CN114560470B - Silica hollow nanosphere, preparation method and application thereof - Google Patents
Silica hollow nanosphere, preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 38
- 239000002077 nanosphere Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 131
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 23
- 239000005060 rubber Substances 0.000 abstract description 23
- 239000011521 glass Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000011324 bead Substances 0.000 abstract description 7
- 239000012744 reinforcing agent Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a silicon dioxide hollow nanosphere, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Respectively preparing absolute ethanol solutions containing tetraethoxysilane, ammonia water and nano silicon oxide slurry, and sequentially obtaining a solution A, B, C; (2) Dropwise adding part of the solution A into the solution B, and vigorously stirring to obtain a first mixed solution; simultaneously adding the solution C and the rest part of the solution A into the first mixed solution at a speed of less than 1ml/min, and slowly stirring to obtain a second mixed solution; and adding the rest solution A into the second mixed solution, and centrifuging, washing and drying to obtain the product. The method has the advantages of convenience, rapidness, controllable product morphology, no need of high-temperature calcination and the like, and the prepared material is not fragile, has a certain rubber reinforcing effect, can be used as a reinforcing agent after being disintegrated, can replace hollow glass beads, improves the mechanical property of rubber and reduces the density, and is suitable for aerospace rubber with the density of rubber materials needing to be controlled.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a silica hollow nanosphere, a preparation method and application thereof.
Background
The polymer material is an important matching material for supporting the aerospace industry in China and mainly comprises rubber, engineering plastics, adhesive, sealant and the like. The rubber is taken as an ideal sealing and damping material, is widely applied to the aerospace field, and mainly comprises natural rubber, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, ethylene propylene rubber, silicone rubber, fluorosilicone rubber and the like. For example: the carboxyl nitroso fluororubber can be used as an adhesive of solid propellant fuel, a non-combustible coating of chemical medium resistant, a heat-resistant and cold-resistant sealing material prepared from silicon rubber, and ethylene propylene rubber can be used as an inner heat insulation lining layer of a solid rocket engine and the like.
The rubber applied to the field also needs a critical performance-density under the condition of good special effect and mechanical property. Under the condition of similar other performances, the adoption of the low-density material can bring better quality bonus to the engine, namely, longer range under low quality, higher acceleration, more flexible adjustment and the like.
The common means for reducing the rubber density adopted by the domestic rubber at the present stage is to adopt a mode of adding hollow glass beads. The hollow glass beads have the advantages of light weight, insulation, no toxicity and the like, but are easy to crack in the rubber refining process due to the size of the hollow glass beads at the micron level, larger glass residues are generated, the residues are impurities in rubber materials, the compatibility with the rubber is not strong, the hollow glass beads can be used as a defect when the rubber is stressed, and the rubber is stressed and cracked to lose efficacy.
Disclosure of Invention
The invention aims to provide an alternative scheme of a rubber filler, so as to solve the problems existing in the prior hollow glass microsphere used as the rubber filler.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention provides a preparation method of a silicon dioxide hollow nanosphere, which comprises the following steps:
(1) Preparing a solution: dispersing tetraethoxysilane in absolute ethyl alcohol to obtain a solution A; dispersing ammonia water in absolute ethyl alcohol to obtain a solution B; dispersing nano silicon oxide slurry in absolute ethyl alcohol to obtain a solution C; preferably, the preparation of the solution A is also assisted by ultrasonic dispersion, and the preparation of the solution B and the solution C is also assisted by magnetic stirring dispersion;
in the solution A, the concentration of the tetraethoxysilane is 1-50% V/V, preferably 10% V/V;
in the solution B, the volume ratio of the ammonia water to the absolute ethyl alcohol is 2:5-7, preferably 2:6, and the ammonia concentration of the ammonia water is 25-28wt%, preferably 28wt%;
in the solution C, the volume ratio of the nano silicon oxide slurry to the absolute ethyl alcohol is 1:70-90, preferably 1:80, the silicon dioxide content in the nano silicon oxide slurry is 15-20wt% and the particle size is 3-20nm;
(2) Preparing a silica hollow nanosphere: the first step: dropwise adding part of the solution A into the solution B, and vigorously stirring at a speed of 150-200rpm for 8-12min to obtain a first mixed solution; and a second step of: adding the solution C and the rest part of the solution A into the first mixed solution at the speed of less than 1ml/min, and slowly stirring at the speed of 50-100rpm for 0.8-1.2h to obtain a second mixed solution; and a third step of: adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring at a speed of 50-100rpm for 1.5-2.5h, centrifuging, washing the precipitate, drying, preferably centrifuging for 3-10min at 10000-12000r/min, washing with water and alcohol for 3 times, and drying at 60 ℃ to obtain the silica hollow nanospheres;
in the preparation of the silica hollow nanospheres, the volume ratio of the solution A to the solution B to the solution C added three times is 1-2:8-12:10-15:70-90:7-9, preferably 2:8:10:80:8.
