CN103288358B - Super-hydrophilic self-cleaning antifogging antireflection coating and preparation method thereof - Google Patents
Super-hydrophilic self-cleaning antifogging antireflection coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 190
- 239000011248 coating agent Substances 0.000 title claims abstract description 188
- 238000004140 cleaning Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 193
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 186
- 239000002131 composite material Substances 0.000 claims abstract description 183
- 239000007787 solid Substances 0.000 claims abstract description 171
- 239000002105 nanoparticle Substances 0.000 claims abstract description 123
- 235000011034 Rubus glaucus Nutrition 0.000 claims abstract description 53
- 235000009122 Rubus idaeus Nutrition 0.000 claims abstract description 53
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 49
- 239000012798 spherical particle Substances 0.000 claims description 162
- 239000002245 particle Substances 0.000 claims description 153
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 128
- 239000005357 flat glass Substances 0.000 claims description 117
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 95
- 238000000151 deposition Methods 0.000 claims description 79
- 239000000725 suspension Substances 0.000 claims description 75
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 73
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 73
- 230000008021 deposition Effects 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000008187 granular material Substances 0.000 claims description 65
- 229910052757 nitrogen Inorganic materials 0.000 claims description 64
- 239000012153 distilled water Substances 0.000 claims description 56
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 43
- 238000012545 processing Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 229920000867 polyelectrolyte Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 240000007651 Rubus glaucus Species 0.000 claims 4
- 239000011521 glass Substances 0.000 abstract description 54
- 244000235659 Rubus idaeus Species 0.000 abstract description 49
- 238000002834 transmittance Methods 0.000 abstract description 8
- 240000002853 Nelumbo nucifera Species 0.000 abstract description 6
- 235000006508 Nelumbo nucifera Nutrition 0.000 abstract description 6
- 235000006510 Nelumbo pentapetala Nutrition 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000003618 dip coating Methods 0.000 abstract description 2
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 abstract 2
- 239000002086 nanomaterial Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000008188 pellet Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to a super-hydrophilic self-cleaning antifogging antireflection coating and a preparation method thereof. The super-hydrophilic self-cleaning antifogging antireflection coating is prepared by electrostatic assembly and a dip-coating method, and the required instruments and equipment are simple and cheap, so that industrialization is expected to be realized. The surface of the super-hydrophilic self-cleaning antifogging antireflection coating has a structure similar to that of a lotus leaf surface in nature, and the antireflection coating is formed by assembling titanium dioxide-silicon dioxide composite nanoparticles and solid silicon dioxide spherical nanoparticles, wherein the appearance of the titanium dioxide-silicon dioxide composite nanoparticles is similar to that of a natural raspberry fruit. The super-hydrophilic self-cleaning antifogging antireflection coating can be used on glass products. The light transmittance of the glass sheet coated with the super-hydrophilic self-cleaning antifogging antireflection coating can be improved from 91.3% to 97.3%, and the super-hydrophilic antifogging coating has an excellent super-hydrophilic antifogging function.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly the cleaning anti-reflection coating and preparation method thereof of super hydrophilic self-cleaning fog.
Background technology
The atomization of glass refers to that moisture or vapor condensation form small water droplet at glass article surface.And self-cleaning fog glass (Anti-fogging glass) just refers to that simple glass is after special processing, glass surface is made to have super water-wet behavior, the small water droplet formed due to atomization is paved rapidly, thus reach the effect of the transmittance not affecting mirror image, visibility meter and glass, simultaneously also without the need to making cleaning glass through traditional artificial scouring.At present, developed country Jun You renowned company is specializing in research and development and the making of self-cleaning fog glass in the world, as Pilkington company of Britain, Japanese TOTO company, PPG company of the U.S., German GEA company, VTA company, UIC company etc.; The transparent composite self-cleaning antifog glass of people's developments such as U.S. W.L.Tonar, be form the photocatalyst Clear coating with photocatalysis on the surface of glass baseplate, then formation have hydrophilic transparent porous inorganic oxide (SiO on the surface of photocatalyst Clear coating
2and Al
2o
3) film.But these technology all make use of TiO
2photocatalysis characteristic impels glass surface to reach super hydrophilic, and applicable elements can be restricted, because the environment needing illumination just can carry out katalysis; And the light transmission of these coatings is all bad.
