CN102649623A - Anti-reflection super-hydrophilic self-cleaning anti-fog glass and preparation method thereof - Google Patents
Anti-reflection super-hydrophilic self-cleaning anti-fog glass and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to anti-reflection super-hydrophilic self-cleaning antifogging glass and a preparation method thereof. The invention adopts two methods of heating water bath at normal pressure or heating water in a sealing way, and effectively etches glass sheets with various components by alkaline aqueous solution to obtain the anti-reflection super hydrophilic self-cleaning antifogging glass. The anti-reflection super-hydrophilic self-cleaning anti-fog glass is a rough coating with the thickness of 50-160 nanometers, which is formed by mutually cross-connecting silica nanosheets with the thickness of 10-30 nanometers on the surface of the glass, wherein the cross-connecting positions of the silica nanosheets have a pore structure, and the pore diameter of each pore is 10-200 nanometers. The light transmittance of the anti-reflection super-hydrophilic self-cleaning antifogging glass can be improved from 90% to 98%. The surface of the anti-reflection super-hydrophilic self-cleaning antifogging glass is provided with the titanium dioxide coating, so that the anti-reflection super-hydrophilic self-cleaning antifogging glass with the performance of photocatalytic degradation of organic matters is obtained.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly anti-reflection ultra hydrophilic automatically cleaning antifog glass and preparation method thereof.
Background technology
Self-cleaning glass (Self-cleaning glass) is meant that simple glass is behind process special physics or chemical process processing; Make its surface produce unique physics-chem characteristic, thereby make glass need not just can reach the glass of cleaning effect through conventional artificial scouring method.
The atomizing of glass is meant that moisture or vapor condensation form small water droplet at glass article surface.And antifog glass (Anti-fogging glass) just is meant that simple glass is after the process special processing; Make the surface have ultra water-wet behavior; The small water droplet that forms owing to atomizing is paved rapidly, thereby reached the effect of the transmittance that does not influence mirror image, visibility meter and glass.
Self-cleaning glass mainly is divided into two big types on the preparation method: ultra hydrophilic self-cleaning glass; Super-hydrophobic automatic cleaning glass.Common preparation method adds one deck inorganic coating at glass article surface.
If this coating is the super-hydrophobicity material, then similar lotus leaf effect, its roll angle is little, can make small water droplet be gathered into large water drop.When the globule reaches certain size, can glide by self gravitation, or be removed through modes such as external force such as wind, rain brush.This method effect is obvious; But poor in timeliness: because the gathering of little water droplet or dry up, evaporate and all need for some time; Water droplet can be stayed on the glasswork, and like ground influence imaging and visibility meter as the prism, and this method weather resistance is undesirable at present; The life-time service life-span of glassy product can't be guaranteed, thereby automatically cleaning effect truly can't be guaranteed as durable consumer goods.
If this coating is the Superhydrophilic material, then can make the contact angle of little water droplet on glass surface level off to zero degree, when water touches glass surface; At its surface spreading, form uniform moisture film rapidly, the hydrophilic character of performance excess of export; Can not influence mirror image; The thin influence to transmittance of water layer simultaneously also greatly reduces, and takes away spot through the gravity fall of even moisture film, and this mode can be removed most of spot.Utilize ultra hydrophilic principle simultaneously, also can prevent the formation of little water droplet, reach antifog effect.
Glass automatically cleaning and antifog research have just been begun abroad in the sixties in 20th century; Aspect fundamental research; At present; All there is renowned company in developed country in the research and development of specializing in self-cleaning glass and making in the world, like Britain Pilkington company, Japanese TOTO company, U.S. PPG company, German GEA company, VTA company, UIC company etc.; Aspect application and development, Japan takes the lead in launching exploitation, promotes, uses TiO
2The photochemical catalysis self-cleaning glass, also good this Products Development of glass merchants such as Britain Pilkington company, U.S. PPG company, processing, the big market of producing and applying.Britain Pilkington glass company is at Application and Development TiO
2Photocatalytic self-cleaning glass aspect has been walked in Europe, U.S. glass merchant's prostatitis; And before the end of the year 2002, arrive Europe and other national (like the U.S.) glass markets to this product promotion; Carry out open batch and sell, subsequently in the North America, area such as Japan in Oceanian Australia, Asia and country release (Chen Libin, building glass and industrial glass 2004; No.6,12～15); Transparent composite self-cleaning antifog glass (W.L.Tonar et al.Electrochromic Device Having A Self-cleaning Hydrophilic Coating.United States Patent Application Publication US2001/00210066A1, the 2001-09-13 of people such as U.S. W.L.Tonar development; K.Toru.Vehicle Mirror.United States Patent US5594585:1997-01-14; K.Toru.Anti-fog Element.US5854708:1998-12-29; K.Takahama et al.Method of Forming Hydrophilic Inorganic Coating Film And Inorganic Coating Composition.United States Patent Application Publication US2001/008696A1; 2001-07-13); Be to form photocatalyst Clear coating, form the transparent porous inorganic oxide (SiO of possess hydrophilic property again on the surface of photocatalyst Clear coating with katalysis on the surface of glass baseplate
2And Al
2O
3) film.Yet these technology have all been utilized TiO
2Photocatalysis characteristic impels the surface to reach ultra hydrophilic, and applicable elements can be restricted, and just can carry out katalysis because need the environment of illumination; Though and this cavernous structure surface can improve wetting ability, be easy to be killed in a disaster evaporable material or nanometer dust are blocked the aperture, and weather resistance is undesirable.
Though domestic research is started late, also obtained significant progress, about patent and technological achievement have up to a hundred, and constantly there is the glass antidimmer product to release.Form small water droplet on the glasswork and cause atomizing, the transparency reduces, and adopt following measure usually: the layer of surface promoting agent is sprayed at glass surface in (1), to remove deposition water droplet and dust above that; (2) apply the organic suction antifogging coating of one deck at glass surface; (3) heating unit is installed, through heating evaporation glass surface water droplet; (4) ultrasonic dispersing and heating unit are installed, the glass surface water droplet is disperseed simultaneously and heats, reach the purpose of rapid evaporation.Yet these methods all have limitation separately: method (1) needs regularly repeatedly the spary tensio-active agent and seems not convenient; Method (2) is owing to use organic substance to cause glasswork wear resistance and thermotolerance bad; Need 7～10 minutes because the heating evaporation water droplet is common in the method (3), poor in timeliness, and need external energy, energy expenditure is big, thereby impracticable; The device of method (4) is complicated, and element is many, cost high (Liu pays and wins acute hearing, and Li Yu puts down 2002 the 3rd phases 16～19 of national building materials technical journal-" glass ").The ambient cure nano self-cleaning glass technology of Zhongke Nano Tech Engineering Center Co., Ltd's (section's nanometer in the abbreviation) obtains remarkable break-throughs; In conjunction with the glass deep processing technology; Accomplish the making of big plate face self-cleaning glass, be applied to construction projects such as Grand National Theatre and car show Room glass.The water of middle section nanometer self-cleaning glass is 6.5 degree at the contact angle of glass surface, and abroad the contact angle of the self-cleaning glass of certain leading company is 17 degree, and is visible, and the wetting ability of middle section nanometer self-cleaning glass is better than the product of external certain leading company far away.(Chen Libin, building glass and industrial glass 2004, No6,12～15).Unfortunately this technology will utilize the photocatalysis characteristic of TiO2 to improve the wetting ability of stromal surface; Must in the environment of UV-irradiation is arranged, just show good hydrophilicity can; Be to be difficult to reach this effect in the environment of dark; And do not reach ultra hydrophilic (contact angle less than 5 degree) of real meaning, therefore limited its scope of application.Generally speaking, present these technological automatically cleanings and anti-fog effect and weather resistance are also undesirable.Therefore to have the coating of long-acting anti-fog function be the developing direction of current antifog technology for development and exploitation, and research and development easily, wear resistance and good weatherability and novel automatically cleaning antifog glass that cost is low be very necessary and significant.
