CN103288358B

CN103288358B - Super-hydrophilic, self-cleaning and mist-proof anti-reflection coating and preparation method thereof

Info

Publication number: CN103288358B
Application number: CN201210042082.7A
Authority: CN
Inventors: 贺军辉; 李晓禹
Original assignee: Technical Institute of Physics and Chemistry of CAS
Current assignee: Technical Institute of Physics and Chemistry of CAS
Priority date: 2012-02-22
Filing date: 2012-02-22
Publication date: 2015-03-18
Anticipated expiration: 2032-02-22
Also published as: CN103288358A

Abstract

The invention belongs to the technical field of nanometer material preparation, and in particular relates to a super-hydrophilic, self-cleaning and mist-proof anti-reflection coating and a preparation method thereof. The anti-reflection coating is prepared in an electrostatic combination manner by using a dip-coating method. The required instruments and equipment are simple and low in cost, thereby being possibly suitable for industrialization. The surface structure of the anti-reflection coating is similar to that of a lotus leaf in the nature. The anti-reflection coating is formed by combining a titanium dioxide-silicon dioxide composite nanoparticle having the shape similar to the structure of natural raspberry fruits with solid spherical silica nanoparticles. The anti-reflection coating provided by the invention can be applied to a glass product. A glass sheet coated with the anti-reflection coating has the light transmittance improved from 91.3% to 97.3%, and has an excellent super-hydrophilic mist-proof function.

Description

Cleaning anti-reflection coating of super hydrophilic self-cleaning fog and preparation method thereof

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.

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:

(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:

(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%;

(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:

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%;

(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:

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;

(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;

(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

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;

(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.