In recent years, scientist has the surface topology of the lotus leaf of self-cleaning function by research, find that lotus leaf microcosmic surface is very coarse, and be made up of super-hydrophobicity material, so, scientist starts the spheroidal particle that preparation has uneven surface (being namely similar to the shape of raspberry), and utilizes this spheroidal particle to prepare automatic cleaning coating.The silica pellets of amino functional is carried out assembling preparation raspberry shape particle on Epoxy functionalized silicon-dioxide macroparticle surface by chemical bond by Ming etc., and utilize this composite particles to construct there is the coarse based superhydrophobic thin films (W.Ming of two yardstick, D.Wu, R.van Benthem, and G.de With, Nano Letters, 2005,5,2298.), but this method generally needs surface modification process, this not only adds experimental procedure, also improves preparation cost.Present invention applicant once utilized size two kinds of particle diameter SiO
2particle assembling raspberry shape spheroidal particle (publication number: CN101168475A) and preparation raspberry shape composite particles (application number 200910092551.4), they all successfully to assemble the silica dioxide coating of the porous of super hydrophilic and anti-fog performance, although they all have excellent super hydrophilic antifogging performance, but its self-cleaning performance must rely on precipitation, limited to when there is no precipitation or the little area applications of precipitation.Therefore Study and Development has the self-cleaning fog functional coating taking into account illumination and precipitation restriction is very necessary and significant.
Summary of the invention
An object of the present invention is to provide the cleaning anti-reflection coating had with the super hydrophilic self-cleaning fog of the titania-silica composite nanoparticle of raspberry fruit similar, and the transmittance scribbling the sheet glass of this coating can bring up to 97% from 91%.
Two of object of the present invention is to provide and adopts electrostatic self-assembled method, by the alternately assembling of nanoparticle and polyelectrolyte, thus preparation method and technique is simple, cheaper starting materials, cost are low, applied widely surface is provided to have the preparation method with the cleaning anti-reflection coating of the super hydrophilic self-cleaning fog of the titania-silica composite nanoparticle of raspberry fruit similar.
Present invention employs the solid SiO that particle diameter is approximately 20nm
2nano spherical particle and to have with the particle diameter of raspberry fruit similar be the titania-silica composite nanoparticle of 30 ~ 110nm, utilizes easy Layer-by-Layer (LbL) layer-by-layer original position to prepare the cleaning anti-reflection coating of super hydrophilic (the contact angle convergence of water droplet on the glass surface scribbling this coating 0 degree) self-cleaning fog of coarse structure.The present invention is by regulating solid SiO
2the assembling number of plies of the titania-silica composite nanoparticle of nano spherical particle and nucleocapsid structure, can prepare the stratum two coarse coating of multiple types like lotus leaf surface structure, the nearly zero degree of hydrophilic contact corner connection.The transmittance scribbling the sheet glass of the automatically cleaning cleaning anti-reflection coating of super hydrophilic antifogging of the present invention can bring up to 97% from 91%.The invention provides a kind of at visible region anti-reflection, there is the multi-functional coatings preparation method of super hydrophilic self-cleaning fog performance simultaneously, preparation technology is simple, cost is low, successful, the technical superiority such as applied widely.
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog of the present invention combines the photocatalytic self-cleaning performance of titanium dioxide excellence and Nano particles of silicon dioxide layer just has the advantage of super hydrophilicity without the need to ultraviolet lighting.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog of the present invention is under the condition of precipitation, drop can be sprawled at coatingsurface fast thus take away pollutent, and when without precipitation, the photocatalysis performance of TiO 2 particles can degradation of contaminant, still can play self-cleaning performance.
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog of the present invention adopts solid SiO
2suspension prepared by the titania-silica composite nanoparticle of nano spherical particle and nucleocapsid structure, takes the method for dip-coating by solid SiO
2the titania-silica composite nanoparticle of nano spherical particle and nucleocapsid structure and polyelectrolyte are deposited on substrate (as sheet glass) by electrostatic assembly, eventually pass calcining and prepare described cleaning anti-reflection coating.Required plant and instrument is simple, cheap, is easy to industrialization.
The surface of the cleaning anti-reflection coating of super hydrophilic self-cleaning fog of the present invention has the structure similar to the lotus leaf surface of occurring in nature, and this cleaning anti-reflection coating is assembled by the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar and the spherical nanoparticle of solid silicon-dioxide.