Summary of the invention
One of the object of the invention provides a kind of have simultaneously high transmittance and high hydrophilic anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Two of the object of the invention provides the preparation method of the anti-reflection ultra hydrophilic automatically cleaning antifog glass of purpose one, and this preparing method's technology is simple, low in raw material cost, cost are low, applied widely.
Anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention; Be that have thickness on the surface of glass be that the thickness that the mutual cross connection of the silica nanometer sheet of 10～30 nanometers forms is the rough coatings of 50～160 nanometers; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is 10～200 nanometers.The thickness of said rough coatings can be regulated in 50～160 nanometer range easily.
Above-mentioned thickness is that the rough coatings and the aperture of 50～160 nanometers is the pore structure of 10～200 nanometers, has constituted the coating of rough porous structure jointly.Because the surface has the coating of the rough porous structure of said nano thickness; Make glass have anti-reflection ultra hydrophilic automatically cleaning anti-fog function; Thereby improved the transmittance of original sheet glass greatly, the transmittance of this sheet glass can bring up to 98% from original 90%.
On the surface of above-mentioned anti-reflection ultra hydrophilic automatically cleaning antifog glass thickness being arranged further is the coating of titanium dioxide of 5～100 nanometers, and the anti-reflection ultra hydrophilic automatically cleaning antifog glass with coating of titanium dioxide has the performance of photocatalysis to degrade organic matter.
Anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention because the surface has the coating of the rough porous structure of said nano thickness, thereby has improved the wetting ability of original sheet glass greatly.The 3 μ L globules drop in the surface of simple glass sheet; Through after the sprawling of 0.5 second time; The contact angle of water droplet and sheet glass is greater than 20 °; And the 3 μ L globules drop in the surface of anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention, and through after the sprawling of 0.5 second time, the contact angle of water droplet and anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention is minimum can be less than 5 °.
The preparation method of anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention is under the alkaline aqueous solution condition; Adopt normal pressure heated water bath or two kinds of methods of heated sealed hydro-thermal; Sheet glass to various components carries out effective etching; Form the coating of rough porous structure in glass sheet surface, thereby prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention.
The process that employing normal pressure heated water bath method prepares anti-reflection ultra hydrophilic automatically cleaning antifog glass is following:
To being that the container of inner bag is (by the polytetrafluoroethylmaterial material manufacturing with the polytetrafluoroethylmaterial material; Can effectively resist the corrosion of acid or alkali) in; Adding concentration is the alkaline aqueous solution of 2～15 grams per liters, sheet glass is immersed in the alkaline aqueous solution lid of covered container; And between the lid of container and the container body space is arranged, so that the pressure in the container keeps identical normal atmosphere with the outer pressure of container; Then the container of cover lid being put into water-bath heats; In temperature is under 60～110 ℃ sheet glass to be carried out effective etching (preferred etching time is 1～10 hour); In temperature is under 60～110 ℃, directly takes out sheet glass from container, cleans and sheet glass dried up that (available a large amount of tap water are rinsed well; And the pressurized air that the available air compressor is discharged dries up sheet glass), obtain described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
The concentration of the alkaline aqueous solution that uses is different, and the time of selecting different etchings be different to the etching degree of sheet glass, thereby the sheet glass after the etching have visibly different to light transmitance and to the wetting ability of water.
The process that employing heated sealed hydrothermal method prepares anti-reflection ultra hydrophilic automatically cleaning antifog glass is following:
To being that the container of inner bag is (by the polytetrafluoroethylmaterial material manufacturing with the polytetrafluoroethylmaterial material; Can effectively resist the corrosion of acid or alkali) in; Adding Vinylpyrrolidone polymer and concentration is the alkaline aqueous solution of 2～15 grams per liters; Stirring obtains mixed solution, and Vinylpyrrolidone polymer is that concentration in the alkaline aqueous solution of 2～15 grams per liters is 0～15 grams per liter in concentration; Sheet glass is immersed in the above-mentioned mixed solution; The lid of covered container is put into water heating kettle (can be stainless steel hydro-thermal still) with the container of cover lid, tightens the lid of water heating kettle; Under sealed state; Putting into baking oven to water heating kettle, is under 60～110 ℃ sheet glass to be carried out effective etching (preferred etching time is 1～10 hour) in temperature, naturally cools to room temperature then; Open hydro-thermal kettle cover; Take out with the polytetrafluoroethylmaterial material is the container of inner bag; Take out sheet glass more from container; Clean and sheet glass is dried up (available a large amount of tap water are rinsed well, and the pressurized air that the available air compressor is discharged dries up sheet glass), obtain described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
The concentration of the alkaline aqueous solution that uses is different, and the temperature of selecting different etchings is different to the etching degree of sheet glass, and the adding of Vinylpyrrolidone polymer helps to improve the homogeneity of glass sheet surface etching.Thereby the sheet glass after the etching have visibly different to light transmitance and to the wetting ability of water.
The anti-reflection ultra hydrophilic automatically cleaning antifog glass that above-mentioned two kinds of methods obtain; Be that have thickness on the surface of glass be that the thickness that the mutual cross connection of the silica nanometer sheet of 10～30 nanometers forms is the rough coatings of 50～160 nanometers; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is 10～200 nanometers.The thickness of said rough coatings can be regulated in 50～160 nanometer range easily.
Alkaline aqueous solution described in the present invention comprises all alkaline aqueous solutions, for example: aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or ammoniacal liquor etc.The purity of employed Pottasium Hydroxide, sodium hydroxide is preferably 60～100%.
Vinylpyrrolidone polymer described in the present invention is as stablizer or protective material, and the high molecular polymer that also comprises other composition is as stablizer or protective material, and the molecular weight of said high molecular polymer is in 100～100000 scopes.The purity of described Vinylpyrrolidone polymer is preferably 90～100%.
Sheet glass described in the present invention comprises the simple glass sheet of various compositions, the simple glass sheet of various structures, the simple glass sheet of various size and the simple glass sheet of various prepared.
