CN106082697B - A kind of energy conservation coated glass and preparation method thereof - Google Patents
A kind of energy conservation coated glass and preparation method thereof Download PDFInfo
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- CN106082697B CN106082697B CN201610473847.0A CN201610473847A CN106082697B CN 106082697 B CN106082697 B CN 106082697B CN 201610473847 A CN201610473847 A CN 201610473847A CN 106082697 B CN106082697 B CN 106082697B
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- 239000011521 glass Substances 0.000 title claims abstract description 74
- 238000004134 energy conservation Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims abstract description 27
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910002012 Aerosil® Inorganic materials 0.000 claims abstract description 14
- 239000004964 aerogel Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- -1 polyethylene Pyrrolidones Polymers 0.000 claims 2
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000003667 anti-reflective effect Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 3
- ADUFBHYKXMWOSH-UHFFFAOYSA-N [O--].[O--].[Ti+4].[V+5] Chemical compound [O--].[O--].[Ti+4].[V+5] ADUFBHYKXMWOSH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 239000010410 layer Substances 0.000 description 28
- 230000005855 radiation Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005344 low-emissivity glass Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical class [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Joining Of Glass To Other Materials (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses a kind of energy saving coated glasses to be sequentially depositing vanadium dioxide thermochromic layer and aerosil layer using glass as substrate on glass.Present invention incorporates the different modes for reducing by the two kinds of heat propagations of heat transfer and blocking radiant heat, provide it is a kind of have both it is heat-insulated with thermochromic function energy saving coated glass.The introducing of aerosil layer slows down the oxidation of titanium dioxide vanadium layers, while can play the role of antireflective.The invention also discloses the preparation methods of the energy conservation coated glass, carry out hydrophilic treated to glass substrate first；Vanadium dioxide precursor layer is coated by glass baseplate surface of the sol-gel method after hydrophilic treated；Again by sol-gel method in vanadium dioxide precursor layer surface coating silicon dioxide aerogel precursor body layer；Finally thermally treated to obtain energy saving coated glass, heat treatment temperature is 550~580 DEG C, and the time is 1~10h.
Description
Technical field
The present invention relates to the preparation fields of glass, and in particular to a kind of energy conservation coated glass and preparation method thereof.
Background technique
Building energy consumption occupies significant proportion in social total energy consumption, and by the energy that door and window scatters and disappears be it is therein most
Major part, so glass energy-saving is the hot spot of current research.The optical transparence and some higher thermal conductivity having due to building glass
How much the inlet of rate, indoor infrared infrared radiant energy is determined by it, therefore the heat-proof quality of glass has become measurement building glass
The whether energy-efficient important indicator of glass.In cold winter, glass while obtaining the direct heat radiation of more sun, if
Method reduces the loss of mid and far infrared heat radiation within doors, and interior can be made to be able to maintain convenient temperature；And in the summer of high temperature, people
Wish a large amount of far-infrared thermal radiation being blocked in outdoor again, to reduce the energy consumption burden of the refrigeration equipments such as air-conditioning.
Coated glass, it is in glass surface coating one or more layers metal, alloy or metal compound film, to change
The optical property of glass meets certain particular requirement.Coated glass presses the different characteristics of product, can be divided into: solar-control glazing,
Low emissivity glass, electropane etc..Solar-control glazing is usually to plate one or more layers such as chromium, titanium or not in glass surface
The film of the metals such as rust steel or its compound composition, makes product in color abundant, has transmissivity appropriate for visible light, right
Near infrared ray has higher reflectivity, has higher absorption rate to ultraviolet light, is mainly used for building and glass curtain wall.Low emissivity glass
It is the film system being made of in glass surface plating metals or its compounds such as multilayer silver, copper or tin, product has visible light higher
Transmissivity, centering far infrared has very high reflectivity, has good heat-proof quality, is mainly used for building, automobile, ship
The equal vehicles.Electropane is to can be used for the heating of glass in conductive films such as glass surface coating tin indium oxides, remove
Frost, demisting and liquid crystal display etc..Solar-control glazing and low emissivity glass are using relatively broad, existing sunlight control glass
Glass and low emissivity glass are typically all single layer plate glass, are had the drawback that in poor impact resistance, carrying and installation process easily
It is contaminated with scratch, translucency is strong, reflectivity is high, light pollution is big, heat insulation performance is low, film plating layer is easy to fall off influences to use the longevity
Life etc..