According to the preparation method, TEOS is used as a precursor, ammonia water is used as a catalyst, nano silicon oxide slurry is used as an auxiliary agent and a structure is formed, and the sequence, quality and speed of feeding are controlled to control the generation of a core-shell structure and the size of a cavity at normal temperature. Specifically, the process for preparing the silica hollow nanospheres comprises the following steps: 1) The first step is for producing SiO 2 The seeds required for growth are formed, the size of the seeds can be adjusted by adjusting the adding amount of the solution A in the first step, specifically, the more the adding amount of the solution A is, the faster the adding speed is, the larger the volume and the more the number of the seeds are; 2) In the second step, the size of the cavity can be adjusted by adjusting the addition amount of the solution A and the solution C, in particular, the additionThe more the solution A and the solution C are, the faster the adding speed is, the larger the hollow cavity of the hollow sphere is, and the sphere is more easily broken; 3) In the third step, the thickness of the shell can be adjusted by adjusting the adding amount of the solution A, specifically, the more the solution A is added, the faster the adding speed is, and the thicker the shell is. 4) The size of the nanospheres can be adjusted by adjusting the overall addition proportion. Specifically, the smaller amount of solution A added in the first step can enlarge the nanospheres, and the larger the amount of solution A added in the third step, the larger the nanospheres.
The method can finally prepare the silica hollow nanospheres with the thickness of about 50-500 nm. The invention provides the preparation method of the hollow silica nanospheres, which is controllable in size and shape, convenient and quick, can be realized at normal temperature, and does not need conditions such as high-temperature calcination and the like.
The hollow silica nanospheres prepared by the method can be used as a reinforcing agent, and can also be used as a filling agent for reducing density and heat conductivity.
Compared with the traditional hollow glass beads, the material disclosed by the invention is not fragile, has a certain rubber reinforcing effect, can be used as a reinforcing agent after being cracked, can replace the hollow glass beads, and is used for improving the mechanical property of rubber and reducing the density of rubber. Can be used as a reinforcing agent, a heat insulating material or a density-reducing filler in aerospace rubber.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The embodiment provides a preparation method of a silica hollow nanosphere, which comprises the following steps:
(1) Preparing a solution: 2ml of tetraethyl orthosilicate (TEOS) is ultrasonically dispersed in 18ml of absolute ethyl alcohol for 30S to obtain a solution A; 20mL 28wt% ammonia water is magnetically stirred for 3min and dispersed in 60mL absolute ethanol to obtain solution B; 100 μl of nano silicon oxide slurry (containing 15wt% of silicon dioxide and having a particle size of 3-20 nm) was magnetically stirred for 3min and dispersed in 8mL of absolute ethanol to obtain solution C;
(2) Preparing a silica hollow nanosphere: firstly, part of the solution A is dropwise added into the solution B, and the solution A is vigorously stirred at a speed of 150rpm for 10min to obtain a first mixed solution; then simultaneously adding the solution C and the rest part of the solution A into the first mixed solution at a speed of less than 1ml/min through two peristaltic pumps, and slowly stirring at a speed of 50rpm for 1h to obtain a second mixed solution; and finally, adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring the solution A, the solution B and the solution C which are added three times in sequence at a volume ratio of 2:8:10:80:8 at a speed of 50rpm for 2 hours, centrifuging the solution A for 5min at 12000r/min, washing the solution A with water and washing the solution B with alcohol for 3 times respectively, and drying the solution C at 60 ℃ to obtain the 100nm silicon dioxide hollow nanospheres.