With the anti-reflection ultra hydrophilic automatically cleaning antifog glass that obtains after the above-mentioned etching as substrate; Adopt the method for dip-coating; Titania sol liquid is coated in the surface of anti-reflection ultra hydrophilic automatically cleaning antifog glass, and the thickness of coated titanium oxide is 5～100 nanometers, drying; Calcining, obtaining thickness is the anti-reflection ultra hydrophilic automatically cleaning antifog glass with photocatalysis to degrade organic matter performance of the coating of titanium dioxide of 5～100 nanometers.Its process is following:
The above-mentioned anti-reflection ultra hydrophilic automatically cleaning antifog glass that after normal pressure heated water bath method or heated sealed hydrothermal method etching, obtains is put into titania sol liquid leave standstill (general time of repose is 0.5～10 minute); Then anti-reflection ultra hydrophilic automatically cleaning antifog glass is slowly lifted taking-up from titania sol liquid; And put into ethanol and leave standstill (general time of repose be 0.5～10 minute); After anti-reflection ultra hydrophilic automatically cleaning antifog glass taken out from ethanol; Dry up the back with pressurized air and accomplish a dip-coating process, after the drying, the titania sol liquid of coating is transformed into titania gel; Repeat above-mentionedly anti-reflection ultra hydrophilic automatically cleaning antifog glass is put into titania sol liquid to leave standstill, lift taking-up, put into ethanol and leave standstill, take out and dry up process, can realize secondary dip-coating, three dip-coatings and repeatedly dip-coating from ethanol.At last; The anti-reflection ultra hydrophilic automatically cleaning antifog glass that is coated with titania gel is put into retort furnace; Under 400～550 degrees centigrade, calcine and came the activation titania gel in 0.5～6 hour, obtaining thickness is the anti-reflection ultra hydrophilic automatically cleaning antifog glass with photocatalysis to degrade organic matter performance of the coating of titanium dioxide of 5～100 nanometers.Wherein, the content that is coated in the titania sol liquid on anti-reflection ultra hydrophilic automatically cleaning antifog glass surface can be regulated through the number of times that increases dip-coating.
Described titania sol liquid is according to tetrabutyl titanate: methyl ethyl diketone: water: ethanol: the volume ratio of concentrated hydrochloric acid (the quality percentage composition is 37%) is 1: 0.2: 0.4: 16: 0.1 ratio, and with what obtain after the said components mixing.
The present invention with the cheap and simple glass sheet that is prone to obtain as substrate; Under the alkaline aqueous solution condition; Sheet glass is carried out etching, adopt normal pressure heated water bath and two kinds of methods of heated sealed hydro-thermal, can carry out effective etching the glass of various components; Form the coating of rough porous structure at glass surface, thereby prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.Preparing method of the present invention is simple, only needs can accomplish once going on foot, and technology is simple, cost is low, applied widely.Prepared glass has high transmittance, and high transmission rate reaches 98.0%; Has high wetting ability; Promptly the 3 μ L globules drop in the surface of anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention; Through after the sprawling of 0.5 second time; The contact angle of water droplet and anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention is minimum can be less than 5 °, thereby can effectively reduce the tension force of water at glass surface, make water spread over glass surface rapidly and take away the purpose that dirt reaches the cleaning glass surface.
Anti-reflection ultra hydrophilic automatically cleaning antifog glass of the present invention can be used to comprise the glass window, glass sunroof, glass curtain wall, Household bathroom mirror, windshield, rear vision mirror, background glass, ophthalmic lens of family, apartment and commerce and public place building etc.Be particularly suitable for as anti-reflection antifouling packaging glass of solar cell and vacuum solar heat-collecting pipe glass.
Description of drawings
Fig. 1. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters, when the etching temperature of selection is 95 ℃, through the stereoscan photograph of the structure of the glass sheet surface after the different etching time.Fig. 1 a, Fig. 1 c, Fig. 1 e and Fig. 1 g are respectively the stereoscan photograph through the glass sheet surface structure after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.Fig. 1 b, Fig. 1 d, Fig. 1 f and Fig. 1 h are respectively the stereoscan photograph of cross section structure of glass sheet surface of the correspondence of 1a, Fig. 1 c, Fig. 1 e and Fig. 1 g.
Fig. 2. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters, when the etching temperature of selection is 95 ℃, be respectively light transmittance curve figure through the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.
Fig. 3 .3 μ L globule drops among the embodiment 1 (when the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters; When the etching temperature of selecting is 95 ℃; Respectively through 3 hours, 4.5 hours, 6 hours and 7 hours) etching glass sheet surface afterwards, the digital photograph of the contact angle situation of water droplet and sheet glass.
Fig. 4. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters, when the etching temperature of selection is 95 ℃, be respectively light transmittance curve figure through the sheet glass after 5 hours, 6 hours, 7 hours and the 8 hours etchings.
Fig. 5 .3 μ L globule drops among the embodiment 1 (when the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; When the etching temperature of selecting is 95 ℃; Respectively through 5 hours, 6 hours, 7 hours and 8 hours) etching glass sheet surface afterwards, the digital photograph of the contact angle situation of water droplet and sheet glass.
Fig. 6. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 5.0 grams per liters, when the etching temperature of selection is 95 ℃, be respectively light transmittance curve figure through the sheet glass after 5 hours, 6 hours and the 7 hours etchings.
Fig. 7. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 8.75 grams per liters, when the etching temperature of selection is 95 ℃, be respectively light transmittance curve figure through the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.
Fig. 8. in the embodiment of the invention 1, when the concentration of potassium hydroxide aqueous solution is 10.0 grams per liters, when the etching temperature of selection is 95 ℃, be respectively light transmittance curve figure through the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.
Fig. 9. in the embodiment of the invention 4, when the concentration of potassium hydroxide aqueous solution was 6.25 grams per liters, the etching time of selection was 2 hours, the stereoscan photograph of the structure of the glass sheet surface after the process different etching temperature.Fig. 9 a, Fig. 9 c and Fig. 9 e be the stereoscan photograph of the low enlargement ratio of the structure of the glass sheet surface after over etching under 85 ℃, 90 ℃ and 95 ℃ of temperature respectively.Fig. 9 b, Fig. 9 d and Fig. 9 f are respectively the stereoscan photograph of high enlargement ratio of glass sheet surface structure of the correspondence of Fig. 9 a, Fig. 9 c and Fig. 9 e.
Figure 10. in the embodiment of the invention 4; When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; The etching time of selecting is 2 hours, respectively the light transmittance curve figure of the sheet glass after over etching under 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 105 ℃ of temperature.
Figure 11 .3 μ L globule drops among the embodiment 4 (when the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; The etching time of selecting is 2 hours; Respectively under 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 105 ℃ of temperature) glass sheet surface after over etching, the digital photograph of the contact angle situation of water droplet and sheet glass.
Figure 12. in the embodiment of the invention 4; When the concentration of potassium hydroxide aqueous solution is 8.75 grams per liters; The etching time of selecting is 2 hours, respectively the light transmittance curve figure of the sheet glass after over etching under 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 105 ℃ of temperature.
Figure 13. in the embodiment of the invention 4, when the concentration of potassium hydroxide aqueous solution was 12.5 grams per liters, the etching time of selection was 2 hours, respectively the light transmittance curve figure of the sheet glass after over etching under 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 105 ℃ of temperature.
Figure 14. in the embodiment of the invention 8, respectively with the sheet glass after the etching in titania sol liquid through a dip-coating (Figure 14 a), the stereoscan photograph of the structure on the surface of sheet glass after calcining after secondary dip-coating (Figure 14 b) and three dip-coatings (Figure 14 c) etching afterwards.
