CN103570248B - Anti-reflection antifogging glass and preparation method thereof - Google Patents
Anti-reflection antifogging glass and preparation method thereof Download PDFInfo
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- CN103570248B CN103570248B CN201210254006.2A CN201210254006A CN103570248B CN 103570248 B CN103570248 B CN 103570248B CN 201210254006 A CN201210254006 A CN 201210254006A CN 103570248 B CN103570248 B CN 103570248B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 230000003667 anti-reflective effect Effects 0.000 claims abstract description 104
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 238000009832 plasma treatment Methods 0.000 claims abstract description 12
- 239000005357 flat glass Substances 0.000 claims description 208
- 239000007864 aqueous solution Substances 0.000 claims description 109
- KXEOSTAFIDYVEF-UHFFFAOYSA-N [Si](O)(O)(O)O.[F] Chemical compound [Si](O)(O)(O)O.[F] KXEOSTAFIDYVEF-UHFFFAOYSA-N 0.000 claims description 107
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Abstract
The invention relates to anti-reflection antifogging glass and a preparation method thereof. The preparation method of the anti-reflection antifogging glass comprises the steps of effectively etching glass sheets with various components in a constant-temperature acid atmosphere, etching a porous structure layer extending from the surface of each glass sheet to the inside of each glass sheet on the surface of each glass sheet to reduce the refractive index of the surface of each glass sheet and achieve the effect of reducing reflection and increasing the reflection, so that the light transmittance of each glass sheet can be improved from 91% to 99%, and adjacent holes in the porous structure layer extending to the inside of each glass sheet are communicated or not communicated; then, carrying out oxygen plasma treatment and annealing treatment to prepare the anti-reflection antifogging glass; the surface of the antireflective antifog glass sheet still maintains the smoothness inherent to the glass sheet. The contact angle between the surface of the anti-reflection antifogging glass and water is 5-6 degrees, so that the tension of water on the surface of the glass can be effectively reduced, the water can be rapidly spread on the surface of the glass, and the aim of preventing fog is fulfilled.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly anti-reflection antifog glass and preparation method thereof.
Background technology
Along with the day of fossil energy is becoming tight, the increasingly attention of the whole world to energy development, various new cleaning fuel has attracted the sight of various countries scientist.Sun power is the inexhaustible renewable energy sources of the mankind, and solar electrical energy generation becomes study hotspot in the last few years, is expected to the mainstay becoming future electrical energy supply.But solar cell faces two key issues: one is how to improve photoelectric transformation efficiency, and two is the costs how reducing solar cell large-scale application.In recent years, scientist finds after deliberation, at solar panel surface coverage one deck antireflective coating, sunlight reflection can be reduced, increase full spectrum through, improve solar panels to the assimilated efficiency of solar spectrum, improve short-circuit photocurrent, thus utilize luminous energy to be the effective ways improving its photoelectric transformation efficiency to greatest extent.Along with the large-area applications of these solar cells, people, in the urgent need to working out a kind of antireflection coatings of excellence, can improve solar battery efficiency.
Antireflective coating has very important effect in solar cells, comprises two parts: one is that glass substrate applies antireflective coating, and two is apply antireflective coating on silicon plate.For silicon plate, light makes light loss up to 1/3rd in the reflection of silicon face, if the antireflection film having one deck suitable at silicon face, utilizes the principle of film interference that the reflection of light can be made greatly to reduce, thus reaches the object improving its photoelectric transformation efficiency.The Typical Representative of monocrystalline silicon high-efficient battery be the back point contact battery of Stanford University, the passivated emitter battery (PERL) of University of New South Wales and German Fraunhofer solar energy research localization back surface field battery etc.The perfect major cause being high-efficiency solar silion cell and developing of inverted pyramid technology, double-layer reflection-decreasing membrane technique and sunken light theory.Equally, the light transmittance of common glass substrates is about 90%, more effectively can utilize the sunlight of each wavelength after coating antireflective coating.
What studies in China was more is inorganic individual layer antireflective film, as SiN, SiO
2, Ta
2o, TiO
2, Al
2o
3deng; External employing double layer antireflection film is as MgF
2, ZnS, ZrO
2, TiO
2etc. there being good effect.With organic polymer material as antireflective film, external more existing research report, but its photoelectric transformation efficiency is also very low.The method preparing antireflective coating has from top to bottom and two kinds from bottom to top, and bottom-to-top method comprises the methods such as LBL self-assembly, lift, spraying, spin coating, and they all can construct the coating with higher light transmittance.But this coating generally has the shortcoming such as adhesivity and bad mechanical strength, limit its application industrially.Top-to-bottom method comprises photoresist material and etching etc., but the usual cost of these methods is higher.
The atomization of glass refers to that moisture or vapor condensation form small water droplet at glass article surface.And antifog glass (Anti-foggingglass) just refers to that simple glass is after special processing, surface is made to have super water-wet behavior, the small water droplet formed due to atomization is paved rapidly, thus reaches the effect of the transmittance not affecting mirror image, visibility meter and glass.Antifog coating can be divided into super-hydrophobic and super hydrophilic two classes.