The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is the SiO being approximately 28 ~ 97nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is approximately 1 ~ 13nm
2spherical small-particle is composited.
The particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is approximately 30 ~ 110nm.
The particle diameter of the described spherical nanoparticle of solid silicon-dioxide is approximately 20nm.
Described particle diameter is approximately the solid SiO of 20nm
2nano spherical particle and particle diameter are approximately the SiO in the titania-silica composite nanoparticle of 30 ~ 110nm
2spherical macroparticles can be according to
(
w, Fink A, Bohn E.Journal of Colloid & Interface Science, 1968,26:62 ~ 69) method is prepared.
When the titania-silica composite nanoparticle of described nucleocapsid structure, through calcining after uniform adsorption forms coating on substrate (as sheet glass), the titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle had with natural raspberry fruit similar, and this titania-silica composite nanoparticle is the SiO being approximately 28 ~ 97nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is approximately 1 ~ 13nm
2spherical small-particle is composited.
Coating described in the present invention is by solid SiO
2the polyelectrolyte that the negative charge of nano spherical particle surface band and substrate deposit or the titania-silica composite nanoparticle of nucleocapsid structure with positive charge electrostatic attraction self-assembly and formed, each has walked all thoroughly washs with distilled water, dries up with nitrogen.
Described polyelectrolyte is diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate.
The preparation method of the cleaning anti-reflection coating of super hydrophilic self-cleaning fog of the present invention comprises the following steps:
(1) tetraethoxy is hydrolyzed under ammonia-catalyzed, prepares the SiO being approximately 28 ~ 97nm containing single dispersing particle diameter
2the suspension of nano spherical particle, suspension stirring at room temperature (the general time of stirring is 2 ~ 6 hours), dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1 ~ 4: 1, stirring reaction (time of general stirring reaction is 2 ~ 6 hours), centrifugation, supersound washing, obtains the titania-silica composite nanoparticle of nucleocapsid structure; The titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water the suspension (be preferably and contain the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%) of the titania-silica composite nanoparticle containing nucleocapsid structure;
(2) tetraethoxy is hydrolyzed under ammonia-catalyzed, prepares the solid SiO being approximately 20nm containing single dispersing particle diameter
2the suspension of nano spherical particle;
(3) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited at surface of plate glass, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck obtaining depositing on sheet glass is the sheet glass of sodium polystyrene sulfonate coating;
(4) sheet glass that step (3) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO being approximately 20nm containing particle diameter that step (2) prepares
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (3) is on the sheet glass of sodium polystyrene sulfonate layer, altogether deposited 1 ~ 3 layer is approximately 20nm solid SiO by diallyl dimethyl ammoniumchloride coating and particle diameter
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer; Or
The sheet glass being sodium polystyrene sulfonate coating by last one deck that step (3) prepares to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then be immersed in the solid SiO being approximately 20nm containing particle diameter that step (2) prepares
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is on the sheet glass of sodium polystyrene sulfonate coating, is altogether deposited 2 layers and be approximately the solid SiO of 20nm by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer;
(5) what step (4) prepared deposits 1 ~ 3 layer is approximately 20nm solid SiO by diallyl dimethyl ammoniumchloride coating and particle diameter altogether
2the sheet glass of bilayer that nano spherical particle layer is formed to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, at solid SiO
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then be immersed in the solid SiO being approximately 20nm containing particle diameter that step (2) prepares
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (4) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether deposited 2 layers and be approximately the solid SiO of 20nm by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer; Then this sheet glass is put into retort furnace, calcine under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar; Or
What step (4) prepared altogether deposits 2 layers and is approximately the solid SiO of 20nm by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter
2retort furnace put into by the sheet glass of the bilayer that nano spherical particle layer is formed, calcine under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar;
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining; The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is the SiO being approximately 28 ~ 97nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is approximately 1 ~ 13nm
2spherical small-particle is composited.
Before sheet glass is put into retort furnace, the sheet glass that the present invention can will carry out calcining further to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, at solid SiO
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer, the last one deck obtaining depositing on sheet glass is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure; And then by the titania-silica composite nanoparticle with nucleocapsid structure of preparation and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcine under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into pattern and has the titania-silica composite nanoparticle with natural raspberry fruit similar, obtains the cleaning anti-reflection coating of super hydrophilic self-cleaning fog.