Figure 15. in the embodiment of the invention 8, respectively with the light transmittance curve figure through the sheet glass after the etching after a dip-coating, secondary dip-coating and three dip-coatings in titania sol liquid of the sheet glass after the etching.
Figure 16. in the embodiment of the invention 8; The 3 μ L globules drop in through the glass sheet surface after the etching of dip-coating titania sol liquid, secondary dip-coating titania sol liquid and three dip-coating titania sol liquid, the digital photograph of the contact angle situation of water droplet and sheet glass.
Figure 17. will be in the embodiment of the invention 8 not through the sheet glass after the etching of dip-coating titania sol liquid; With the sheet glass after the etching is put into methylene blue solution respectively through the sheet glass after a dip-coating, secondary dip-coating and three dip-coatings respectively in titania sol liquid; Under ultraviolet lighting, the light absorption ratio change curve of methylene blue solution.
Embodiment
Adopt normal pressure heated water bath method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
In the volume that with the polytetrafluoroethylmaterial material is inner bag is 100 milliliters container; The water and a certain amount of Pottasium Hydroxide pressed powder (purity is 60～100%) that add 80 milliliters; Stir; Be made into the potassium hydroxide aqueous solution that concentration can change in 2～15 grams per liter scopes, sheet glass (sheet glass is of a size of centimetre (length) * 0.1,2.5 centimetres of (wide) * 7.5 centimetre (thickness)) is put into container, the lid of covered container; And between the lid of container and the container body space is arranged, so that the pressure in the container keeps identical normal atmosphere with the outer pressure of container; Then the container of cover lid is put into water-bath and heat, be 60～100 ℃ in temperature and heated 1～10 hour down, sheet glass is carried out effective etching; In temperature is under 60～100 ℃, directly takes out sheet glass from container, with a large amount of tap water sheet glass is rinsed well, and is dried up sheet glass with the pressurized air of air discharge, obtains described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Selecting the alkaline aqueous solution etching time different with selection of different concns, is different to the etching degree of sheet glass, thus the sheet glass after the etching have visibly different to light transmitance and to the wetting ability of water.
When the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters, when the etching temperature of selection is 95 ℃, as shown in Figure 1 through the structure of the glass sheet surface after the different time etching.Fig. 1 a, Fig. 1 c, Fig. 1 e and Fig. 1 g are respectively the stereoscan photograph through the structure of the glass sheet surface after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.From Fig. 1 a, can see; Having occurred by little thickness through 3 hours etchings glass sheet surface afterwards is that the thickness that the mutual cross connection of silica nanometer sheet about 10 nanometers forms is the rough coatings of nanoscale; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in hole is 10～200 nanometers.From Fig. 1 c, can see; Having occurred by thickness through the glass sheet surface after 4.5 hours etchings is that the thickness that the mutual cross connection of silica nanometer sheet of 10～30 nanometers forms is the rough coatings of nanoscale; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is 10～200 nanometers.From Fig. 1 e and Fig. 1 g, can see respectively; Glass sheet surface after 6 hours and the 7 hours etchings does not have obvious variation; Remaining by thickness is that thickness that the mutual cross connection of silica nanometer sheet of 10～30 nanometers forms is that the rough coatings and the aperture of nanoscale is the pore structure of 10～200 nanometers, the coating of the common rough porous structure that constitutes.From stereoscan photograph Fig. 1 b, Fig. 1 d, Fig. 1 f and Fig. 1 h of the cross section structure of the corresponding respectively glass sheet surface of Fig. 1 a, Fig. 1 c, Fig. 1 e and Fig. 1 g, show: through the thickness of the glass sheet surface after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings is that the thickness of the rough coatings (coating of rough porous structure) of nanoscale is respectively 50 nanometers, 100 nanometers, 120 nanometers and 160 nanometers; Glass sheet surface is along with the prolongation of etching time, and the thickness of rough porous structure coating increases gradually.Fig. 2 has showed the light transmittance curve figure through the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.Maximum transmission rate through 3 hours etchings sheet glass afterwards is 91.6% of 405 nano wave length places; Maximum transmission rate through 4.5 hours etchings sheet glass afterwards is 94.7% of 406 nano wave length places; Maximum transmission rate through the sheet glass after 6 hours etchings is 96.1% of 550 nano wave length places, is 92.7% of 662 nano wave length places through the maximum transmission rate of the sheet glass after 7 hours etchings; This shows, showed the highest transmittance through 6 hours etchings sheet glass afterwards.Fig. 3 shows: on the 3 μ L globules drop in through the glass sheet surface after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 8.9 °; 7.4 °, 5.2 ° and 7.9 °, the globule is minimum through the contact angle on the glass sheet surface after 6 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters, when the etching temperature of selection is 95 ℃, as shown in Figure 4 through the light transmittance curve figure of the sheet glass after 5 hours, 6 hours, 7 hours and the 8 hours etchings.Maximum transmission rate through 5 hours etchings sheet glass afterwards is 98.0% of 560 nano wave length places; Maximum transmission rate through 6 hours etchings sheet glass afterwards is 97.2% of 580 nano wave length places; Maximum transmission rate through 7 hours etchings sheet glass afterwards is 95.6% of 626 nano wave length places; Maximum transmission rate through 8 hours etchings sheet glass afterwards is 94.4% of 626 nano wave length places, this shows, has showed the highest transmittance through 5 hours etchings sheet glass afterwards.Fig. 5 shows: on the 3 μ L globules drop in through the glass sheet surface after 5 hours, 6 hours, 7 hours and the 8 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 6.1 °; 4.9 °, 5.4 ° and 5.4 °, the globule is minimum through the contact angle on the glass sheet surface after 6 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 5.0 grams per liters, when the etching temperature of selection is 95 ℃, as shown in Figure 6 through the light transmittance curve figure of the sheet glass after 5 hours, 6 hours and the 7 hours etchings.Maximum transmission rate through 5 hours etchings sheet glass afterwards is 98.0% of 565 nano wave length places; Maximum transmission rate through the sheet glass after 6 hours etchings is 95.4% of 595 nano wave length places, is 89.6% of 800 nano wave length places through the maximum transmission rate of the sheet glass after 7 hours etchings; This shows, showed the highest transmittance through 5 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 5 hours, 6 hours and the 7 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The contact angle of water droplet and sheet glass is respectively 5.2 °; 5.7 ° and 5.8 °, the globule is minimum through the contact angle on the glass sheet surface after 5 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 2.0 grams per liters; When the etching temperature of selecting is 95 ℃; Transmittance through the sheet glass after 4 hours, 6 hours, 8 hours and the 10 hours etchings is: the maximum transmission rate through the sheet glass after 4 hours etchings is 92.0% of 562 nano wave length places; Maximum transmission rate through the sheet glass after 6 hours etchings is 94.6% of 567 nano wave length places, is 96.6% of 640 nano wave length places through the maximum transmission rate of the sheet glass after 8 hours etchings; Maximum transmission rate through 10 hours etchings sheet glass afterwards is 95.6% of 740 nano wave length places.This shows, showed the highest transmittance through 8 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 