If this coating is super-hydrophobicity material, then similar lotus leaf effect, water droplet is little at the surface scrolls angle of coating, and small water droplet can be made to be gathered into large water drop.When the globule reaches certain size, understand by himself Gravitational sliding, or by external force as the mode such as wind, rain brush is removed.The method successful, but poor in timeliness: due to little water droplet gathering or dry up, evaporate and all need for some time, water droplet can be stayed on glasswork, imaging and visibility meter is affected as prism, and the method weather resistance is undesirable at present, the Long Service Life of glassy product as durable consumer goods cannot be ensured, thus automatically cleaning effect truly cannot be ensured.
Superhydrophilic coating then can make little water droplet contact angle on the glass surface minimum and level off to zero degree, when water touches glass surface, rapidly at its surface spreading, form uniform moisture film, the character that performance excess of export is hydrophilic, can not affect mirror image, and the thin impact on transmittance of water layer simultaneously also greatly reduces, take away spot by the gravity fall of uniform water film, which can remove most of spot.Utilize super hydrophilic principle simultaneously, also can prevent the formation of little water droplet, reach antifog effect.
The antifog research of glass has just been started abroad in the sixties in 20th century, in fundamental research, at present, developed country Jun You renowned company is specializing in research and development and the making of antifog 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.; Transparent composite self-cleaning antifog glass (W.L.Tonareta1.ElectrochromicDeviceHavingASelf-cleaningHy drophilicCoating.UnitedStatesPatentApplicationPublicatio nUS2001/00210066A1, the 2001-09-13 of people's developments such as U.S. W.L.Tonar; K.Toru.VehicleMirror.UnitedStatesPatentUS5594585:1997-01-14; K.Toru.Anti-fogElement.US5854708:1998-12-29; K.Takahamaeta1.MethodofFormingHydrophilicInorganicCoatin gFilmAndInorganicCoatingComposition.UnitedStatesPatentAp plicationPublicationUS2001/008696A1,2001-07-13), be form the photocatalyst Clear coating with katalysis 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 surface to reach super hydrophilic, and applicable elements can be restricted, because the environment needing illumination just can carry out katalysis; Though and wetting ability can be improved in this cavernous structure surface, the material that being easy to is killed in a disaster volatilizees or nanometer dust block aperture, and weather resistance is undesirable.
Although domestic research is started late, also achieve significant progress, RELATED APPLICATIONS and technological achievement have item up to a hundred, and constantly have glass antidimmer product to release.On glasswork, form small water droplet cause atomization, the transparency reduces, and usually adopts following measures: (1) sprays layer of surface promoting agent at glass surface, to remove the water droplet and dust that are deposited thereon; (2) the organic water suction antifogging coating of one deck is applied at glass surface; (3) heating unit is installed, by heating evaporation glass surface water droplet; (4) ultrasonic wave dispersion and heating unit are installed, glass surface water droplet are disperseed simultaneously and heats, reaching the object of rapid evaporation.But these methods have respective limitation: method (1) needs regularly repeatedly spary tensio-active agent and seems not convenient; Method (2) due to use organic substance cause glasswork wear resistance and thermotolerance bad; Because heating evaporation water droplet needs 7 ~ 10 minutes, poor in timeliness usually in method (3), and need external energy, energy expenditure is large, thus impracticable; The device of method (4) is more complicated, and element is many, cost high (it is clever that Liu pays victory, and Li Yu puts down national building materials technical journal-" glass " the 3rd phase 16 ~ 19 in 2002).
Generally speaking, although anti-reflection antifog glass has a good application prospect, there is such or such problem in current preparation method, as anti-reflection and anti-fog effect and weather resistance also undesirable.Therefore Study and Development easily, wear resistance and good weatherability and the novel anti-reflection antifog glass that cost is low is very necessary and significant.The present invention adopts gas phase etching method to prepare antireflection layer, and the method is simple and with low cost, the antireflection layer satisfactory mechanical property of preparation, is given the mechanical property of the glass antifogging anti performance after etching and enhancing by plasma clean and annealing.
Summary of the invention
An object of the present invention is to provide a kind ofly has high transmittance and high hydrophilic anti-reflection antifog glass simultaneously.This glass can have good mechanical property.
Two of object of the present invention is to provide the preparation method of the anti-reflection antifog glass of object one, and this preparation method's technique is simple, cheaper starting materials, cost are low, applied widely.
Anti-reflection antifog glass of the present invention obtains after carrying out oxygen plasma treatment and anneal to anti-reflective glass sheet, described anti-reflective glass sheet is the porous structure layer having one deck to be extended to the inside of sheet glass by the surface of sheet glass in the surface etch of sheet glass, and the adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or do not communicate; The good smoothness that the surface of described anti-reflection antifog glass sheet still keeps sheet glass intrinsic.
The thickness of the described porous structure layer having one deck to be extended to the inside of sheet glass by the surface of sheet glass in the surface etch of sheet glass be preferably 40nm ~ 100nm(more preferably thickness be 60nm); This porous structure layer greatly improves the transmittance of original sheet glass, makes the transmittance of sheet glass can bring up to 99% from original 91%.