As Publication No. CN102785415A Chinese patent literature in disclose a kind of adjustable vanadium dioxide of transmissivity
Based coextruded film further relates to the application for being used as intelligent power saving glass using the hypovanadic oxide-based composite film.The transmissivity is adjustable
Hypovanadic oxide-based composite film, including vanadium dioxide film, the first inorganic transparent being arranged on the vanadium dioxide film be thin
Film, and the second inorganic transparent film being arranged on the vanadium dioxide film, the first inorganic transparent film and second inorganic
Bright film can be the same or different, independently selected from zinc oxide, zinc sulphide, Al-Doped ZnO, indium-doped tin oxide, indium-doped oxygen
Change zinc, titanium dioxide, titanium sesquioxide and fluorine-doped tin oxide.
The transmitance of visible light can be improved using above-mentioned design and enhance the infrared ability of regulation and control of sunlight, transmitted
The adjustable hypovanadic oxide-based composite film of rate, but since vanadium dioxide only has selection saturating the energy of 300~2500nm wave band
The property crossed still is only limitted to have good performance of control in the wave band after above-mentioned transparent membrane is compound.Simultaneously as first,
The thickness of second inorganic transparent film can not play heat-insulated effect all in nanoscale.
Summary of the invention
Present invention incorporates the different modes for reducing by the two kinds of heat propagations of heat transfer and blocking radiant heat, provide one kind and have both
The heat-insulated energy saving coated glass with thermochromic function.
The invention discloses a kind of energy saving coated glasses, using glass as substrate, the successively spin coating titanium dioxide on the glass
Vanadium thermochromic layer and aerosil layer.
The present invention proposes SiO2Aeroge-VO2Composite energy-saving coated glass structure, from prevention directly conduction and heat radiation two
Aspect carries out energy conservation measure, utilizes SiO2Aerogel layer realization is heat-insulated, utilizes VO2Layer realizes the selectivity to different-waveband energy
Through acquisition high-efficient energy-saving function.Wherein, VO2Thermochromism may be implemented the energy conservation of 300nm~2500nm wave band, but nothing
Method prevents wavelength in the thermal conductivity heat transfer in 2 μm~50 μm regions, with heat-insulated SiO2After aerogel film is compound, it can prevent simultaneously
The heat transfer of the heat radiation of 300nm~2500nm wave band and 2 μm~50 μm regions, to further improve energy-efficient performance；In addition,
While introducing heat-proof quality, barrier vanadium dioxide thermochromic layer directly contacts aerosil layer with air,
Slow down the process that vanadium dioxide is oxidized, increases its function durability.Meanwhile it is found through experiment that, with aerosil layer
As teleblem, antireflective, improvement VO can be played the role of2Transmitance of the film in visible light region.
Preferably, the vanadium dioxide thermochromic layer with a thickness of 50~100nm；
The aerosil layer with a thickness of 1.0~2.0 μm, porosity is 80~88%.In the porosity and hole
Under the premise of the unobvious variation of gauge structure, thicker aerogel film can bring better heat insulation, i.e., with the increasing of thickness
Add, the overall thermal conductivity of coated glass is lower, but composite membrane has no in the transmitance of visible region and is substantially reduced.
The invention also discloses the preparation methods of the energy saving coated glass, comprising the following steps:
(1) hydrophilic treated is carried out to glass substrate；
(2) glass baseplate surface by sol-gel method after hydrophilic treated coats vanadium dioxide precursor layer；
(3) through sol-gel method before the vanadium dioxide precursor layer surface coating silicon dioxide aeroge of step (2)
Drive body layer；
(4) glass substrate for successively coating vanadium dioxide precursor layer and aerosil precursor layer is subjected to heat
Processing；
The temperature of the heat treatment is 550~580 DEG C, and the time is 1~10h.
