CN111099597B - Active nano silicon dioxide microsphere, solution, preparation method and application thereof - Google Patents
Active nano silicon dioxide microsphere, solution, 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 171
- 239000004005 microsphere Substances 0.000 title claims abstract description 88
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 64
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 6
- -1 silicate ester Chemical class 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000005466 alkylenyl group Chemical group 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 229960005150 glycerol Drugs 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 24
- 239000002086 nanomaterial Substances 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000000919 ceramic Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 238000007865 diluting Methods 0.000 description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 240000002853 Nelumbo nucifera Species 0.000 description 9
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 9
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002103 nanocoating Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000012620 biological material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 240000007472 Leucaena leucocephala Species 0.000 description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- Wood Science & Technology (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Silicon Compounds (AREA)
Abstract
The invention relates to an active nano silicon dioxide microsphere, a solution, a preparation method and application thereof, and mainly aims to solve the problem of using
The nano silicon dioxide microspheres prepared by the method can not directly react with the modified glass, ceramics and silicon surface, so that the problem of difficulty in preparing the coating with the micro-nano characteristic structure is solved. The invention better solves the problem by adopting the technical scheme that the active nano-silica microspheres comprise nano-silica microspheres and an active layer on the surfaces of the nano-silica microspheres, and the active layer contains condensable siloxane, and can be used for preparing coatings with micron or nano structure characteristics on the surfaces of glass, ceramics and silicon.
Description
Technical Field
The invention relates to a solution of nano silicon dioxide microspheres capable of directly carrying out chemical reaction with glass, ceramic or silicon surfaces so as to prepare coatings with micron and nano structural characteristics on the solid surfaces, and a preparation method and application thereof.
Background
The molecular structure, the nano-structure and the micro-structure of the material jointly determine the function of the material. The nano structure is a mesoscopic system which is constructed or built according to a certain rule based on a material unit with a micron and nano scale and comprises a one-dimensional structure, a two-dimensional structure and a three-dimensional structure. Since the nano-structure may give the material a quantum size effect, a small size effect, a surface effect, a quantum coupling effect, a synergistic effect and the like, the construction of the material with the micro-and nano-sized features by various methods is one of the hot spots of the research of the materials science in recent years.
Micro-and nanostructures can impart very rich properties and functionalities to materials. Natural biomaterials such as shells, bones, teeth, etc. have excellent overall properties and functions because they have a complex and elaborate multi-scale hierarchical structure. In the hierarchical structure of these natural biomaterials, small inorganic particles play a very important role. For example, in mollusk shells 95% of calcium carbonate ceramic disks are stacked on top of each other like coins, with a very thin layer of biopolymer between each layer of ceramic disks to bind them together. And each ceramic disk platelet has its own complex nanostructure. Furthermore, the nanostructure system can easily control the performance thereof by an external field. Due to the special role played by nano-inorganic particles on natural biomaterials as well as other materials. The use of inorganic nanoparticles to prepare a wide variety of materials with nano-micro structures has attracted a great deal of attention from scientists.
Wetting is one of the most common phenomena in nature. The phenomenon of infiltration plays an extremely important role both in the daily life of people and in industrial and agricultural production. The physicochemical structure of the surface interface determines the solid surface wettability. Many scientists at home and abroad find that the micro-and nano-structures on the surfaces of animals and plants endow organisms with peculiar wetting behaviors, such as the self-cleaning effect of lotus leaves, by researching the relationship between the wetting properties of various animals and plants in nature and peculiar structures of the surfaces. Many researchers have found that the surface of lotus leaves has specific micron and nanometer size waxy protrusions. Due to the unique micro-nano structure, the lotus leaf surface has super-hydrophobicity. If water drops fall on the lotus leaf surface, the water drops roll off quickly and cannot wet the lotus leaf surface, and meanwhile dust falling on the lotus leaf surface is adhered away, so that the lotus leaf has self-cleaning performance, and people often see that the lotus leaf surface in summer is very clean and rarely stained with dust and water.
In order to realize the peculiar properties of the biosurfaces/interfaces on the material surface, many scientists use various methods to prepare structures with micron and nanometer sizes on the material surface. For example, the Jiangre research group of the chemical research institute of Chinese academy of sciences proposes a simple and effective method for self-assembling a one-dimensional array carbon nanotube into a three-dimensional micrometer-scale patterned surface. The national laboratory Liujun research group in the North of the Taiping American utilizes a wet chemical method to build a complex multi-scale hierarchical ordered nanostructure through the distribution sequential nucleation and growth of crystals.