The surface of described anti-reflective glass sheet and the contact angle of water are 35 ° ~ 45 °.
The surface of described anti-reflection antifog glass and the contact angle of water are 5 ° ~ 6 °.
Anti-reflection antifog glass of the present invention, due to the surface treatment of oxygen plasma, makes Si-OH key instead of Si-F key, thus improves the wetting ability of original sheet glass greatly.The 3 μ L globules drop in the surface of common glass sheet, after the sprawling of 0.5 second time, the contact angle of water droplet and glass sheet surface is greater than 15 °, and the 3 μ L globules drop in the surface of anti-reflection antifog glass of the present invention, after the sprawling of 0.5 second time, the contact angle on water droplet and anti-reflection antifog glass surface of the present invention can be reduced to 5.8 °.
The preparation method of anti-reflection antifog glass of the present invention is in the acid atmosphere of constant temperature, the sheet glass of various component is effectively etched, the porous structure layer that one deck extends to the inside of sheet glass by the surface of sheet glass is gone out in the surface etch of sheet glass, then carry out oxygen plasma treatment and anneal, thus prepare anti-reflection antifog glass of the present invention.
Anti-reflection antifog glass of the present invention adopts the method for constant temperature gas phase etching to be prepared, and its preparation method comprises the following steps:
(1) fluorine silicic acid aqueous solution is placed in reaction vessel (reaction vessel of use is preferably the reactor that tetrafluoroethylene is inner bag), then the sheet glass level cleaned up is suspended from the top of fluorine silicic acid aqueous solution in reaction vessel, covers the lid of reaction vessel; The reaction vessel of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 5 ~ 20 DEG C, sheet glass is etched (preferably the time of etching is 18 ~ 48 hours), (preferred thickness is 40nm ~ 100nm to go out in the surface etch of sheet glass the porous structure layer that one deck extends to the inside of sheet glass by the surface of sheet glass, more preferably thickness is 60nm), the adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate; Open the lid of water heating kettle after etching terminates, take out reaction vessel, then take out sheet glass from reaction vessel, sheet glass also dries up by cleaning, obtains anti-reflective glass sheet;
(2) the anti-reflective glass sheet that step (1) obtains is placed in oxygen plasma cleanser (if power is the oxygen plasma cleanser of 120W), under the voltage of 400 ~ 700V, clean described anti-reflective glass sheet (time of preferably cleaning is 5 ~ 8 minutes), the flow of oxygen is 800 ~ 1000mL/min;
(3) the anti-reflective glass sheet that step (2) obtains after oxygen plasma treatment is placed in retort furnace, at 700 DEG C ~ 720 DEG C, calcining carries out anneal in 100 ~ 150 seconds, obtains the anti-reflection antifog glass of satisfactory mechanical property; The good smoothness that the surface of the antifog glass sheet that gained is anti-reflection still keeps sheet glass intrinsic.
The volume of described fluorine silicic acid aqueous solution in reaction vessel is 20mL ~ 40mL, and the volume of described fluorine silicic acid aqueous solution and the volume ratio of reaction vessel are 0.04 ~ 0.08.
The concentration of the aqueous solution of described silicofluoric acid is 0.75mol/L ~ 1.75mol/L.
The present invention, after carrying out oxygen plasma treatment and anneal to anti-reflective glass sheet, can further improve wetting ability and the mechanical property of anti-reflective glass sheet, makes it have good anti-reflection, anti-fog performance and weather resistance.
Sheet glass described in the present invention comprises common glass sheet prepared by various composition, various structure, various size and various technique.Also comprise the sheet glass of special composition, as ultra-clear glasses (low iron glass) simultaneously.
The present invention is using the cheap and common glass sheet easily obtained as substrate, adopt the method for constant temperature, under the sour gas condition that silicofluoric acid volatilization generates, the sheet glass of various component is effectively etched, pass through deep etching, go out in the surface etch of sheet glass the porous structure layer that one deck extends to the inside of sheet glass by the surface of sheet glass, to reduce the specific refractory power of glass sheet surface, reach the effect of anti-reflection; Carry out oxygen plasma treatment and anneal again, prepare anti-reflection antifog glass; Oxygen plasma treatment makes the surface of etching glass and the contact angle of water be reduced to 5 ° ~ 6 ° from 35 ° ~ 45 °, has good anti-fog performance simultaneously.Preparation method of the present invention is simple, cost is low, applied widely.Prepared anti-reflection antifog glass has high transmittance, and most high transmission rate reaches 99%; There is high wetting ability, namely the 3 μ L globules drop in the surface of anti-reflection antifog glass of the present invention, after the sprawling of 0.5 second time, the contact angle on the surface of water droplet and anti-reflection antifog glass of the present invention can be reduced to 5.8 °, thus effectively can reduce the tension force of water at glass surface, make water spread over glass surface rapidly and reach antifog object.Pencil hardness test shows, the hardness on described anti-reflection antifog glass surface is more than or equal to 6H, and have good physical strength, application prospect is extensive.Durability test shows, the surface after etching has good weather resistance, and bimestrial outdoor placement transmittance only reduces by 2.26%.Continuous experiment test shows, etching method of the present invention has good repeatability.