4 hours, 6 hours, 8 hours and the 10 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The contact angle of water droplet and sheet glass is respectively 11.2 °; 7.7 °, 5.2 ° and 6.8 °, the globule is minimum through the contact angle on the glass sheet surface after 8 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 8.75 grams per liters, when the etching temperature of selection is 95 ℃, as shown in Figure 7 through the light transmittance curve figure of the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.Maximum transmission rate through 3 hours etchings sheet glass afterwards is 93.6% of 480 nano wave length places; Maximum transmission rate through 4.5 hours etchings sheet glass afterwards is 95.0% of 480 nano wave length places; Maximum transmission rate through the sheet glass after 6 hours etchings is 97.6% of 515 nano wave length places, is 96.6% of 540 nano wave length places through the maximum transmission rate of the sheet glass after 7 hours etchings; This shows, showed the highest transmittance through 6 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 10.9 °; 7.4 °, 5.0 ° and 6.1 °, the globule is minimum through the contact angle on the glass sheet surface after 6 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 10 grams per liters, when the etching temperature of selection is 95 ℃, as shown in Figure 8 through the light transmittance curve figure of the sheet glass after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings.Maximum transmission rate through 3 hours etchings sheet glass afterwards is 97.0% of 518 nano wave length places; Maximum transmission rate through 4.5 hours etchings sheet glass afterwards is 96.8% of 582 nano wave length places; Maximum transmission rate through the sheet glass after 6 hours etchings is 94.2% of 677 nano wave length places, is 87.3% of 617 nano wave length places through the maximum transmission rate of the sheet glass after 7 hours etchings; This shows, showed the highest transmittance through the sheet glass after 3 hours etchings, along with the prolongation of etching time, the numerical value of high transmission rate reduces on the contrary.On the 3 μ L globules drop in through the glass sheet surface after 3 hours, 4.5 hours, 6 hours and the 7 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 5.5 °; 4.8 °, 7.6 ° and 7.9 °, the globule is minimum through the contact angle on the glass sheet surface after 4.5 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 15 grams per liters; When the etching temperature of selecting is 95 ℃; Transmittance through the sheet glass after 1 hour, 2 hours, 3 hours and the 4 hours etchings is: the maximum transmission rate through the sheet glass after 1 hour etching is 96.6% of 516 nano wave length places; Maximum transmission rate through 2 hours etchings sheet glass afterwards is 97.2% of 565 nano wave length places; Maximum transmission rate through the sheet glass after 3 hours etchings is 94.2% of 635 nano wave length places, is 92.2% of 667 nano wave length places through the maximum transmission rate of the sheet glass after 4 hours etchings; This shows, showed the highest transmittance through the sheet glass after 2 hours etchings, along with the prolongation of etching time, the numerical value of high transmission rate reduces on the contrary.On the 3 μ L globules drop in through the glass sheet surface after 1 hour, 2 hours, 3 hours and the 4 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 7.5 °; 5.1 °, 6.6 ° and 8.9 °, the globule is minimum through the contact angle on the glass sheet surface after 2 hours etchings.
Embodiment 2.
Adopt normal pressure heated water bath method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Under the experiment condition identical, investigate of the influence of different etching temperatures to the sheet glass etching with embodiment 1.
When the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters; When the etching temperature of selecting is 60 ℃; Transmittance through the sheet glass after 4 hours, 6 hours, 8 hours and the 10 hours etchings is: the maximum transmission rate through the sheet glass after 4 hours etchings is 91.0% of 402 nano wave length places; Maximum transmission rate through 6 hours etchings sheet glass afterwards is 93.7% of 456 nano wave length places; Maximum transmission rate through the sheet glass after 8 hours etchings is 96.6% of 543 nano wave length places, is 94.7% of 662 nano wave length places through the maximum transmission rate of the sheet glass after 10 hours etchings; This shows, showed the highest transmittance through 8 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 4 hours, 6 hours, 8 hours and the 10 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 9.9 °; 7.2 °, 5.1 ° and 7.6 °, the globule is minimum through the contact angle on the glass sheet surface after 8 hours etchings.
When the concentration of potassium hydroxide aqueous solution is 7.5 grams per liters; When the etching temperature of selecting is 100 ℃; Transmittance through the sheet glass after 2 hours, 3 hours, 4 hours and the 5 hours etchings is: the maximum transmission rate through the sheet glass after 2 hours etchings is 93.6% of 423 nano wave length places; Maximum transmission rate through 3 hours etchings sheet glass afterwards is 95.7% of 478 nano wave length places; Maximum transmission rate through the sheet glass after 4 hours etchings is 96.8% of 555 nano wave length places, is 94.2% of 676 nano wave length places through the maximum transmission rate of the sheet glass after 5 hours etchings; This shows, showed the highest transmittance through 4 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 2 hours, 3 hours, 4 hours and the 5 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 11.2 °; 6.4 °, 5.0 ° and 7.5 °, the globule is minimum through the contact angle on the glass sheet surface after 4 hours etchings.
Adopt normal pressure heated water bath method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Under the experiment condition identical, investigate of the influence of different alkaline aqueous solutions to the sheet glass etching with embodiment 1.
Aqueous sodium hydroxide solution is used for the etching glass sheet.
When the concentration of aqueous sodium hydroxide solution is 7.5 grams per liters; When the etching temperature of selecting is 95 ℃; Transmittance through the sheet glass after 2 hours, 3 hours, 4 hours and the 5 hours etchings is: the maximum transmission rate through the sheet glass after 2 hours etchings is 91.9% of 403 nano wave length places; Maximum transmission rate through 3 hours etchings sheet glass afterwards is 94.6% of 434 nano wave length places; Maximum transmission rate through the sheet glass after 4 hours etchings is 97.1% of 557 nano wave length places, is 93.5% of 658 nano wave length places through the maximum transmission rate of the sheet glass after 5 hours etchings; This shows, showed the highest transmittance through 4 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 2 hours, 3 hours, 4 hours and the 5 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 9.2 °; 7.1 °, 5.3 ° and 8.9 °, the globule is minimum through the contact angle on the glass sheet surface after 4 hours etchings.
Ammonia soln is used for the etching glass sheet.
When the concentration of ammonia soln is 2 grams per liters; When the etching temperature of selecting is 95 ℃; Transmittance through the sheet glass after 2 hours, 3 hours, 4 hours and the 5 hours etchings is: the maximum transmission rate through the sheet glass after 2 hours etchings is 92.6% of 408 nano wave length places; Maximum transmission rate through 3 hours etchings sheet glass afterwards is 94.6% of 428 nano wave length places; Maximum transmission rate through the sheet glass after 4 hours etchings is 96.6% of 552 nano wave length places, is 94.7% of 668 nano wave length places through the maximum transmission rate of the sheet glass after 5 hours etchings; This shows, showed the highest transmittance through 4 hours etchings sheet glass afterwards.On the 3 μ L globules drop in through the glass sheet surface after 2 hours, 3 hours, 4 hours and the 5 hours etchings respectively; From the teeth outwards through after the sprawling of 0.5 second time; The digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 10.2 °; 7.2 °, 4.8 ° and 6.6 °, the globule is minimum through the contact angle on the glass sheet surface after 4 hours etchings.