The nano silicon dioxide microspheres are a commonly used unit for constructing a micro-nano structure. By using
The silicon dioxide microsphere synthesized by the method has the characteristics of uniform structure size, adjustable particle size, low refractive index and the like. Many researchers have attempted to build coatings with micro-and nano-features on the surface of materials using nano-silica microspheres. The preparation of SiO with different grain diameters by adopting a sol-gel method for the blue2The particles are obtained by surface modification of composite particles with different shapes, and the super-hydrophobic coating film with the lotus effect is prepared by utilizing the surface self-assembly function of fluorosilicone. The fluoroalkyl functionalized nano mesoporous silica particles are prepared by taking tetraethoxysilane and fluoroalkyl siloxane as silicon sources, such as Wubao tiger and the like, and the nano particle coating has good permeability-increasing performance on optical glass and is an optical anti-reflection material with excellent performance.
Although nanosilica has a number of advantages, it has a distinct disadvantage: the silica particles themselves cannot react directly with the glass, ceramic and silicon surfaces to be modified to form a bond of some strength. In order to fix silica microsphere coatings with certain micron nanostructures, which have been formed on modified surfaces, with chemical bonds, many researchers have tried many approaches. In order to fix the silicon dioxide microsphere structure with the micro-nano structure, such as Hawai of the university of Compound denier, the coating is soaked by tetrachlorosilane solution. Although the silica microspheres can be immobilized by such a method, tetrachlorosilane may block nano voids in the micro-nano structure.
The invention develops an alcoholic solution system of nano silicon dioxide microspheres with surface reactivity. The alcoholic solution can be directly coated on glass, ceramic and silicon surfaces, and a coating with a micro-nano structure is directly formed on the solid surfaces. The method can be used for preparing rough coatings with changed wettability and can also be used for preparing anti-reflecting coatings on the surfaces of lenses. In addition, the method is expected to be applied to the fields of catalysis, coating, biology and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the nano-silica microspheres for constructing the surface micro-nano structure in the prior art can not directly react with the modified glass, ceramic and silicon surface, and the invention provides the active nano-silica microspheres which have surface activity and can be used for the modified glass, ceramic and silicon surface.
The second technical problem to be solved by the invention is that the nano-silica microspheres for constructing the surface micro-nano structure in the prior art can not directly react with the modified glass, ceramic and silicon surface, and provides an active nano-silica microsphere solution containing surface activity, which comprises active nano-silica microspheres, a surfactant, acid and alcohol.
The third technical problem to be solved by the present invention is to provide a method for preparing an active nano silica microsphere solution corresponding to the second technical problem.
The third technical problem to be solved by the present invention is to provide an application of the active nano-silica microsphere solution corresponding to the second technical problem.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: an active nano-silica microsphere comprises a nano-silica microsphere and an active layer on the surface of the nano-silica microsphere, wherein the active layer contains condensable siloxane.
In the above technical solution, the condensable siloxane is derived from or selected from siloxanes, and the molecular formula of the siloxane is preferably:
in the formula (I), R1And R2Is selected from C1-C10Alkoxy group of (a); r3And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy group of (2).
In order to solve the second technical problem, the invention adopts the following technical scheme: an active nano silicon dioxide microsphere solution comprises the following components in parts by weight:
(1) 0.01-20 parts of active nano silicon dioxide microspheres in one of the technical schemes for solving the technical problems;
(2) 0.001-1 part of a surfactant;
(3) 0.005-5 parts of acid.
In the above technical solution, in the active nano-silica microsphere solution, the active nano-silica microspheres are prepared by modifying the surfaces of the nano-silica microspheres with siloxane under alkaline or acidic conditions, and the siloxane has a molecular general formula:
in the formula (I), R1And R2Is selected from C1-C10Alkoxy of (3), preferably C1-C3Alkoxy group of (a); r2And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy of (3), preferably C1-C3Alkoxy group of (2).
In the technical scheme, the active nano silicon dioxide microspheres are more preferably 0.01-1 part.
In the technical scheme, the surfactant is preferably 0.01-0.1 part; the general molecular formula of the surfactant is preferably:
in the formula (II), R5Is selected from C10-18Alkyl or alkenyl of (a), 1 to 20 siloxy units or C8-18N is selected from 1 to 20, and m is selected from 0 to 20.
In the technical scheme, the acid is preferably 0.01-0.1 part;
in the above technical scheme, R1And R2Preferably C1-C3Linear alkoxy groups of (1).
In the above technical scheme, R3And R4Preferably C1-C3Linear alkoxy groups of (1).