Anti-reflection antifog glass of the present invention, may be used for the glass window, glass sunroof, glass curtain wall, Household bathroom mirror, windshield, rear vision mirror, background glass, ophthalmic lens etc. that comprise family, apartment and business and public place building.Be particularly suitable as anti-reflection packaging glass of solar cell and vacuum solar heat-collecting pipe glass.
Accompanying drawing explanation
Fig. 1. in the embodiment of the present invention 1, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 0.75mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 2. in the embodiment of the present invention 2, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 48h, and when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the aqueous solution generation of 1.50mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 3. in the embodiment of the present invention 3, the light transmittance curve figure of clean blank glass and when etching temperature is 5 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 4. in the embodiment of the present invention 4, the light transmittance curve figure of clean blank glass and when etching temperature is 20 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 5. in the embodiment of the present invention 5, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 20mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 6. in the embodiment of the present invention 6, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 40mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 7. in the embodiment of the present invention 7, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 18h, when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 8. in the embodiment of the present invention 8, the light transmittance curve figure of clean blank glass and when etching temperature is 15 DEG C, etching time is 48h, when the volume of fluorine silicic acid aqueous solution is 30mL, concentration is that the gas of the fluorine silicic acid aqueous solution generation of 1.00mol/L is to the light transmittance curve figure of sheet glass etching back glass sheet.
Fig. 9. in the embodiment of the present invention 9, the light transmittance curve figure of clean blank glass and reflectance curve figure, and when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, when the volume of fluorine silicic acid aqueous solution is 30mL, when etching time is 30h, the gas that fluorine silicic acid aqueous solution produces is to the light transmittance curve figure of glass etching back glass sheet and reflectance curve figure.
Figure 10. in the embodiment of the present invention 10, a be when the concentration of fluorine silicic acid aqueous solution be 1.0mol/L, volume is 30mL, etching temperature is 15 DEG C, and the gas that different etching time (0 hour, 18 hours, 24 hours, 30 hours, 36 hours and 48 hours) fluorine silicic acid aqueous solutions produces is to the light transmittance curve figure of glass etching back glass sheet; B is when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, when the volume of fluorine silicic acid aqueous solution is 30mL, the gas that fluorine silicic acid aqueous solution produces is at the contact angle figure of different etching times (0 hour, 18 hours, 24 hours, 30 hours, 36 hours and 48 hours) to the maximum transmission rate of glass etching back glass sheet and the surface of the globule and etching back glass sheet; C is the enlarged view at black box place in a figure.
Figure 11. in the embodiment of the present invention 10, when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, when the volume of fluorine silicic acid aqueous solution is 30mL, the stereoscan photograph of the structure of the glass sheet surface after the different etching time; A figure, b figure, c figure, d figure, e figure and f figure are respectively the stereoscan photograph of the glass sheet surface structure after 0 hour, 18 hours, 24 hours, 30 hours, 36 hours and 48 hours etchings; G figure is the amplification picture of e figure; H figure is the cross section picture of e figure.
Figure 12. in the embodiment of the present invention 11, when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, and when the volume of fluorine silicic acid aqueous solution is 30mL, when etching time is 30h, the gas that fluorine silicic acid aqueous solution produces is to the etching of glass; A figure is the surface that the 3 μ L globules drop in blank glass sheet, the digital photograph of the contact angle situation of water droplet and glass sheet surface; B figure is the surface that the 3 μ L globules drip sheet glass anti-reflection after etching, the digital photograph of the contact angle situation of water droplet and the rear anti-reflection glass sheet surface of etching; C figure is the surface that the 3 μ L globules drop in anti-reflection antifog glass, the digital photograph of the contact angle situation on the surface of water droplet and anti-reflection antifog glass; D figure is the anti-fog performance test of anti-reflection antifog glass, is anti-reflection antifog glass above in figure, is blank glass below in figure.
Figure 13. the wear resisting property test of the sheet glass of the embodiment of the present invention 11 correspondence, a figure represents the SEM picture of 6H pencil scratch test, and b figure represents the SEM enlarged image of 6H pencil scratch test.
Figure 14. in the embodiment of the present invention 12, when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, when the volume of fluorine silicic acid aqueous solution is 30mL, the gas glass etching that fluorine silicic acid aqueous solution produces obtained anti-reflection sheet glass after 24 hours, through oxygen plasma treatment 8 minutes, be then placed in retort furnace and calcine 135 seconds under 720 ° of C, obtain anti-reflection antifog glass.The light transmittance curve figure of anti-reflection antifog glass sheet light transmittance curve figure and the anti-reflection after two months antifog glass sheet of outdoor placement.
Figure 15 .a figure is in the embodiment of the present invention 13, when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, when the volume of fluorine silicic acid aqueous solution is 30mL, the gas that fluorine silicic acid aqueous solution produces etches 30 hours to sheet glass, do not change fluorine silicic acid aqueous solution, within every 30 hours, exchange clean sheet glass for and carry out repeating etching, obtain the light transmittance curve figure of anti-reflective glass sheet; B figure is the enlarged view of a figure black box part.