Embodiment 4.
Adopt the heated sealed hydrothermal method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
In the volume that with the polytetrafluoroethylmaterial material is inner bag is 100 milliliters container; Add 80 milliliters water, a certain amount of Pottasium Hydroxide pressed powder (purity is 60～100%) and a certain amount of Vinylpyrrolidone polymer (purity is 90～100%); Stir and obtain containing the potassium hydroxide aqueous solution of Vinylpyrrolidone polymer; Wherein: the concentration of potassium hydroxide aqueous solution changes in 2～15 grams per liter scopes, and the concentration of Vinylpyrrolidone polymer changes in 0～15 grams per liter scope; Sheet glass (sheet glass is of a size of centimetre (length) * 0.1,2.5 centimetres of (wide) * 7.5 centimetre (thickness)) is immersed in the above-mentioned potassium hydroxide aqueous solution that contains Vinylpyrrolidone polymer, and the lid of covered container is put into stainless steel hydro-thermal still with the container of building lid; Tighten the lid of water heating kettle, under sealed state, put into baking oven to water heating kettle; Heated 1～3 hour down in differing temps (60～110 ℃), after the time, naturally cool to room temperature; Open hydro-thermal kettle cover, taking out with the polytetrafluoroethylmaterial material is the container of inner bag, from this container, takes out sheet glass again; Rinse well with a large amount of tap water, the gas of getting rid of with air dries up sheet glass.
Select different concns alkaline aqueous solution, select the temperature and different etching times of different etchings, be different to the etching degree of sheet glass, and the adding of Vinylpyrrolidone polymer helps to improve the homogeneity of glass sheet surface etching.Thereby the sheet glass after the etching have visibly different to light transmitance and to the wetting ability of water.
When the concentration of potassium hydroxide aqueous solution was 6.25 grams per liters, the concentration of Vinylpyrrolidone polymer was at 0.6 grams per liter, and is as shown in Figure 9 through the structure of the glass sheet surface after 2 hours etchings under differing temps.Fig. 9 a, Fig. 9 c and Fig. 9 e are respectively the stereoscan photograph through the low range of the structure of the glass sheet surface after 85 ℃, 90 ℃ and the 95 ℃ of etchings.From these pictures, can see; What glass sheet surface etched is that thickness that the mutual cross connection of silica nanometer sheet of nanoscale forms is that the rough coatings and the aperture of nanoscale is the pore structure of 10～200 nanometers by thickness, and the coating of the common rough porous structure that constitutes is more uniform.Fig. 9 b, Fig. 9 d and Fig. 9 f are respectively the powerful stereoscan photograph through the structure of the glass sheet surface after 85 ℃, 90 ℃ and the 95 ℃ of etchings; From figure, can see: through the not too big considerable change of rough porous structure of the glass sheet surface after 85 ℃, 90 ℃ and the 95 ℃ of etchings; It is that the thickness that the mutual cross connection of silica nanometer sheet of 10～30 nanometers forms is the rough coatings of 10～30 nanoscales that glass sheet surface after over etching has all formed thickness; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is 10～200 nanometers.Figure 10 has showed through 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 105 ℃ of light transmittance curve figure through 2 hours etchings sheet glass afterwards.Maximum transmission rate through the sheet glass after 80 ℃ of etchings is 90.8% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 95.1% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.5% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 96.9% of 538 nano wave length places; Maximum transmission rate through the sheet glass after 100 ℃ of etchings is 89.7% of 700 nano wave length places, is 86.4% of 615 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 90 ℃ and the 95 ℃ of etchings.It is shown in figure 11: on the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 15.3 °, 9.6 ° from the teeth outwards; 5.0 °; 4.5 °, 9.2 ° and 16.4 °, the globule is minimum through the contact angle on the glass sheet surface after 95 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution was 8.75 grams per liters, the concentration of Vinylpyrrolidone polymer was at 0.6 grams per liter, and is shown in figure 12 through the structure of the glass sheet surface after 2 hours etchings under differing temps.Figure 12 has showed the light transmittance curve figure through the sheet glass after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings.Maximum transmission rate through the sheet glass after 80 ℃ of etchings is 93.8% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 96.0% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 95.5% of 512 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 97.4% of 560 nano wave length places; Maximum transmission rate through the sheet glass after 100 ℃ of etchings is 92.2% of 600 nano wave length places, is 85.5% of 740 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 95 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 15.8 °, 12.6 ° from the teeth outwards; 6.2 °; 9.5 °, 18.2 ° and 8.3 °, the globule is minimum through the contact angle on the glass sheet surface after 90 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution was 12.5 grams per liters, the concentration of Vinylpyrrolidone polymer was at 0.6 grams per liter, and is shown in figure 13 through the light transmittance curve figure of the glass sheet surface after 2 hours etchings under differing temps.Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 93.0% of 536 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 93.8% of 536 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 96.7% of 566 nano wave length places; Maximum transmission rate through the sheet glass after 100 ℃ of etchings is 89.1% of 667 nano wave length places, is 78.7% of 800 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed the highest transmittance through the sheet glass after 95 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 12.1 °, 9.1 ° from the teeth outwards; 4.8 °; 8.6 °, 5.8 ° and 4.2 °, the globule has less contact angle from the teeth outwards through the sheet glass after 90 ℃ and the 105 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution is 15 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 60 ℃ of etchings is 91.2% of 535 nano wave length places; Maximum transmission rate through the sheet glass after 80 ℃ of etchings is 92.6% of 539 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.7% of 556 nano wave length places; Maximum transmission rate through the sheet glass after 100 ℃ of etchings is 88.1% of 672 nano wave length places, is 76.7% of 800 nano wave length places through the maximum transmission rate of the sheet glass after 110 ℃ of etchings; This shows, showed the highest transmittance through the sheet glass after 90 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 60 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃ and the 110 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 18.1 °, 14.1 ° from the teeth outwards; 4.4 °; 8.2 °, 6.8 ° and 5.7 °, the globule has less contact angle from the teeth outwards through the sheet glass after 90 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution is 2 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 85 ℃ of etchings is 90.7% of 535 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 91.2% of 536 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 93.3% of 538 nano wave length places; Maximum transmission rate through the sheet glass after 100 ℃ of etchings is 95.1% of 556 nano wave length places, is 93.7% of 660 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed the highest transmittance through the sheet glass after 100 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 17.1 °, 14.1 ° from the teeth outwards; 9.4 °; 6.2 °, 5.8 ° and 65.7 °, the globule has less contact angle from the teeth outwards through the sheet glass after 100 ℃ of etchings.
Adopt the heated sealed hydrothermal method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Under identical experiment condition, investigate of the influence of different etching times to the sheet glass etching.
When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 1 hour etching under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 90.5% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 94.1% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 95.5% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 96.2% of 538 nano wave length places, is 96.7% of 700 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 91.4% of 615 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 95 ℃ and the 100 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 15.8 °, 9.0 ° from the teeth outwards; 5.3 °; 4.2 °, 4.9 ° and 13.4 °, the globule is minimum through the contact angle on the glass sheet surface after 95 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 3 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 92.5% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 94.9% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.1% of 400 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 96.6% of 538 nano wave length places, is 95.3% of 700 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 88.2% of 615 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 90 ℃ and the 95 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 10.8 °, 7.0 ° from the teeth outwards; 5.1 °; 4.3 °, 6.9 ° and 12.4 °, the globule is minimum through the contact angle on the glass sheet surface after 95 ℃ of etchings.