Example 2
The embodiment provides a preparation method of a silica hollow nanosphere, which comprises the following steps:
(1) Preparing a solution: an ethyl orthosilicate-absolute ethanol solution with the concentration of 1%V/V of ethyl orthosilicate is prepared according to the method of the example 1 to obtain a solution A; preparing an ammonia water-absolute ethanol solution with the volume ratio of ammonia water (ammonia concentration is 25 wt%) to absolute ethanol of 2:5 to obtain a solution B; preparation of nano silicon oxide Slurry (SiO) 2 The content of the nanometer silica slurry is 20wt%) and the volume ratio of the absolute ethyl alcohol is 1:70, and a solution C is obtained;
(2) Preparing a silica hollow nanosphere: firstly, adding part of the solution A into the solution B dropwise, and vigorously stirring at a speed of 200rpm for 8min to obtain a first mixed solution; then adding the solution C and the rest part of the solution A into the first mixed solution at the speed of less than 1ml/min, and slowly stirring at the speed of 100rpm for 0.8h to obtain a second mixed solution; and finally, adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring the solution A, the solution B and the solution C which are added three times in sequence at a volume ratio of 1:12:15:70:7 at a speed of 100rpm for 1.5h, centrifuging the solution A for 10min at 10000r/min in sequence, washing the solution A with water and alcohol for 3 times respectively, and drying the solution A, the solution B and the solution C at 60 ℃ to obtain the silica hollow nanospheres.
Example 3
The embodiment provides a preparation method of a silica hollow nanosphere, which comprises the following steps:
(1) Preparing a solution: an ethyl orthosilicate-absolute ethanol solution with the concentration of 50% V/V of ethyl orthosilicate is prepared according to the method of the example 1 to obtain a solution A; preparing an ammonia water-absolute ethanol solution with the volume ratio of ammonia water (ammonia concentration is 28 wt%) to absolute ethanol of 2:7 to obtain a solution B; preparation of nano silicon oxide Slurry (SiO) 2 15wt% of the content of the absolute ethyl alcohol) and the volume ratio of the absolute ethyl alcohol to be 1:90 to obtain a solution C;
(2) Preparing a silica hollow nanosphere: firstly, adding part of the solution A into the solution B dropwise, and vigorously stirring at a speed of 200rpm for 12min to obtain a first mixed solution; then adding the solution C and the rest part of the solution A into the first mixed solution at the speed of less than 1ml/min, and slowly stirring at the speed of 50rpm for 1.2h to obtain a second mixed solution; and finally, adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring the solution A, the solution B and the solution C for 2.5h at a speed of 50rpm, centrifuging for 3min at 12000r/min, washing with water and alcohol for 3 times, and drying at 60 ℃ to obtain the silica hollow nanospheres.
Comparative example 1
The difference from example 1 is that step (2) is: firstly, dropwise adding the solution A into the solution B, and vigorously stirring at a speed of 150rpm for 10min to obtain a first mixed solution; then adding the solution C into the first mixed solution at a speed of less than 1ml/min through a peristaltic pump, and slowly stirring at a speed of 50rpm for 1h to obtain a second mixed solution; the volume ratio of the solution A to the solution B to the solution C is 20:80:8, and the solution A, the solution B and the solution C are sequentially centrifuged for 5min at 12000r/min, washed with water and alcohol for 3 times and then dried at 60 ℃, so that the hollow silica pellets are obtained, but the solid silica pellets are obtained.
Comparative example 2
The difference from example 1 is that step (2) is: firstly, part of the solution A is dropwise added into the solution B, and the solution A is vigorously stirred at a speed of 150rpm for 10min to obtain a first mixed solution; then simultaneously adding the solution C and the rest part of the solution A into the first mixed solution at the speed of 4ml/min through two peristaltic pumps, and slowly stirring at the speed of 50rpm for 1h to obtain a second mixed solution; and finally, adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring the solution A, the solution B and the solution C which are added three times in sequence at a volume ratio of 2:8:10:80:8 at a speed of 50rpm for 2 hours, centrifuging the solution A for 5min at 12000r/min, washing the solution with water and alcohol for 3 times respectively, and drying at 60 ℃ to obtain silica pellets with uniform sizes, and part of mesopores, part of hollows and part of solids.