Figure 16. in the embodiment of the present invention 14, when the concentration of fluorine silicic acid aqueous solution is 1.0mol/L, etching temperature is 15 DEG C, and when the volume of fluorine silicic acid aqueous solution is 30mL, the gas that fluorine silicic acid aqueous solution produces etches the light transmittance curve figure of the ultra-clear glasses sheet after 30 hours to ultra-clear glasses.
Embodiment
Embodiment 1.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 0.75mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is 52nm porous structure layer, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 36.5 °.
Fig. 1 is the light transmittance curve figure of the anti-reflective glass sheet obtained after over-richness is the gas etching of the fluorine silicic acid aqueous solution generation of 0.75mol/L.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; Through the fluorine silicic acid aqueous solution of 0.75mol/L, to decompose the maximum transmission rate of anti-reflective glass sheet that the gas etching that produces obtains after 48 hours be the transmittance at 402nm wavelength place is 95.5%.
Embodiment 2.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.50mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 76nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 40.1 °.
Fig. 2 is the light transmittance curve figure of the anti-reflective glass sheet obtained after over-richness is the gas etching of the fluorine silicic acid aqueous solution generation of 1.50mol/L.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; Through the fluorine silicic acid aqueous solution of 1.50mol/L, to decompose the maximum transmission rate of anti-reflective glass sheet that the gas etching that produces obtains after 48 hours be the transmittance at 678nm wavelength place is 95.6%.
Embodiment 3.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 5 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 48nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 36.3 °.
Fig. 3 is the light transmittance curve figure of the anti-reflective glass sheet obtained after the gas being the fluorine silicic acid aqueous solution generation of 1.00mol/L through over-richness etches at 5 DEG C.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; At 5 DEG C, through the fluorine silicic acid aqueous solution of 1.00mol/L, to decompose the maximum transmission rate of anti-reflective glass sheet that the gas etching that produces obtains after 48 hours be the transmittance at 403nm wavelength place is 93.8%.
Embodiment 4.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 20 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 70nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 39.6 °.
Fig. 4 is the light transmittance curve figure of the anti-reflective glass sheet obtained after over-richness is the gas etching of the fluorine silicic acid aqueous solution generation of 1.00mol/L.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; At 20 DEG C, through the fluorine silicic acid aqueous solution of 1.00mol/L, to decompose the maximum transmission rate of anti-reflective glass sheet that the gas etching that produces obtains after 48 hours be the transmittance at 400nm wavelength place is 92.7%.
Embodiment 5.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 20mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 20 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 57nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 39.0 °.
Fig. 5 is the light transmittance curve figure of the anti-reflective glass sheet that the gas etching that produces at 15 DEG C of the fluorine silicic acid aqueous solution being 1.00mol/L through 20mL concentration obtains after 48 hours.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; When liquor capacity is 20mL, the maximum transmission rate of the anti-reflective glass sheet that the gas etching decomposing generation through the fluorine silicic acid aqueous solution of 1.00mol/L at 15 DEG C obtained after 48 hours is the transmittance at 658nm wavelength place is 94.9%.
Embodiment 6.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 40mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 84nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 44.9 °.
Fig. 6 is the light transmittance curve figure of the anti-reflective glass sheet obtained after over-richness is the gas etching of the fluorine silicic acid aqueous solution generation of 1.00mol/L.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; When liquor capacity is 40mL, through the fluorine silicic acid aqueous solution of 1.00mol/L, to decompose the maximum transmission rate of anti-reflective glass sheet that the gas etching that produces obtains after 48 hours be the transmittance at 630nm wavelength place is 94.5%.
Embodiment 7.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 18 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 40nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 35.3 °.
Fig. 7 is the light transmittance curve figure that the fluorine silicic acid aqueous solution being 1.00mol/L through over-richness carries the anti-reflective glass sheet that the gas etching that produces at 15 DEG C obtains after 18 hours.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; When etching time is 18 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.00mol/L decomposes the gas etching produced is the transmittance at 402nm wavelength place is 95.9%.
Embodiment 8.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 48 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 100nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 37.0 °.
Fig. 8 is the light transmittance curve figure of the anti-reflective glass sheet that the gas etching that produces at 15 DEG C of the fluorine silicic acid aqueous solution being 1.00mol/L through 30mL concentration obtains after 48 hours.Be 91.2% without the blank glass of cleaning of etching at the transmittance at 506nm wavelength place; When etching time is 48 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.00mol/L decomposes the gas etching produced is the transmittance at 578nm wavelength place is 97.6%.
Embodiment 9.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 30 hours to sheet glass, going out in the surface etch of sheet glass the thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is the porous structure layer of 60nm, adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate.The lid of water heating kettle is opened after etching terminates, take out container, then take out sheet glass from container, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.When the 3 μ L globules drop on anti-reflective glass sheet, the surface of described anti-reflective glass sheet and the contact angle of water are 35.4 °.