The suspension of the described titania-silica composite nanoparticle containing nucleocapsid structure, in its suspension, the massfraction of the titania-silica composite nanoparticle of nucleocapsid structure is 0.4%.
The described time of carrying out calcining under temperature is 400 ~ 550 degrees Celsius is 1 ~ 3 hour.
The particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is approximately 30 ~ 110nm.
Described sheet glass, such as, the glass window of family and commercial building, glass sunroof, glass curtain wall, Household bathroom mirror, windshield, automobile rearview mirror, vehicle rear-view glass or eye plate etc.
The present invention using the cheap and sheet glass easily obtained as substrate, then by layer upon layer electrostatic self-assembly string of deposits polyelectrolyte and solid SiO
2nano spherical particle.Due to the increase of the porosity between nanoparticle, make the transmittance of the sheet glass of the cleaning anti-reflection coating scribbling super hydrophilic self-cleaning fog can bring up to 97% from 91%.
Below in conjunction with drawings and Examples, the present invention is further illustrated, and the ST wherein in accompanying drawing represents that particle diameter is the titania-silica composite nanoparticle with raspberry fruit similar that has of 75nm, and S represents that particle diameter is the solid SiO of 20nm
2nano spherical particle, is designated as the number of plies of coating under outside bracket.
Accompanying drawing explanation
Fig. 1. the particle diameter of (a-b) embodiment of the present invention 1 is the transmission electron microscope picture of the titania-silica composite nanoparticle of the nucleocapsid structure of 75nm; (c-d) the titania-silica composite nanoparticle of to be particle diameter the be nucleocapsid structure of 75nm calcines the transmission electron microscope picture after 3 hours under temperature is 550 degrees Celsius; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.
Fig. 2. depositing (ST/S) of the embodiment of the present invention 1
2the scanning electron microscopic picture of the sheet glass of coating, is designated as the number of plies of coating under outside bracket.
Fig. 3. the embodiment of the present invention 2 deposit S
3(ST/S)
2the scanning electron microscopic picture of the sheet glass of coating, is designated as the number of plies of coating under outside bracket.
Fig. 4. the embodiment of the present invention 3 deposit S
3(ST/S)
2the scanning electron microscopic picture of the sheet glass of ST coating, is designated as the number of plies of coating under outside bracket.
Fig. 5. the embodiment of the present invention 1 ~ 3 deposits (ST/S)
2, S
3(ST/S)
2, S
3(ST/S)
2sT coating and the transmitted light spectrogram not having cated sheet glass.
Fig. 6. the embodiment of the present invention 1 ~ 3 deposits (ST/S)
2, S
3(ST/S)
2, S
3(ST/S)
2sT coating and the reflected light spectrogram not having cated sheet glass.
Fig. 7. the common glass sheet that (a) is clean and deposit S
3(ST/S)
2the anti-fog performance photo of the sheet glass (embodiment 3) of ST coating.Method takes out after two samples are put into the refrigerator of-5 degrees Celsius to be simultaneously placed on room temperature environment, common glass sheet (under) produce rapidly the little water droplet of atomization, and cated sheet glass (on) do not produce atomization, keep transparent always.B () is clean common glass sheet (left side) and deposits S
3(ST/S)
2the photo of the reflective situation of the sheet glass (right, embodiment 3) of ST coating.
Fig. 8. (a) deposits S
3(ST/S)
2the abosrption spectrogram of the photocatalytic degradation methylene blue experiment of the sheet glass (embodiment 3) of ST coating, (b) shows the time comparison diagram not having cated glass and cated glass light transmitance to recover.
Fig. 9. the particle diameter of (a-b) embodiment of the present invention 4 is the transmission electron microscope picture of the titania-silica composite nanoparticle of the nucleocapsid structure of 30nm; (c-d) the titania-silica composite nanoparticle of to be particle diameter the be nucleocapsid structure of 30nm calcines the transmission electron microscope picture after 2.5 hours under temperature is 550 degrees Celsius; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.