In the above technical solution, the acid is preferably an inorganic acid; more preferably at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the above technical scheme, the alcoholic solution of the active nano-silica microspheres preferably further comprises, in parts by weight: (4) 74-99.94 parts of alcohol; the alcohol may be methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and more preferably ethanol, propanol, isopropanol.
In the technical scheme, the nano active silica microsphere solution is a solution formed by uniformly mixing active nano silica microspheres, a surfactant, acid and alcohol.
In the above technical solution, the nano active silica microsphere solution preferably contains the following components: the weight percentage content of the active nano silicon dioxide microspheres is 0.01 to 20 percent by weight, the weight percentage content of the surface active agent is 0.001 to 1 percent by weight, the weight percentage content of the acid is 0.005 to 5 percent by weight, and the balance is alcohol
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a method for preparing the active nano-silica microsphere solution according to any one of the above two technical solutions, comprising the following steps:
(1) preparation of active nano silicon dioxide microsphere
a) Dissolving silicate ester with required amount in alcohol, reacting in the presence of a catalyst, and removing the catalyst to obtain nano silicon dioxide microsphere alcohol solution;
b) adding silicate ester, water and a catalyst into the nano-silica microsphere alcoholic solution obtained in the step a), and reacting for 2-20 hours to obtain the active nano-silica microspheres;
(2) preparation of active nano silicon dioxide microsphere solution
Uniformly mixing the active nano silicon dioxide microspheres, the surfactant, the acid and the solvent in required amount; obtaining the active nano silicon dioxide microsphere solution.
In the above technical solution, the catalyst is preferably selected from a basic catalyst or an acidic catalyst, and more preferably at least one of ammonia water, sodium hydroxide, hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid; for example, the catalyst in step a) is preferably aqueous ammonia; the catalyst in step b) is preferably at least one of sodium hydroxide, hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid.
In order to solve the fourth technical problem, the technical scheme adopted by the invention is as follows: an application method of the active nano-silica microsphere solution according to any one of the above two technical solutions.
In the above technical solution, the application method is not particularly limited, and for example, but not limited to, the method is directly applied to modifying glass, ceramic and silicon surface; for example, the active nano-silica microsphere solution can be used for forming a coating on the surface of the modified solid material by adopting a method such as soaking, spraying or spin coating. And then curing the coating by heating in a hot air, an oven, a hot plate, and the like. The temperature of the application is preferably from 15 ℃ to 100 ℃.
In the above technical scheme, the concentration of the active nano-silica microspheres in the active nano-silica microsphere solution is preferably 0.5 wt% to 5 wt% based on the weight of the active nano-silica microspheres.
In the above technical scheme, the active nano silica microspheres are not sensitive to alcohol, and may be alcohol known by those skilled in the art, such as methanol, ethanol, propanol, isopropanol, and the like.
The active nano silicon dioxide microspheres prepared by the invention have good structural regularity and good reaction activity performance, and can construct a coating with a regular structure, and the prepared coating has a regular structure and does not contain organic components, so that the ageing resistance is good. The alcoholic solution of the active nano silicon dioxide microspheres can construct a regular coating with a micro-nano characteristic structure and certain strength on the surfaces of various materials. The active nano silicon dioxide microspheres have the advantages of easily obtained raw materials, economic synthetic route, lower final product cost and the like.
The alcohol solution containing 5 wt% of active nano silicon dioxide microspheres prepared by the invention can form a coating with a regular structure and certain strength on glass and silicon surfaces at 65 ℃, and a better technical effect is achieved.
Drawings
FIG. 1 is a scanning electron microscope (410nm) image of the nano-silica microspheres synthesized in example 1.
FIG. 2 shows active nano-silica microspheres (550nm) prepared on the basis of nano-silica microspheres
The present invention will be further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano-silica microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of the nano-silica microspheres to be 410nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. After 5 drops of reaction liquid are diluted by ethanol, the average diameter of the active nano-silica microsphere particles is 550nm by a Malvern particle sizer.
[ example 2 ]
Adding 8ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 70 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 70 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. 5 drops of the reaction solution were diluted with ethanol and the silica particles were measured for diameter of 400nm using a Malvern particle sizer.