The fluorine silicic acid aqueous solution of Fig. 9 to be clean blank glass and 30mL concentration be 1.00mol/L decomposes the gas that produces etches the anti-reflective glass sheet obtained after 30 hours at 15 DEG C light transmittance curve figure and reflectance curve figure to sheet glass.Found out by Fig. 9, the transmittance of the anti-reflective glass obtained after etching brings up to 99.0% by 92.1%, and reflectivity is reduced to 0.52% by 9%.
Embodiment 10.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.0mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, sheet glass is etched, the lid of water heating kettle is opened after etching terminates, take out container, take out sheet glass from container again, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.
Described etching time is respectively 18 hours, 24 hours, 30 hours, 36 hours and 48 hours, select different etching times, it is different that fluorine silicic acid aqueous solution decomposes the etching degree of gas to sheet glass produced, go out in the surface etch of sheet glass the porous structure layer that thickness that one deck extends to the inside of sheet glass by the surface of sheet glass is respectively 40nm, 52nm, 60nm, 78nm and 100nm respectively, and the adjacent Kong Yukong in the porous structure layer that extends of the described inside to sheet glass communicates or does not communicate; The anti-reflective glass sheet obtained after etching has the visibly different transmittance to light and the wetting ability to water.
At a figure and c figure in Figure 10 is respectively 15 DEG C, 30mL concentration is the light transmittance curve figure that the fluorine silicic acid aqueous solution of 1.0mol/L decomposes the anti-reflective glass sheet obtained after the gas produced etches sheet glass under different etching time conditions.When etching time is 18 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.0mol/L decomposes the gas etching produced is the transmittance at 402nm wavelength place is 95.9%; When etching time is 24 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.0mol/L decomposes the gas etching produced is the transmittance at 402nm wavelength place is 98.5%; When etching time is 30 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.0mol/L decomposes the gas etching produced is the transmittance at 477nm wavelength place is 99.0%; When etching time is 36 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.0mol/L decomposes the gas etching produced is the transmittance at 406nm wavelength place is 98.2%; When etching time is 48 constantly little, the maximum transmission rate of the anti-reflective glass sheet obtained after the 30mL concentration fluorine silicic acid aqueous solution that is 1.0mol/L decomposes the gas etching produced is the transmittance at 578nm wavelength place is 97.6%.As can be seen here, when etching time is 30 hours, the anti-reflective glass sheet obtained after the gas etching that 30mL concentration is the fluorine silicic acid aqueous solution decomposition generation of 1.0mol/L illustrates the highest transmittance.
B figure in Figure 10 shows: when the 3 μ L globules drop on clean blank glass, the contact angle on the surface of the globule and blank glass sheet is 13.94 °.When the 3 μ L globules drop in through 30mL concentration be 1.0mol/L fluorine silicic acid aqueous solution produce gas etched 18 hours respectively, 24 hours, 30 hours, on the surface of the anti-reflective glass sheet obtained after 36 hours and 48 hours, the contact angle on the surface of the globule and anti-reflective glass sheet is respectively 35.34 °, 40.15 °, 35.36 °, 37.42 ° and 37.01 °, the globule is being that the contact angle that 1.0mol/L fluorine silicic acid aqueous solution decomposes on the surface of the anti-reflective glass sheet that the gas etching that produces obtains after 24 hours is maximum through 30mL concentration, be that the contact angle that 1.0mol/L fluorine silicic acid aqueous solution decomposes on anti-reflective glass sheet surface that the gas etching that produces obtains after 18 hours is minimum through 30mL concentration.
At 15 DEG C, 30mL concentration be the structure on the surface of the anti-reflective glass sheet obtained after 1.0mol/L fluorine silicic acid aqueous solution decomposes the gas etching different time produced as shown in figure 11.The stereoscan photograph that a schemes, b figure, c figure, d figure, e figure and f figure are respectively the surface tissue of the anti-reflective glass sheet obtained after 0 hour, 18 hours, 24 hours, 30 hours, 36 hours and 48 hours etch.G figure is the amplification picture of e figure; H figure is the cross section picture of e figure.
Can see from a figure Figure 10, the very level and smooth and gully shape defect having some less and closed in the surface of blank glass, the defect on the surface of the anti-reflective glass sheet obtained after etching through 18 hours is opened and is become larger wider slight crack gradually.When etching time extends to 30 constantly little, slight crack is wider darker, and as can be seen from enlarged view, inside exists the hierarchical structure of porous.When etching time extends to 48 constantly little again, wider slight crack can be found out from f figure.Being found out by h figure, is that after 1.0mol/L fluorine silicic acid aqueous solution decomposes the gas etching 30 hours produced, the thickness of the porous structure layer etched is 60nm through 30mL concentration.
Embodiment 11.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.0mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 30 hours to sheet glass, the lid of water heating kettle is opened after etching terminates, take out container, take out sheet glass from container again, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.The good smoothness that the surface of gained anti-reflective glass sheet still keeps sheet glass intrinsic.