Adopt the heated sealed hydrothermal method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Under identical experiment condition, investigate of the influence of the concentration of aqueous solution of different Vinylpyrrolidone polymers to the sheet glass etching.
When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; Do not add Vinylpyrrolidone polymer; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 91.5% of 408 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 93.1% of 426 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 95.5% of 540 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 96.8% of 598 nano wave length places, is 91.7% of 625 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 87.2% of 724 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 95 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 9.8 °, 7.0 ° from the teeth outwards; 5.6 °; 4.6 °, 5.9 ° and 6.1 °, the globule is minimum through the contact angle on the glass sheet surface after 95 ℃ of etchings.
When the concentration of potassium hydroxide aqueous solution is 6.25 grams per liters; The concentration of Vinylpyrrolidone polymer is at 15 grams per liters; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 92.8% of 405 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 94.1% of 447 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.2% of 514 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 97.2% of 556 nano wave length places, is 93.7% of 650 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 92.4% of 715 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 95 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 8.8 °, 6.7 ° from the teeth outwards; 6.1 °; 5.0 °, 5.9 ° and 6.4 °, the globule is minimum through the contact angle on the glass sheet surface after 95 ℃ of etchings.
Adopt the heated sealed hydrothermal method, prepare anti-reflection ultra hydrophilic automatically cleaning antifog glass.
Under identical experiment condition, investigate of the influence of different basic solns to the sheet glass etching.
Aqueous sodium hydroxide solution is used for the etching glass sheet.
When the concentration of aqueous sodium hydroxide solution is 6.25 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 92.5% of 456 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 94.1% of 488 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.5% of 540 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 92.2% of 598 nano wave length places, is 89.7% of 650 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 87.4% of 745 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 90 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 8.8 °, 8.0 ° from the teeth outwards; 4.6 °; 5.2 °, 5.9 ° and 5.4 °, the globule is minimum through the contact angle on the glass sheet surface after 90 ℃ of etchings.
Ammonia soln is used for the etching glass sheet.
When the concentration of ammonia soln is 2 grams per liters; The concentration of Vinylpyrrolidone polymer is at 0.6 grams per liter; Transmittance through the glass sheet surface after 2 hours etchings under differing temps is: the maximum transmission rate through the sheet glass after 80 ℃ of etchings is 93.5% of 445 nano wave length places; Maximum transmission rate through the sheet glass after 85 ℃ of etchings is 94.5% of 496 nano wave length places; Maximum transmission rate through the sheet glass after 90 ℃ of etchings is 96.8% of 546 nano wave length places; Maximum transmission rate through the sheet glass after 95 ℃ of etchings is 93.2% of 602 nano wave length places, is 91.7% of 636 nano wave length places through the maximum transmission rate of the sheet glass after 100 ℃ of etchings, is 88.4% of 724 nano wave length places through the maximum transmission rate of the sheet glass after 105 ℃ of etchings; This shows, showed higher transmittance through the sheet glass after 90 ℃ of etchings.On the 3 μ L globules drop in through the glass sheet surface after 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and the 105 ℃ of etchings respectively; Through after the sprawling of 0.5 second time, the digital photograph that the globule is sprawled situation shows that the contact angle of water droplet and sheet glass is respectively 9.2 °, 8.3 ° from the teeth outwards; 4.8 °; 5.4 °, 5.7 ° and 5.9 °, the globule is minimum through the contact angle on the glass sheet surface after 90 ℃ of etchings.
Embodiment 8.
According to tetrabutyl titanate: methyl ethyl diketone: water: ethanol: the volume ratio of concentrated hydrochloric acid (the quality percentage composition is 37%) is 1: 0.2: 0.4: 16: 0.1 ratio obtains titania sol liquid after said components mixed.
The anti-reflection ultra hydrophilic automatically cleaning antifog glass that obtains after the etching among the embodiment 1 is put into above-mentioned titania sol liquid to leave standstill about 1 minute; Then anti-reflection ultra hydrophilic automatically cleaning antifog glass is slowly lifted taking-up from titania sol liquid; And put into ethanol and leave standstill about 1 minute, after anti-reflection ultra hydrophilic automatically cleaning antifog glass is taken out from ethanol, dry up the back with pressurized air and accomplish a dip-coating process; After the drying, the titania sol liquid of coating is transformed into titania gel; Repeat above-mentionedly anti-reflection ultra hydrophilic automatically cleaning antifog glass is put into titania sol liquid to leave standstill, lift taking-up, put into ethanol and leave standstill, take out and dry up process twice from ethanol.At last; The anti-reflection ultra hydrophilic automatically cleaning antifog glass that is coated with titania gel is put into retort furnace; Under 400 degrees centigrade, calcine and came the activation titania gel in 2 hours; Obtain the coating of titanium dioxide that thickness is 5～100 nanometers on the surface of anti-reflection ultra hydrophilic automatically cleaning antifog glass, thereby obtain having the anti-reflection ultra hydrophilic automatically cleaning antifog glass of photocatalysis to degrade organic matter performance.Figure 14 is with the stereoscan photograph through the structure of the glass sheet surface after a dip-coating (a), secondary dip-coating (b) and three dip-coatings (c) and the etching after calcining in titania sol liquid of the sheet glass after the etching; Therefrom can see; Along with the increase of dip-coating number of times, the titania gel behind inner activated in the hole that glass sheet surface is made up of nanometer sheet increases gradually.Through regulating the number of times of dip-coating, can realize that the coating of titanium dioxide thickness that applies changes in 5～100 nanometer range.Figure 15 is respectively with the light transmittance curve figure through a dip-coating, secondary dip-coating and three dip-coatings and the sheet glass after calcining in titania sol liquid of the sheet glass after the etching; This result shows: along with the increase of dip-coating number of times, the transmittance that is coated with the sheet glass after the etching of the titania gel after activated reduces gradually.Figure 16 is that the 3 μ L globules drop in through the glass sheet surface after the etching of a dip-coating titania sol liquid, secondary dip-coating titania sol liquid and three dip-coating titania sol liquid after the calcining; Water droplet on the surface of sheet glass through after the sprawling of 0.5 second time; The globule is sprawled the digital photograph of situation, and the contact angle of the globule and sheet glass is respectively 3.6 °, 4.0 ° and 4.3 °; This result shows: along with the increase of dip-coating number of times, its contact angle increases gradually.
The photocatalytic activity of the sheet glass after the etching that is coated with the titania gel after activated after the test calcining.Use methylene blue as the mimic organic pollutant.One 25 watts high voltage mercury lamp is as light source, and its radiative predominant wavelength is 365 nanometers, light intensity be 2.5 milliwatts/centimetre
2To put into 15 milliliters methylene blue solution through the sheet glass after the etching of dip-coating titania sol liquid, secondary dip-coating titania sol liquid and three dip-coating titania sol liquid respectively, the concentration of methylene blue solution is 10mg/L.Under high voltage mercury lamp radiation, every at a distance from 15 minutes, the solution of taking-up 2mL is tested its ultraviolet-visible absorption spectroscopy from above-mentioned methylene blue solution.Figure 17 shows: in titania sol liquid, through the sheet glass after the etching of dip-coating methylene blue is not had obviously higher degradation efficiency through the ratio of the sheet glass after the dip-coating; And along with the number of times of dip-coating increases, its photocatalysis performance also has increase to a certain degree.