[ example 3 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 40 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 40 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 508nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 610nm by a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 4 ]
Adding 15ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 450nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 650nm by a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 5 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 10ml of acetic acid, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing at 50 ℃ for 5 hours to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 400 using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 6 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 430nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of ethyl orthosilicate and 0.05 g of water, and continuing for 5 hours at 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was measured to be 400 using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 7 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of dimethoxydimethylsilane and 0.05 g of water, and continuing for 5 hours at the temperature of 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was 430 by using a malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 8 ]
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃ to obtain nano silicon dioxide microspheres, diluting 5 drops of reaction liquid with ethanol, and testing the diameter of silicon dioxide particles to be 230nm by using a Malvern granulometer. Removing ammonia water in the reaction solution by rotary evaporation, then adding 0.05 g of sodium hydroxide, 5ml of trimethoxy methyl silane and 0.05 g of water, and continuing for 5 hours at the temperature of 50 ℃ to obtain the active nano silicon dioxide microspheres. The diameter of the silica particles was 450 by using a Malvern particle sizer after diluting 5 drops of the reaction solution with ethanol.
[ example 9 ]
The nanospheres and the active nanospheres synthesized in example 1 were observed by scanning electron microscopy. The microspheres in fig. 1 are nanosilica microspheres synthesized in example 1, and the microspheres have an average diameter of about 410nm and a relatively smooth surface. The microspheres in fig. 2 are the active nano-silica microspheres obtained in example 1. It can be seen from the electron microscope photograph that the outer diameter of the active nano-silica microspheres is slightly larger than that of the nano-silica microspheres, the condensation degree between the hydrolyzed silanes of the active layer part is lower, and the surface is not compact and is rough. The nano-micron pore structure between the active nano-silica microspheres is very clear.
Example 10 construction of micro-nano coating by active nano-silica microspheres
Diluting the active nano silicon dioxide microsphere reaction solution to 1 wt% by using ethanol, adding 0.1 wt% of surfactant OFX5211, and then adjusting the pH of the solution to be equal to 3 by using hydrochloric acid. Dropping the active nanometer silicon dioxide microsphere alcohol solution on a glass slide, spreading the solution, and respectively standing overnight at room temperature, 65 ℃, 90 ℃, 150 ℃ and 300 ℃. It was found that a translucent coating having a certain strength could be formed at 65 c and 90 c, while a coating having a certain strength could not be formed at room temperature, 150 c and 300 c. The nano silica microspheres prepared in comparative example 1 could not form a coating having a certain strength at various temperatures. The treated slides were rinsed with ethanol and then blown dry with compressed air. Treated slides were tested for appearance and contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
Table 1 contact angle test of micro-nano coating constructed on glass surface by silicon dioxide microsphere
| Alcoholic solution of active microspheres | Contact angle 1 | |
| Example 1 | 68 | 37 |
| Example 2 | 65 | 34 |
| Example 3 | 70 | 36 |
| Example 4 | 63 | 32 |
| Example 5 | 66 | 31 |
| Example 6 | 61 | 29 |
| Example 7 | 65 | 38 |
| Example 8 | 62 | 32 |
| Glass slide | 34 | 32 |
As can be seen from table 1, the composition of the present invention can effectively form a coating layer having a micro-nano structure with a certain strength on the glass surface. The contact angle of the coating is tested, and the contact angle of the surface of the glass slide with the nano silicon dioxide microsphere coating is obviously higher than that of the glass surface. When the contact angle is measured with hot water, the value of the contact angle is substantially the same as the untreated glass surface. This phenomenon is consistent with the Wenzel and Cassie models. The nano silicon dioxide microspheres are used for processing the surface of the glass to form a micro-nano structure.
Example 11 construction of micro-nano coating by active nano-silica microspheres
Diluting the active nano silicon dioxide microsphere reaction solution to 1 wt% by using ethanol, adding 0.1 wt% of surfactant OFX5211, and then adjusting the pH of the solution to be equal to 3 by using hydrochloric acid. Dripping the active nano silicon dioxide microsphere alcohol solution on a silicon wafer, spreading the solution, and respectively standing overnight at room temperature, 65 ℃, 90 ℃, 150 ℃ and 300 ℃. The treated silicon wafer was rinsed with ethanol and then blown dry with compressed air. Treated slides were tested for appearance and contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
Table 2 contact angle test of micro-nano coating constructed on silicon surface by silicon dioxide microsphere
| Alcoholic solution of active microspheres | Contact angle 1 | |
| Example 1 | 61 | 36 |
| Example 2 | 63 | 32 |
| Example 3 | 67 | 37 |
| Example 4 | 59 | 30 |
| Example 5 | 60 | 29 |
| Example 6 | 62 | 33 |
| Example 7 | 64 | 34 |
| Example 8 | 68 | 30 |
As can be seen from table 2, the composition of the present invention can effectively form a coating layer having a micro-nano structure with a certain strength on the surface of a silicon wafer. The contact angle of the coating is tested to find that the contact angle of the surface of the silicon wafer is obviously higher than that of the surface of the silicon wafer after the nano silicon dioxide microsphere coating is constructed on the surface of the silicon wafer. When the contact angle is measured with hot water, the value of the contact angle is substantially the same as that of the surface of the untreated wafer. This phenomenon is consistent with the Wenzel and Cassie models. Shows that the glass surface treated by the nano silicon dioxide microspheres can form a micro-nano structure
Comparative example 1
Adding 10ml of ethyl orthosilicate and 45ml of ethanol into a 250ml four-neck flask, heating to 60 ℃, adding 15ml of ammonia water and 25ml of ethanol into a reaction bottle, reacting for 5 hours at 60 ℃, taking 5 drops of reaction liquid, diluting with ethanol, and testing the diameter of the silicon dioxide particles to be 350nm by using a Malverometer.