Preferably, the hydrophilic treatment process of the glass substrate is as follows in step (1):
1): by dilute hydrochloric acid, hydrogen peroxide and deionized water mixed configuration acid solution；
2): by ammonium hydroxide, hydrogen peroxide and deionized water mixed configuration alkaline solution；
3): glass substrate being placed in an acidic solution, heating is taken out after impregnating 1~60min, is placed on again after washed
In alkaline solution, 1~60min, the glass substrate after being washed after taking-up, being dried to obtain hydrophilic treated are impregnated in heating.
Preferably, the volume ratio of dilute hydrochloric acid, hydrogen peroxide and deionized water is 1:2:5 in the acid solution；
In the alkaline solution, the volume ratio of ammonium hydroxide, hydrogen peroxide and deionized water is 1:2:5.
The dilute hydrochloric acid is the hydrochloric acid solution that mass percent is lower than 20%, and the hydrogen peroxide is that mass percent is
27.5%~30% aqueous hydrogen peroxide solution, the mass percent of the ammonium hydroxide are 25%~28%.
Preferably, specific step is as follows for coating vanadium dioxide precursor layer in step (2):
A), the pH value for vanadium source and solvent A being mixed to get vanadium solution, and adjusting vanadium solution is 3.5~4, after mixing evenly
Be added polyvinylpyrrolidone, be sufficiently stirred, it is still aging after obtain vanadium colloidal sol；
The vanadium source includes vanadyl acetylacetonate, vanadic sulfate；
The solvent A includes anhydrous methanol, hydrochloric acid；
The concentration of the vanadium solution is 0.125~0.130mol/L；
The mass ratio of the polyvinylpyrrolidone and vanadium solution is 3.20~3.28:100；
B), after the vanadium colloidal sol stirring of step A) preparation, coated in the glass baseplate surface after hydrophilic treated, then through drying
Processing obtains the vanadium dioxide precursor layer.
Preferably, step A) in, the pH value that hydrochloric acid adjusts vanadium solution is added.
Preferably, step A) in, the still aging time is 1~2d.
Further preferably, step B) in, after the stirring of vanadium colloidal sol, the glass after hydrophilic treated is coated in by the way of spin coating
Substrate surface；
The spin coating is divided into two stages, and the revolving speed of first stage is 300~400r/min, and the time is 10~15s, the
The revolving speed of two-stage is 2800~3000r/min, and the time is 25~30s；
The temperature of the drying is 25~40 DEG C.
The purpose of substep spin coating is: the slow-speed of revolution makes colloidal dispersion uniform, and high revolving speed is for controlling film thickness.
Preferably, specific step is as follows for spin-on silicon dioxide aerogel precursor body layer in step (3):
A) silicon source and solvent B are mixed to get silicon solution, then are mixed with ethanedioic acid solution, it is after mixing evenly, still aging
Obtain silica solution；
The silicon source includes methyltrimethoxysilane, and solvent B includes anhydrous methanol, ethyl alcohol etc.；
Silicon source concentration is 1.147~1.162mol/L in the silicon solution；
The concentration of the ethanedioic acid solution is 0.001mol/L, the volume ratio of silicon solution and ethanedioic acid solution is 11.3~
12.5:1；
B) silica solution that step a) is obtained is mixed with ammonia spirit and guarantees NH in silica solution4 +Content is 0.0mol, is stirred
Drying control chemical additive is added after mixing uniformly, static ageing obtains gel after mixing evenly；
The ammonia spirit concentration is 14.79~14.84mol/L；
The drying control chemical additive is glycerine；
The molar ratio of the drying control chemical additive and silica solution is 0.1~0.15:1；
C) gel that step b) is obtained is dissolved in dehydrated alcohol first through magnetic agitation, then after the stirring of homogeneous blender,
Re-coating obtains the aerosil precursor layer on vanadium dioxide precursor layer surface after dry.