The anti-reflective glass sheet obtained is placed in the oxygen plasma cleanser that power is 120W, cleans described anti-reflective glass sheet 5 minutes under voltage is 800V, the flow of oxygen is 800mL/min.Then the anti-reflective glass sheet obtained after oxygen plasma treatment is placed in retort furnace, at 720 DEG C, calcining carries out anneal in 135 seconds, obtains anti-reflection antifog glass sheet.Found out by a figure of Figure 12, the 3 μ L globules drop in the surface of blank glass sheet, and the contact angle on the surface of water droplet and blank glass sheet is 13.9 °.Found out by the b figure of Figure 12, when the 3 μ L globules drop in the surface of anti-reflective glass sheet, the contact angle on the surface of water droplet and anti-reflective glass sheet is 37.01 °.Found out by the figure c of Figure 12, when the 3 μ L globules drop in anti-reflection antifog glass sheet surface, the contact angle of water droplet and anti-reflection antifog glass sheet is 5.8 °.
Clean blank glass and anti-reflection antifog glass sheet are put into refrigerator, at-18 DEG C freezing 4 hours, at room temperature carry out antifog test after taking-up, test result is as shown in the d figure in Figure 12.
The wear resistance of anti-reflection antifog glass sheet is carried out scratch test with the pencil of 6H (constant pressure is for 7.5N, pencil and coatingsurface at 45 °), test result is as the arrow indication in a figure and b figure in Figure 13, the microstructure that pencil streaks rear etching still exists, and the porous microstructure on anti-reflection antifog glass sheet surface can not crossed out by 6H pencil.
Embodiment 12.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.0mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 24 hours to sheet glass, the lid of water heating kettle is opened after etching terminates, take out container, take out sheet glass from container again, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet.
The anti-reflective glass sheet obtained is placed in the oxygen plasma cleanser that power is 120W, cleans described anti-reflective glass sheet 8 minutes under voltage is 800V, the flow of oxygen is 800mL/min.Then the anti-reflective glass sheet obtained after oxygen plasma treatment is placed in retort furnace, at 720 DEG C, calcining carries out anneal in 135 seconds, obtains anti-reflection antifog glass sheet; The good smoothness that the surface of the antifog glass sheet that gained is anti-reflection still keeps sheet glass intrinsic.
Anti-reflection antifog glass sheet is placed open air after two months, with tap water and with the anti-reflection antifog glass sheet light transmittance curve figure after air blow drying by Figure 14.The maximum transmission rate of the anti-reflection antifog glass sheet after placement is the transmittance at 416nm wavelength place is 96.26%, reduced by only 2.26% than the anti-reflection antifog glass sheet before not placing.Illustrate that the anti-reflection surface of anti-reflection antifog glass sheet has good weather resistance.
Embodiment 13.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.0mol/L, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by sheet glass is the container of inner bag, sheet glass level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 30 hours to sheet glass, the lid of water heating kettle is opened after etching terminates, take out container, take out sheet glass from container again, sheet glass is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up sheet glass), obtain anti-reflective glass sheet 1.
Do not change the fluorine silicic acid aqueous solution in container, the sheet glass (sheet glass is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) of another sheet cleaning displaced the anti-reflective glass sheet 1 that four foot supports obtain rapidly and repeat aforesaid method, obtaining anti-reflective glass 2.So carry out eight circulations.
Figure 15 for not change fluorine silicic acid aqueous solution, the light transmittance curve figure of gained 8 anti-reflective glass sheets.The maximum transmission rate of anti-reflective glass sheet 1 is the transmittance at 475nm wavelength place is 98.95%, the maximum transmission rate of anti-reflective glass sheet 2 is the transmittance at 477nm wavelength place is 98.80%, the maximum transmission rate of anti-reflective glass sheet 3 is the transmittance at 477nm wavelength place is 98.50%, the maximum transmission rate of anti-reflective glass sheet 4 is the transmittance at 466nm wavelength place is 98.49%, the maximum transmission rate of anti-reflective glass sheet 5 is the transmittance at 473nm wavelength place is 98.30%, the maximum transmission rate of anti-reflective glass sheet 6 is the transmittance at 403nm wavelength place is 97.92%, the maximum transmission rate of anti-reflective glass sheet 7 is the transmittance at 471nm wavelength place is 97.53%, the maximum transmission rate of anti-reflective glass sheet 8 is the transmittance at 470nm wavelength place is 97.50%.As seen from Figure 15, preparation method of the present invention has good repeatability.
Embodiment 14.
To in the container take polytetrafluoroethylmaterial material as the volume of inner bag being 500mL, add the fluorine silicic acid aqueous solution that 30mL concentration is 1.00mol/L, the ultra-clear glasses sheet (ultra-clear glasses sheet is of a size of centimetre (length) × 0.1,2.5 centimetres of (wide) × 7.5 centimetre (thickness)) cleaned is placed on four foot supports, being put into together with support with tetrafluoroethylene by ultra-clear glasses sheet is the container of inner bag, ultra-clear glasses sheet level is suspended from the top of fluorine silicic acid aqueous solution in container, the lid of covered container, the container of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 15 DEG C, etching is carried out 30 hours to sheet glass, the lid of water heating kettle is opened after etching terminates, take out container, take out ultra-clear glasses sheet from container again, ultra-clear glasses sheet is cleaned up and dry up (available a large amount of tap water or distilled water flushing clean, and the pressurized air that available air compressor is discharged dries up ultra-clear glasses sheet), obtain anti-reflection ultra-clear glasses sheet.