The silica microsphere reaction solution was diluted to 1% wt with ethanol, 0.1% wt surfactant OFX5211 was added, and the PH of the solution was adjusted to about 3 with hydrochloric acid. Dripping the nanometer silicon dioxide microsphere alcohol solution on a glass slide, spreading the solution, and standing overnight at room temperature, 65 deg.C, 90 deg.C, 150 deg.C, and 300 deg.C respectively. The treated slides were rinsed with ethanol and then blown dry with compressed air. The treated slides were tested for contact angle. Where contact angle 1 is measured with water at room temperature and contact angle 2 is measured with hot water at 70 deg.c.
TABLE 3 contact angle of glass surface treated with alcoholic solution of silica microspheres
| Temperature of heating | Contact angle 1 | |
| At room temperature | 34 | 32 |
| 65℃ | 35 | 33 |
| 90℃ | 33 | 31 |
| 150℃ | 36 | 32 |
| 300℃ | 35 | 31 |
| Untreated slides | 34 | 32 |
As can be seen from table 3, the contact angle of the glass slides treated with the silica microsphere composition without the active layer was substantially the same as that of the untreated glass slides. Therefore, the silica microspheres without the active layer cannot form a coating with certain strength on the glass surface.
Claims (8)
1. An active nano silicon dioxide microsphere solution comprises the following components in parts by weight:
(1) 0.01-20 parts of active nano silicon dioxide microspheres;
(2) 0.001-1 part of a surfactant;
(3) 0.005-5 parts of acid;
the active nano-silica microspheres comprise nano-silica microspheres and an active layer on the surfaces of the nano-silica microspheres, wherein the active layer contains condensable siloxane;
the molecular general formula of the surfactant is as follows:
in the formula (II), R5Is selected from C10-18Alkyl or alkenyl of (a), 1 to 20 siloxy units or C8-18N is selected from 1 to 20, and m is selected from 0 to 20.
2. The active nano-silica microsphere solution according to claim 1, wherein the active nano-silica microspheres are obtained by modifying nano-silica microspheres with siloxane represented by formula (I) under alkaline or acidic conditions:
in the formula (I), R1And R2Is selected from C1-C10Alkoxy group of (a); r3And R4Selected from hydrogen, alkyl, C-alkenyl or C1-C10Alkoxy group of (2).
3. The active nanosilica microsphere solution according to claim 1, characterized in that the acid is selected from inorganic acids or organic carboxylic acids.
4. The active nanosilica microsphere solution according to claim 3, characterized in that the acid is selected from hydrochloric acid, sulphuric acid, phosphoric acid or acetic acid.
5. The active nano-silica microsphere solution according to claim 1, wherein the active nano-silica microsphere solution further comprises, in parts by weight: (4) 74-99.94 parts of alcohol.
6. The active nanosilica microsphere solution of claim 5, wherein the alcohol is at least one or more mixed alcohols selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, ethylene glycol, glycerol, 1, 2-propanediol, 1, 3-propanediol, and butanediol.
7. A method for preparing the active nano silicon dioxide microsphere solution of any one of claims 1 to 6, comprising the following steps:
(1) preparation of active nano silicon dioxide microsphere
a) Dissolving silicate ester with required amount in alcohol, reacting in the presence of a catalyst, and removing the catalyst to obtain nano silicon dioxide microsphere alcohol solution;
b) adding silicate ester, water and a catalyst into the nano-silica microsphere alcoholic solution obtained in the step a), and reacting for 2-20 hours to obtain the active nano-silica microspheres;
(2) preparation of active nano silicon dioxide microsphere solution
Uniformly mixing the active nano silicon dioxide microspheres, the surfactant, the acid and the solvent in required amount; obtaining the active nano silicon dioxide microsphere solution.
8. Use of the active nanosilica microsphere solution according to any of claims 1 to 6 for the preparation of coatings.
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