Figure 10. the particle diameter of (a-b) embodiment of the present invention 5 is the transmission electron microscope picture of the titania-silica composite nanoparticle of the nucleocapsid structure of 110nm; (c-d) the titania-silica composite nanoparticle of to be particle diameter the be nucleocapsid structure of 110nm calcines the transmission electron microscope picture after 3 hours under temperature is 550 degrees Celsius; The titania-silica composite nanoparticle of nucleocapsid structure is transformed into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar.
Embodiment
Embodiment 1
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO being respectively 20nm by particle diameter
2two double-layer assembleds that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed form, and its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle, and with alcohol dilution become massfraction be 0.1% ~ 4% suspension for subsequent use;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 70nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtain the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 75nm, the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water and contains the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) what the sheet glass that step (2) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 75nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (2) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (3) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 3 hours is carried out under temperature is 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining.
Observe by transmission electron micrograph titania-silica composite nanoparticle (Fig. 1 a-b) that particle diameter is the nucleocapsid structure of 75nm and change the titania-silica composite nanoparticle (Fig. 1 c-d) of pattern and natural raspberry fruit similar after firing into.
From the surface topography of this cleaning anti-reflection coating of scanning electron microscopic observation, the surface of this cleaning anti-reflection coating has the coarse structure similar with the lotus leaf surface of occurring in nature, and it is the solid SiO of 2nm by particle diameter
2nano spherical particle and particle diameter are that the pattern of 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble (is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited), and surface is particle diameter is the solid SiO of 20nm
2the structure (Fig. 2) of nano spherical particle layer.
As shown in Figure 5, maximum transmission is 96.3% to the transmittance of this cleaning anti-reflection coating, and reflectivity as shown in Figure 6.
Embodiment 2
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO by 3 layers of particle diameter being 20nm
2nano spherical particle and particle diameter are respectively the solid SiO of 20nm
22 double-layer assembleds that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed form, and its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle, and with alcohol dilution become massfraction be 0.1% ~ 4% suspension for subsequent use;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 70nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtain the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 75nm, the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water and contains the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) sheet glass that step (2) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (2) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited haves three layers by diallyl dimethyl ammoniumchloride coating and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) what the sheet glass that step (3) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 75nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, at the solid SiO of skin
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(5) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (4) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 1 hour is carried out under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining.
From the surface topography of this cleaning anti-reflection coating of scanning electron microscopic observation, the coarse structure that this cleaning anti-reflection coating has is the solid SiO of 20nm by 3 layers of particle diameter
2nano spherical particle and particle diameter are respectively the solid SiO of 20nm
2two double-layer assembleds that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed form, and surface is particle diameter is the solid SiO of 20nm
2the structure (Fig. 3) of nano spherical particle layer.
As shown in Figure 5, maximum transmission is 97.1% to the transmittance of this cleaning anti-reflection coating, and reflectivity as shown in Figure 6.
Embodiment 3
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO by 3 layers of particle diameter being 20nm
2nano spherical particle, particle diameter are respectively the solid SiO of 20nm
22 bilayers that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed, be that the pattern of 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble with one deck particle diameter, its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle, and with alcohol dilution become massfraction be 0.1% ~ 4% suspension for subsequent use;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 70nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtain the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 75nm, the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water and contains the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) sheet glass that step (2) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (2) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited haves three layers by diallyl dimethyl ammoniumchloride coating and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) what the sheet glass that step (3) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 75nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, at the solid SiO of one deck
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(5) what the sheet glass that step (4) prepared immersed that step (1) prepares is in the suspension of the titania-silica composite nanoparticle of the nucleocapsid structure of 75nm 2 ~ 10 minutes containing the massfraction particle diameter that is 0.4%, taking-up distilled water wash, nitrogen dries up, at the solid SiO of skin
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; The last one deck deposited on the glass sheet is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;
(6) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (5) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 2 hours is carried out under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining.
From the surface topography of this cleaning anti-reflection coating of scanning electron microscopic observation, the coarse structure that this cleaning anti-reflection coating has is the solid SiO of 20nm by 3 layers of particle diameter
2nano spherical particle, particle diameter is respectively the solid SiO of 20nm
2two bilayers that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed, be that the pattern of 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble with one deck particle diameter, and surface is particle diameter is the titania-silica composite nano-granule sublayer (Fig. 4) of 75nm natural raspberry fruit similar.
