can not introduce other salt ion, makes the product purity height.
The present invention can realize the control of zirconium dioxide shell thickness by the concentration in control zirconium source.
The monodisperse polystyrene that the present invention makes/zirconia core-shell glue composite particles has significantly reduced the use of raw material than the zirconium dioxide particle of identical particle diameter, has reduced production cost.
It is simple that the present invention prepares the method for monodisperse polystyrene/zirconia core-shell glue composite particles, is easy to apply, and solvent for use is inexpensive, be easy to get, safety.
The present invention by high-temperature calcination get final product spherical complete zirconium dioxide hollow particle, as shown in Figure 2.
Further the present invention will be described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1. the transmission electron microscope photo of embodiments of the invention 1 monodisperse polystyrene/zirconia core-shell glue composite ball particle.
Fig. 2. the electron scanning micrograph of the spheric zirconium dioxide hollow ball that the high-temperature calcination of embodiments of the invention 2 nucleocapsid particles process obtains.
Embodiment
Embodiment 1
Dehydrated alcohol and the methyl alcohol volume ratio by 3: 2 is mixed, it is even to add a certain amount of monodisperse polystyrene ball particle (particle diameter 160nm) ultra-sonic dispersion again, mass concentration is 0.4g/L, add a certain amount of deionized water again, make the concentration of deionized water be about 0.2 mol, this dispersion liquid is designated as A liquid; Other gets a certain amount of volume ratio is 3: 2 the dehydrated alcohol and the mixed solvent of methyl alcohol, adds a certain amount of zirconium-n-butylate, make the concentration of zirconium-n-butylate be about 25 mmoles/liter, this dispersion liquid is designated as B liquid.At ambient temperature, B liquid is joined in the A liquid, B liquid and A liquid volume ratio are 4: 1, magnetic agitation 2 hours obtains white opacity liquid, centrifugation, obtain spherical monodisperse polystyrene/zirconia core-shell glue composite ball particle, average diameter of particles is about 190 nanometers, and the zirconium dioxide shell thickness is about 15 nanometers, as shown in Figure 1.
Embodiment 2
Dehydrated alcohol and the acetonitrile volume ratio by 5: 1 is mixed, add a certain amount of monodisperse polystyrene ball particle (particle diameter 120nm) ultra-sonic dispersion again, mass concentration is 0.4g/L, add a certain amount of deionized water again, make the concentration of deionized water be about 1 mol, this dispersion liquid is designated as A liquid; Other gets a certain amount of dehydrated alcohol and acetonitrile by the mixed solvent of 5: 1 volume ratio, adds a certain amount of zirconium iso-propoxide, make the concentration of zirconium iso-propoxide be about 300 mmoles/liter, this dispersion liquid is designated as B liquid.At ambient temperature, B liquid is joined in the A liquid, B liquid and A liquid volume ratio are 4: 1, magnetic agitation 10 hours, obtain white opacity liquid, centrifugation obtains spherical monodisperse polystyrene/zirconia core-shell glue composite ball particle, average diameter of particles is about 210 nanometers, and shell thickness is about 45 nanometers.Gained monodisperse polystyrene/zirconia core-shell glue composite ball particle 500 ℃ of sintering 8 hours, can be got spheric zirconium dioxide hollow ball.The particle diameter of zirconium dioxide hollow particle is 210nm, the about 45nm of shell thickness.As shown in Figure 2.
Embodiment 3
Dehydrated alcohol and the acetone volume ratio by 12: 5 is mixed, add a certain amount of commercially available monodisperse polystyrene ball particle (particle diameter 280nm) ultra-sonic dispersion again, mass concentration is 0.4g/L, add a certain amount of deionized water again, make the concentration of deionized water be about 2 mol, this dispersion liquid is designated as A liquid; Other gets a certain amount of dehydrated alcohol and acetone by the mixed solvent of 12: 5 volume ratio, adds a certain amount of zirconium-n-propylate, make the concentration of zirconium-n-propylate be about 40 mmoles/liter, this dispersion liquid is designated as B liquid.At ambient temperature, B liquid is joined in the A liquid, B liquid and A liquid volume ratio are 4: 1, magnetic agitation 8 hours, obtain white opacity liquid, centrifugation obtains spherical monodisperse polystyrene/zirconia core-shell glue composite ball particle, average diameter of particles is about 320 nanometers, and shell thickness is about 20nm.Gained monodisperse polystyrene/zirconia core-shell glue composite ball particle 700 ℃ of sintering 6 hours, can be got spheric zirconium dioxide hollow ball.The particle diameter of zirconium dioxide hollow particle is 320nm, the about 20nm of shell thickness.
Embodiment 4
Dehydrated alcohol and the acetonitrile volume ratio by 9: 7 is mixed, add a certain amount of monodisperse polystyrene ball particle (particle diameter 160nm) ultra-sonic dispersion again, mass concentration is 0.4g/L, add a certain amount of deionized water again, make the concentration of deionized water be about 3 mol, this dispersion liquid is designated as A liquid; Other gets a certain amount of dehydrated alcohol and acetonitrile by the mixed solvent of 9: 1 volume ratio, adds a certain amount of zirconium-n-propylate, make the concentration of zirconium-n-propylate be about 600 mmoles/liter, this dispersion liquid is designated as B liquid.At ambient temperature, B liquid is joined in the A liquid, B liquid and A liquid volume ratio are 4: 1, magnetic agitation 5 hours, obtain white opacity liquid, centrifugation obtains spherical monodisperse polystyrene/zirconia core-shell glue composite ball particle, average diameter of particles is about 300 nanometers, and shell thickness is about 70nm.Gained monodisperse polystyrene/zirconia core-shell glue composite ball particle at 900 ℃ of sintering 3 hours respectively, can be got spheric zirconium dioxide hollow ball.The particle diameter of zirconium dioxide hollow particle is 295nm, the about 68nm of shell thickness.