The silica hollow nanospheres prepared in example 1 and comparative example 1-2 are used as rubber filler to prepare vulcanized rubber 1# 8, and the raw materials are prepared according to the following proportions in tables 1 and 2:
TABLE 1
TABLE 2
The rubber compound obtained by mixing the raw materials is vulcanized for 2 hours at 150 ℃, and the performance detection results of the obtained materials are shown in table 3.
TABLE 3 statistical table for material property detection
| Density (g/cm) 3 ) | Tensile breaking strength (Mpa) | |
| 1# | 0.96 | 6.5 |
| 2# | 1.12 | 5.6 |
| 3# | 1.07 | 6.1 |
| 4# | 1.15 | 5.4 |
| 5# | 1.23 | 5.4 |
| 6# | 1.40 | 4.7 |
| 7# | 1.32 | 5.1 |
| 8# | 1.45 | 4.5 |
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. The preparation method of the silica hollow nanospheres is characterized by comprising the following steps:
(1) Preparing a solution: dispersing tetraethoxysilane in absolute ethyl alcohol to obtain a solution A; dispersing ammonia water in absolute ethyl alcohol to obtain a solution B; dispersing nano silicon oxide slurry in absolute ethyl alcohol to obtain a solution C;
in the solution A, the concentration of the tetraethoxysilane is 1-50% V/V;
in the solution B, the volume ratio of the ammonia water to the absolute ethyl alcohol is 2:5-7, and the ammonia concentration of the ammonia water is 25-28wt%;
in the solution C, the volume ratio of the nano silicon oxide slurry to the absolute ethyl alcohol is 1:70-90, the silicon dioxide content in the nano silicon oxide slurry is 15-20wt% and the grain diameter is 3-20nm;
(2) Preparing a silica hollow nanosphere: the first step: dropwise adding part of the solution A into the solution B, and vigorously stirring at a speed of 150-200rpm for 8-12min to obtain a first mixed solution; and a second step of: adding the solution C and the rest part of the solution A into the first mixed solution at the speed of less than 1ml/min, and slowly stirring at the speed of 50-100rpm for 0.8-1.2h to obtain a second mixed solution; and a third step of: adding the rest solution A into the second mixed solution at a speed of less than 1ml/min, stirring at a speed of 50-100rpm for 1.5-2.5h, centrifuging, washing, precipitating, and drying to obtain the silica hollow nanospheres;
in the preparation of the silica hollow nanospheres, the volume ratio of the solution A to the solution B to the solution C which are sequentially added for three times is 1-2:8-12:10-15:70-90:7-9.
2. The method for preparing hollow silica nanospheres according to claim 1, wherein in step (1), the concentration of ethyl orthosilicate in the solution a is 10% V/V.
3. The method for preparing hollow silica nanospheres according to claim 1, wherein in the step (1), the volume ratio of ammonia water to absolute ethanol in the solution B is 2:6, and the ammonia concentration of the ammonia water is 28wt%.
4. The method for preparing hollow silica nanospheres according to claim 1, wherein in step (1), the volume ratio of the nano silica slurry to absolute ethanol in the solution C is 1:80.
5. The method for preparing hollow silica nanospheres according to claim 1, wherein in step (1), ultrasonic dispersion is further assisted in the preparation of the solution a, and magnetic stirring dispersion is further assisted in the preparation of the solution B and the solution C.
6. The method for preparing the hollow silica nanospheres according to claim 1, wherein in the step (2), the volume ratio of the solution A to the solution B to the solution C added three times is 2:8:10:80:8.
7. The method for preparing silica hollow nanospheres according to claim 1, wherein in the step (2), 10000-12000r/min is adopted for centrifugation for 3-10min, and then washing with water and alcohol is carried out for 3 times, and then drying is carried out at 60 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931718A (en) * | 2006-10-09 | 2007-03-21 | 中国科学技术大学 | Prepn process of hollow silica ball |
| CN102633265A (en) * | 2012-03-29 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres |
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