The fluorine silicic acid aqueous solution of Figure 16 to be 30mL concentration be 1.00mol/L decomposes the gas that produces etches the anti-reflection ultra-clear glasses sheet obtained after 30 hours light transmittance curve figure to ultra-clear glasses sheet.When etching time is 30 hours, the maximum transmission rate of anti-reflection ultra-clear glasses sheet obtained after the gas etching that the 30mL concentration fluorine silicic acid aqueous solution that is 1.00mol/L produces is the transmittance at 404nm wavelength place is 95.0%, improves 3.5% than the ultra-clear glasses do not etched.
Claims (4)
1. an anti-reflection antifog glass, it is characterized in that: described anti-reflection antifog glass obtains after carrying out oxygen plasma treatment and anneal to anti-reflective glass sheet, described anti-reflective glass sheet is the thickness having one deck to be extended to the inside of sheet glass by the surface of sheet glass in the surface etch of sheet glass is the porous structure layer of 40 ~ 100nm, and the adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or do not communicate; The smoothness that the surface of described anti-reflection antifog glass sheet still keeps sheet glass intrinsic;
Described anti-reflection antifog glass is obtained by following concrete preparation method, and described preparation method comprises the following steps:
(1) be that the fluorine silicic acid aqueous solution of 0.75mol/L ~ 1.75mol/L is placed in reaction vessel by concentration, the volume of described fluorine silicic acid aqueous solution and the volume ratio of reaction vessel are 0.04 ~ 0.08, then the sheet glass level cleaned up is suspended from the top of fluorine silicic acid aqueous solution in reaction vessel, covers the lid of reaction vessel; The reaction vessel of cover lid is put into water heating kettle, cover the lid of water heating kettle and tighten, in sealed states, water heating kettle is put into thermostat container, at temperature is 5 ~ 20 DEG C, etching is carried out 18 ~ 48 hours to sheet glass, go out in the surface etch of sheet glass the porous structure layer that one deck extends to the inside of sheet glass by the surface of sheet glass, the adjacent Kong Yukong in the porous structure layer that the described inside to sheet glass extends communicates or does not communicate; Etching terminates rear taking-up sheet glass, obtains anti-reflective glass sheet;
(2) the anti-reflective glass sheet that step (1) obtains is placed in oxygen plasma cleanser, cleans described anti-reflective glass sheet under the voltage of 400 ~ 700V, the flow of oxygen is 800 ~ 1000mL/min;
(3) the anti-reflective glass sheet that step (2) obtains after oxygen plasma treatment is placed in retort furnace, at 700 DEG C ~ 720 DEG C, calcining carries out anneal in 100 ~ 150 seconds, obtains anti-reflection antifog glass; The good smoothness that the surface of the antifog glass sheet that gained is anti-reflection still keeps sheet glass intrinsic.
2. anti-reflection antifog glass according to claim 1, is characterized in that: the surface of described anti-reflective glass sheet and the contact angle of water are 35 ° ~ 45 °.
3. anti-reflection antifog glass according to claim 1, is characterized in that: the surface of described anti-reflection antifog glass and the contact angle of water are 5 ° ~ 6 °.
4. anti-reflection antifog glass according to claim 1, is characterized in that: the time of the cleaning described in step (2) is 5 ~ 8 minutes.
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| CN108191254B (en) * | 2018-02-11 | 2021-07-06 | 浙江大学 | Preparation method of glass surface porous structure |
| CN111704368A (en) * | 2020-07-14 | 2020-09-25 | 浙江水晶光电科技股份有限公司 | Anti-fog glass with anti-reflection function and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763340A (en) * | 1996-01-19 | 1998-06-09 | Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry | Method for production of SiO2 glass material having regions changed in light refractive index and SiO2 glass material produced by the method |
| EP1018657A1 (en) * | 1998-07-16 | 2000-07-12 | Nippon Sheet Glass Co., Ltd. | Refractive index distribution type optical element and refractive index distribution type rod lens array |
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| JPS5940774B2 (en) * | 1981-09-14 | 1984-10-02 | 工業技術院長 | How to prevent deterioration of anti-reflective glass |
| JPH04119943A (en) * | 1990-09-10 | 1992-04-21 | Alps Electric Co Ltd | Optical element and its production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763340A (en) * | 1996-01-19 | 1998-06-09 | Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry | Method for production of SiO2 glass material having regions changed in light refractive index and SiO2 glass material produced by the method |
| EP1018657A1 (en) * | 1998-07-16 | 2000-07-12 | Nippon Sheet Glass Co., Ltd. | Refractive index distribution type optical element and refractive index distribution type rod lens array |
| CN1274428A (en) * | 1998-07-16 | 2000-11-22 | 日本板硝子株式会社 | Refractive index distribution type optical element and refractive index distribution type rod lens array |
Non-Patent Citations (1)
| Title |
|---|
| 层层自组装结合后处理制备耐磨超亲水增透纳米粒子涂层;许利刚等;《化学学报》;20111130;第69卷(第22期);第2648-2652页 * |
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