As shown in Figure 5, maximum transmission is 97.3% to the transmittance of this cleaning anti-reflection coating, and reflectivity as shown in Figure 6.
Antifog contrast picture as shown in Figure 7.Common glass sheet and the sheet glass scribbling this coating are first put into refrigerator freezing, and then take out observation rapidly, compared with simple glass, the sheet glass scribbling this coating has obvious anti-fog effect.
Photocatalytic self-cleaning performance as shown in Figure 8.This cleaning anti-reflection coating is put into 10mg/L methylene blue solution 5 minutes, after 100mm/min lift, after standing and drying, the transmitance of coating declines to some extent because of the methylene blue of absorption.Under the irradiation of 250W ultraviolet mercury lamp, coating degrades the methylene blue of surface adsorption gradually, and therefore the transmitance of coating is recovered gradually.When irradiation is after 30 minutes, coating transmitance has returned to the transmitance before not adsorbing completely.Fig. 8 b shows the time comparison diagram not having cated glass and cated glass transmitance to recover, and this cleaning anti-reflection coating of this process explanation has good self-cleaning performance.
Embodiment 4
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO by 3 layers of particle diameter being 20nm
2nano spherical particle, particle diameter are respectively the solid SiO of 20nm
22 bilayers that the pattern of nano spherical particle and 30nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed, be that the pattern of 30nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble with one deck particle diameter, its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 28nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtain the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 30nm, the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water and contains the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) sheet glass that step (2) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (2) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited haves three layers by diallyl dimethyl ammoniumchloride coating and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) what the sheet glass that step (3) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 30nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, at the solid SiO of one deck
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(5) what the sheet glass that step (4) prepared immersed that step (1) prepares is in the suspension of the titania-silica composite nanoparticle of the nucleocapsid structure of 30nm 2 ~ 10 minutes containing the massfraction particle diameter that is 0.4%, taking-up distilled water wash, nitrogen dries up, at the solid SiO of skin
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; The last one deck deposited on the glass sheet is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;
(6) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (5) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 2.5 hours is carried out under temperature is 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 28nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining.
Embodiment 5
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO by 3 layers of particle diameter being 20nm
2nano spherical particle, particle diameter are respectively the solid SiO of 20nm
22 bilayers that the pattern of nano spherical particle and 110nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed, be that the pattern of 110nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar assemble with one deck particle diameter, its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle, and with alcohol dilution become massfraction be 0.1% ~ 4% suspension for subsequent use;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 100nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtain the titania-silica composite nanoparticle that particle diameter is the nucleocapsid structure of 110nm, the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water and contains the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4%;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) sheet glass that step (2) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (2) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited haves three layers by diallyl dimethyl ammoniumchloride coating and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) what the sheet glass that step (3) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 110nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, at the solid SiO of one deck
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(5) what the sheet glass that step (4) prepared immersed that step (1) prepares is in the suspension of the titania-silica composite nanoparticle of the nucleocapsid structure of 110nm 2 ~ 10 minutes containing the massfraction particle diameter that is 0.4%, taking-up distilled water wash, nitrogen dries up, at the solid SiO of skin
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; The last one deck deposited on the glass sheet is the sheet glass of the titania-silica composite nano-granule sublayer of nucleocapsid structure;
(6) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (5) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 3 hours is carried out under temperature is 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 100nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 5nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining.
The titania-silica composite nanoparticle (Figure 10 c-d) that titanium dioxide of core-shell structure-silicon-dioxide composite nanoparticle (Figure 10 a-b) that particle diameter is 110nm changes pattern and natural raspberry fruit similar after firing into is observed by transmission electron micrograph.