Dehydrated alcohol and the acetone volume ratio by 7: 1 is mixed, add a certain amount of monodisperse polystyrene ball particle (particle diameter 250nm) ultra-sonic dispersion again, mass concentration is 0.4g/L, add a certain amount of deionized water again, make the concentration of deionized water be about 0.1 mol, this dispersion liquid is designated as A liquid; Other gets a certain amount of dehydrated alcohol and acetone by the mixed solvent of 7: 2 volume ratio, adds a certain amount of zirconium iso-propoxide, make the concentration of zirconium iso-propoxide be about 5 mmoles/liter, this dispersion liquid is designated as B liquid.At ambient temperature, B liquid is joined in the A liquid, B liquid and A liquid volume ratio are 4: 1, magnetic agitation 6 hours, obtain white opacity liquid, centrifugation obtains spherical monodisperse polystyrene/zirconia core-shell glue composite ball particle, average diameter of particles is about 180 nanometers, and shell thickness is about 10nm.
Claims (10)
1. the preparation method of a monodisperse polystyrene/zirconia core-shell glue composite ball particle is characterized in that, this method may further comprise the steps:
(1) dehydrated alcohol and polar solvent are mixed, wherein the volume ratio of dehydrated alcohol and polar solvent is 2: 3～9: 1;
(2) with monodisperse polystyrene colloid ball particle ultra-sonic dispersion in the mixed solvent of step (1) gained, wherein the starting point concentration of monodisperse polystyrene colloid ball particle is 0.01～100 grams per liter;
(3) deionized water is joined in the mixture of step (2) gained, stir, wherein the starting point concentration of water is 0.01～5 mol;
(4) the zirconium alkoxide is dissolved in the mixed solvent of step (1) gained, stirs, its starting point concentration is 1 * 10
-4～5 mol;
(5) at ambient temperature, step (4) liquid mixture prepared is joined in step (3) liquid mixture prepared, wherein the volume ratio of the mixed solution of the mixed solution of step (4) and step (3) is 4: 1, the magnetic agitation reaction, centrifugation obtains monodisperse polystyrene/zirconia core-shell glue composite ball particle.
2. method according to claim 1 is characterized in that: described monodisperse polystyrene/zirconia core-shell glue composite particles obtains spheric zirconium dioxide hollow ball at 400～1000 ℃ of following sintering.
3. method according to claim 1 is characterized in that: the diameter range of described monodisperse polystyrene/zirconia core-shell glue composite particles is 90nm～3200nm, and the zirconium dioxide shell thickness is between 5nm～100nm.
4. method according to claim 1 is characterized in that: the diameter of described monodisperse polystyrene ball particle is 80nm～3000nm.
5. method according to claim 1 is characterized in that: described zirconium alkoxide molecular formula is Zr (OR)
4, wherein R is-C
nH
2n+1, n=2～4.
6. method according to claim 1 is characterized in that: described polar solvent is acetone, acetonitrile or methyl alcohol.
7. method according to claim 1 is characterized in that: the starting point concentration of described water is 0.1～1.5 mol.
8. method according to claim 1 is characterized in that: the starting point concentration of described zirconium alkoxide is 5 * 10
-4～1.5 mol.
9. method according to claim 2 is characterized in that: the diameter of described spheric zirconium dioxide hollow ball is between 90nm～3000nm, and zirconium dioxide hollow ball shell thickness is between 5nm～90nm.
10. method according to claim 2 is characterized in that: described sintering time is 1～6 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302361B (en) * | 2008-06-12 | 2011-12-14 | 中国科学院上海硅酸盐研究所 | Preparation of zircite cladding iron oxide powder |
| CN103274672A (en) * | 2013-04-23 | 2013-09-04 | 西南科技大学 | Preparation method for alumina hollow spheres |
| CN108947569A (en) * | 2018-08-30 | 2018-12-07 | 盛世瑶兰（深圳）科技有限公司 | A kind of hollow heat insulated construction material of high intensity and its application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4660905B2 (en) * | 2000-09-28 | 2011-03-30 | 東ソー株式会社 | Method for producing zirconia microspheres |
| US20020160196A1 (en) * | 2000-10-28 | 2002-10-31 | Regents Of The University Of Minnesota | Microspheres of metal oxides and methods |
| CN100464833C (en) * | 2004-11-11 | 2009-03-04 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
-
2006
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302361B (en) * | 2008-06-12 | 2011-12-14 | 中国科学院上海硅酸盐研究所 | Preparation of zircite cladding iron oxide powder |
| CN103274672A (en) * | 2013-04-23 | 2013-09-04 | 西南科技大学 | Preparation method for alumina hollow spheres |
| CN103274672B (en) * | 2013-04-23 | 2014-08-13 | 西南科技大学 | Preparation method for alumina hollow spheres |
| CN108947569A (en) * | 2018-08-30 | 2018-12-07 | 盛世瑶兰（深圳）科技有限公司 | A kind of hollow heat insulated construction material of high intensity and its application |
| CN108947569B (en) * | 2018-08-30 | 2021-10-01 | 盛世瑶兰（深圳）科技有限公司 | High-strength hollow heat-insulation building material and application thereof |
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| CN100503714C (en) | 2009-06-24 |
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