Claims (10)
1. anti-reflection ultra hydrophilic automatically cleaning antifog glass; It is characterized in that: described anti-reflection ultra hydrophilic automatically cleaning antifog glass is that have thickness on the surface of glass be that the thickness that the mutual cross connection of the silica nanometer sheet of 10～30 nanometers forms is the rough coatings of 50～160 nanometers; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is in 10～200 nanometers.
2. anti-reflection ultra hydrophilic automatically cleaning antifog glass according to claim 1 is characterized in that: it is the coating of titanium dioxide of 5～100 nanometers that there is thickness on the surface of described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
3. the preparation method of an anti-reflection ultra hydrophilic automatically cleaning antifog glass according to claim 1; It is characterized in that: to being in the container of inner bag with the polytetrafluoroethylmaterial material; Adding concentration is the alkaline aqueous solution of 2～15 grams per liters; Sheet glass is immersed in the alkaline aqueous solution, the lid of covered container, and between the lid of container and the container body space is arranged; Then the container of cover lid being put into water-bath and heat, is under 60～110 ℃ sheet glass to be carried out etching in temperature; In temperature is under 60～110 ℃, directly takes out sheet glass from container, cleans and sheet glass is dried up, and obtains described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
4. the preparation method of an anti-reflection ultra hydrophilic automatically cleaning antifog glass according to claim 1; It is characterized in that: to being in the container of inner bag with the polytetrafluoroethylmaterial material; Adding Vinylpyrrolidone polymer and concentration is the alkaline aqueous solution of 2～15 grams per liters; Stirring obtains mixed solution, and Vinylpyrrolidone polymer is that concentration in the alkaline aqueous solution of 2～15 grams per liters is 0～15 grams per liter in concentration; Sheet glass is immersed in the above-mentioned mixed solution, and the lid of covered container is put into water heating kettle with the container of cover lid; Tighten the lid of water heating kettle, under sealed state, put into baking oven to water heating kettle; In temperature is under 60～110 ℃ sheet glass to be carried out etching, naturally cools to room temperature then; Open hydro-thermal kettle cover, take out container, take out sheet glass more from container, clean and sheet glass is dried up, obtain described anti-reflection ultra hydrophilic automatically cleaning antifog glass.
5. according to claim 3 or 4 described preparing methods; It is characterized in that: described anti-reflection ultra hydrophilic automatically cleaning antifog glass is that have thickness on the surface of glass be that the thickness that the mutual cross connection of the silica nanometer sheet of 10～30 nanometers forms is the rough coatings of 50～160 nanometers; And mutual cross connection place of silica nanometer sheet has pore structure, and the aperture in described hole is 10～200 nanometers.
6. according to claim 3 or 4 described preparing methods, it is characterized in that: described alkaline aqueous solution is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or ammoniacal liquor.
7. according to claim 3 or 4 described preparing methods, it is characterized in that: the described etching time that sheet glass is carried out etching is 1～10 hour.
8. preparation method according to claim 4 is characterized in that: the purity of described Vinylpyrrolidone polymer is 90～100%.
9. according to claim 3 or 4 described preparing methods; It is characterized in that: with the anti-reflection ultra hydrophilic automatically cleaning antifog glass that obtains after the etching as substrate; Adopt the method for dip-coating, titania sol liquid is coated in the surface of anti-reflection ultra hydrophilic automatically cleaning antifog glass, drying; Calcining, obtaining thickness is the anti-reflection ultra hydrophilic automatically cleaning antifog glass with photocatalysis to degrade organic matter performance of the coating of titanium dioxide of 5～100 nanometers.
10. preparation method according to claim 9; It is characterized in that: described titania sol liquid is according to tetrabutyl titanate: methyl ethyl diketone: water: ethanol: the quality percentage composition is that the volume ratio of 37% concentrated hydrochloric acid is 1: 0.2: 0.4: 16: 0.1 ratio obtains after said components mixed.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412142A (en) * | 2002-11-26 | 2003-04-23 | 华南理工大学 | Nano self-cleaning super hydrophilic glass product production method |
| CN1693377A (en) * | 2004-05-09 | 2005-11-09 | 中国科学院化学研究所 | Application of super hydrophilicity and/or super lipophilicity nano pore material |
| CN1840497A (en) * | 2005-03-31 | 2006-10-04 | 刘明前 | Self-cleaning nano glass and its production process |
| CN1844000A (en) * | 2006-04-21 | 2006-10-11 | 暨南大学 | Permanent self-cleaning glass with visible light responsibility and preparation method thereof |
| CN101786801A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院理化技术研究所 | Super-hydrophilic anti-fog anti-reflection coating and preparation method and application thereof |
| US20110028305A1 (en) * | 2009-07-29 | 2011-02-03 | Korea Institute Of Machinery And Materials | Fabrication method for functional surface |
-
2011
- 2011-08-18 CN CN201110238349.5A patent/CN102649623B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412142A (en) * | 2002-11-26 | 2003-04-23 | 华南理工大学 | Nano self-cleaning super hydrophilic glass product production method |
| CN1693377A (en) * | 2004-05-09 | 2005-11-09 | 中国科学院化学研究所 | Application of super hydrophilicity and/or super lipophilicity nano pore material |
| CN1840497A (en) * | 2005-03-31 | 2006-10-04 | 刘明前 | Self-cleaning nano glass and its production process |
| CN1844000A (en) * | 2006-04-21 | 2006-10-11 | 暨南大学 | Permanent self-cleaning glass with visible light responsibility and preparation method thereof |
| CN101786801A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院理化技术研究所 | Super-hydrophilic anti-fog anti-reflection coating and preparation method and application thereof |
| US20110028305A1 (en) * | 2009-07-29 | 2011-02-03 | Korea Institute Of Machinery And Materials | Fabrication method for functional surface |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2863163A1 (en) * | 2013-10-18 | 2015-04-22 | GuS Periscopes GmbH & Co. KG | Periscope |
| CN103936294B (en) * | 2014-03-24 | 2016-08-17 | 同济大学 | The preparation method of a kind of coated glass sheet and purifying device using photo-catalysis |
| CN103936294A (en) * | 2014-03-24 | 2014-07-23 | 同济大学 | Preparation method of coated glass sheet and photocatalytic water purifying device |
| CN105084306A (en) * | 2015-07-30 | 2015-11-25 | 西北大学 | Controllable preparation method of large-area laminated micro-nano composite structure |
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| CN105669051B (en) * | 2016-01-06 | 2018-06-05 | 中国科学院重庆绿色智能技术研究院 | Super hydrophilic glass preparation method |
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| CN108261086A (en) * | 2017-01-03 | 2018-07-10 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of Anti-fog mirror, cooking apparatus and Anti-fog mirror |
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