Embodiment 6
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog: the solid SiO by particle diameter being 20nm
2nano spherical particle layer, be respectively the solid SiO of 20nm with particle diameter
2two double-layer assembleds that the pattern of nano spherical particle and 75nm and the titania-silica composite nano-granule sublayer of natural raspberry fruit similar are formed form, and its preparation method comprises the following steps:
(1) by 5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute at 60 c, and under agitation drip 5mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 60 degrees Celsius with vigorous, obtaining is the solid SiO of 20nm containing particle diameter
2the translucent suspension of nano spherical particle, and with alcohol dilution become massfraction be 0.1% ~ 4% suspension for subsequent use;
By 7.5mL ammoniacal liquor, 50 ~ 150mL dehydrated alcohol to join in Erlenmeyer flask stirred at ambient temperature 8 ~ 12 minutes, stir 1 ~ 3 minute under 40 degrees Celsius, and under agitation drip 3mL tetraethoxy (TEOS), stir 10 ~ 14 hours at 40 degrees Celsius with vigorous, obtaining is the solid SiO of 70nm containing particle diameter
2the translucent suspension of nano spherical particle, suspension stirring at room temperature is after 2 hours, and dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1: 1, stirring reaction 6 hours, centrifugation, supersound washing, obtaining is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2the particle diameter that spherical small-particle is composited is the titania-silica composite nanoparticle of the nucleocapsid structure of 75nm, is formed by the titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained and contain the suspension that massfraction is the titania-silica composite nanoparticle of the nucleocapsid structure of 0.4% in water;
(2) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited in glass sheet surface, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck deposited on the glass sheet is the sheet glass of sodium polystyrene sulfonate coating;
(3) sheet glass that step (2) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; The last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(4) what the sheet glass that step (3) prepares is immersed in that step (1) prepares is in the suspension of the titania-silica composite nanoparticle (particle diameter is 75nm) of the nucleocapsid structure of 0.4% 2 ~ 10 minutes containing massfraction, taking-up distilled water wash, nitrogen dries up, at the solid SiO of one deck
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (1) prepares is the solid SiO of 20nm containing particle diameter
2the massfraction of nano spherical particle is take out after 2 ~ 10 minutes in the suspension of 0.1% ~ 4%, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck deposited on the glass sheet is solid SiO
2the sheet glass of nano spherical particle layer;
(5) the titania-silica composite nanoparticle with nucleocapsid structure prepared by step (4) and solid SiO
2retort furnace put into by the sheet glass of nano spherical particle coating, calcining 1 hour is carried out under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar, and the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar is the solid SiO of 70nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1nm
2spherical small-particle is composited.The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is finally obtained after calcining.
Claims (6)
1. a preparation method for the cleaning anti-reflection coating of super hydrophilic self-cleaning fog, it is characterized in that, the method comprises the following steps:
(1) be hydrolyzed under ammonia-catalyzed by tetraethoxy, preparing containing particle diameter is the SiO of 28 ~ 97nm
2the suspension of nano spherical particle, stirring at room temperature suspension, dripping with tetraethoxy mol ratio is under agitation the titanium tetraisopropylate of 1:1 ~ 4:1, stirring reaction, centrifugation, supersound washing, obtains the titania-silica composite nanoparticle of nucleocapsid structure; The titania-silica composite nanoparticle ultrasonic disperse of the nucleocapsid structure obtained is formed in water the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure;
(2) be hydrolyzed under ammonia-catalyzed by tetraethoxy, preparing containing particle diameter is the solid SiO of 20nm
2the suspension of nano spherical particle;
(3) will to clean up and the sheet glass obtained after drying up with nitrogen is immersed in concentration is take out after 2 ~ 10 minutes in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, one deck diallyl dimethyl ammoniumchloride coating is deposited at surface of plate glass, with distilled water wash to remove the diallyl dimethyl ammoniumchloride of physical adsorption, dry up with nitrogen; And then to be immersed in concentration be in the sodium polystyrene sulfonate aqueous solution of 1 ~ 3mg/mL 2 ~ 10 minutes, take out, with distilled water wash, dry up with nitrogen, diallyl dimethyl ammoniumchloride coating deposits again one deck sodium polystyrene sulfonate coating; Repeat the processing step of above-mentioned deposition diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, until altogether deposited 5 ~ 20 layers of bilayer be made up of diallyl dimethyl ammoniumchloride coating and sodium polystyrene sulfonate coating, the last one deck obtaining depositing on sheet glass is the sheet glass of sodium polystyrene sulfonate coating;
(4) sheet glass that step (3) prepares being immersed in concentration is 2 ~ 10 minutes taking-up distilled water washs in the aqueous solution of the diallyl dimethyl ammoniumchloride of 1 ~ 3mg/mL, nitrogen dries up, at surface deposition one deck diallyl dimethyl ammoniumchloride layer of sodium polystyrene sulfonate coating; And then that be immersed in that step (2) prepares is the solid SiO of 20nm containing particle diameter
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of diallyl dimethyl ammoniumchloride layer
2nano spherical particle coating, with distilled water wash to remove the solid SiO of physical adsorption
2nano spherical particle, dries up with nitrogen; Repeat above-mentioned deposition diallyl dimethyl ammoniumchloride layer and the solid SiO of deposition
2the processing step of nano spherical particle coating, until the last one deck obtained in step (3) is on the sheet glass of sodium polystyrene sulfonate layer, altogether deposited the solid SiO that 1 ~ 3 layer by diallyl dimethyl ammoniumchloride coating and particle diameter is 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer; Or
The sheet glass being sodium polystyrene sulfonate coating by last one deck that step (3) prepares to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, in the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of sodium polystyrene sulfonate coating; And then that be immersed in that step (2) prepares is the solid SiO of 20nm containing particle diameter
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (3) is on the sheet glass of sodium polystyrene sulfonate coating, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer;
(5) what step (4) prepared deposits the solid SiO that 1 ~ 3 layer by diallyl dimethyl ammoniumchloride coating and particle diameter is 20nm altogether
2the sheet glass of bilayer that nano spherical particle layer is formed to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, at solid SiO
2the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer; And then that be immersed in that step (2) prepares is the solid SiO of 20nm containing particle diameter
2take out after 2 ~ 10 minutes in the suspension of nano spherical particle, at the solid SiO of surface deposition one deck of the titania-silica composite nano-granule sublayer of nucleocapsid structure
2nano spherical particle layer, with distilled water wash, then dries up with nitrogen; Repeat the titania-silica composite nano-granule sublayer of above-mentioned deposition nucleocapsid structure and solid SiO
2the processing step of nano spherical particle layer, until the last one deck obtained in step (4) is solid SiO
2on the sheet glass of nano spherical particle layer, altogether being deposited 2 layers by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter is the solid SiO of 20nm
2the bilayer that nano spherical particle layer is formed, the last one deck obtaining depositing on sheet glass is solid SiO
2the sheet glass of nano spherical particle layer; Then this sheet glass is put into retort furnace, calcine under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar; Or
Step (4) is prepared altogether to deposit 2 layers be the solid SiO of 20nm by the titania-silica composite nano-granule sublayer of nucleocapsid structure and particle diameter
2retort furnace put into by the sheet glass of the bilayer that nano spherical particle layer is formed, calcine under temperature is 400 ~ 550 degrees Celsius, to remove polyelectrolyte diallyl dimethyl ammoniumchloride and sodium polystyrene sulfonate, the titania-silica composite nanoparticle of nucleocapsid structure transforms into the titania-silica composite nanoparticle of pattern and natural raspberry fruit similar;
The cleaning anti-reflection coating of super hydrophilic self-cleaning fog is obtained after calcining; The titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is the SiO of 28 ~ 97nm by the particle diameter as core
2spherical macroparticles be coated on the TiO that outer field particle diameter is 1 ~ 13nm
2spherical small-particle is composited.
2. preparation method according to claim 1, it is characterized in that: before sheet glass is put into retort furnace, the sheet glass that first will carry out calcining to be immersed in the suspension of the titania-silica composite nanoparticle containing nucleocapsid structure that step (1) prepares 2 ~ 10 minutes, taking-up distilled water wash, nitrogen dries up, at solid SiO
2put into retort furnace again behind the titania-silica composite nano-granule sublayer of surface deposition one deck nucleocapsid structure of nano spherical particle layer to calcine.
3. preparation method according to claim 1 and 2, it is characterized in that: the suspension of the described titania-silica composite nanoparticle containing nucleocapsid structure, in its suspension, the massfraction of the titania-silica composite nanoparticle of nucleocapsid structure is 0.4%.
4. preparation method according to claim 1, is characterized in that: the time of the stirring described in step (1) is 2 ~ 6 hours.
5. preparation method according to claim 1 and 2, is characterized in that: the time of described calcining is 1 ~ 3 hour.
6. preparation method according to claim 1, is characterized in that: the particle diameter of the titania-silica composite nanoparticle of described pattern and natural raspberry fruit similar is 30 ~ 110nm.
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