Preferably, when still aging, being sealed in step a) and guaranteeing that ambient humidity is 60~70%, at room temperature
It is aged 1~2d.
Preferably, when still aging, guaranteeing that ambient humidity is 60~70% in step b), being aged 2~3d at room temperature.
Preferably, gel is stirred through homogeneous blender in step c), stirring rate is 15000~18000r/min.
Further preferably, it in step c), being coated by the way of spin coating, the spin coating is divided into two stages, the
The revolving speed in one stage is 400~500r/min, and the time is 10~15s, and the revolving speed of second stage is 2200~2400r/min, when
Between be 25~30s；
The temperature of the drying is 25~40 DEG C.
Preferably, the heat treatment carries out under vacuum atmosphere in step (4), heating rate is 30~35 DEG C/
min。
Compared with prior art, the present invention has the advantage that
The present invention pass through combine reduce by the two kinds of heat propagations of heat transfer and blocking radiant heat different modes, for 300nm~
The energy of 2500nm wave band, at high temperature, VO2Film has high reflectivity, outside heat can be stopped to enter the room, when low temperature
VO2The reflectivity that film has is low, and outside heat enters the room, and meets power conservation requirement.But the energy of 2 μm~50 mu m wavebands,
When high temperature, VO2Film has metallicity, that is, has high reflectivity in this wave band, and the heat of human-body emitting is reflected back toward
It is indoor；And VO when low temperature2Film conductivity decline does not have low radiation functions, and the heat of human-body emitting is lost by glass pane, institute
With VO2Film does not have low radiation functions, is not suitable for cold district theoretically.And SiO2Aerogel film has heat insulation, can be with
Make up this deficiency.So composite membrane makes coated glass have both heat-insulated and intelligent thermal radiation resistance function, comprehensive energy conservation.Significantly mention
The high energy-saving efficiency of the coated glass.
Aerosil layer is used for teleblem by the present invention, in addition to playing insulative effectiveness, also prevents titanium dioxide vanadium layers
With directly contacting for air, slow down its oxidation process.
The aerosil layer of high transmittance, low-refraction is used for teleblem by the present invention, can play antireflective function
Effect.
Detailed description of the invention
Fig. 1 is the SiO on energy saving coated glass surface prepared by embodiment 12Aeroge-VO2The SEM photograph of composite membrane section；
Fig. 2 be embodiment 1 prepare energy saving coated glass before phase change after 300nm~2500nm wave band light transmission rate figure
Spectrum.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) hydrophilic treated of glass substrate:
The first step, configure dilute hydrochloric acid: hydrogen peroxide: deionized water is the acid solution that volume ratio is 1:2:5, by glass substrate
20min is wherein heated in immersion, is washed with deionized water after taking-up clean.Second, configure ammonium hydroxide: hydrogen peroxide: deionized water volume
Than the alkaline solution for 1:2:5, then glass substrate is added thereto heating and boils 20min, after taking-up again with deionized water repeatedly
It rinses, thermal current drying.
(2) vanadium dioxide precursor layer is coated on the glass substrate using sol-gel method:
The vanadyl acetylacetonate for weighing 0.4972g in the balance is dissolved in 15ml anhydrous methanol, is configured to 0.125mol/L
Vanadium solution, hydrochloric acid is added dropwise, adjusts the pH=3.5 of vanadium solution.Magnetic force is sufficiently stirred at room temperature.It is eventually adding poly-
Vinylpyrrolidone (PVP), the additional amount of PVP accounts for the 4% of vanadium solution quality, after being sufficiently stirred, stands at room temperature old
Change one day and obtains vanadium colloidal sol.
After the vanadium colloidal sol of preparation is stirred, using the method for spin coating on the glass substrate of hydrophilic treated plated film.Its transfer
Speed is divided into two stages, i.e. 300r/min rotates 10s, and high speed 2800r/min rotates 30s plated film.Obtained gel mould is at 50 DEG C
Oven drying handle 10min, obtain vanadium dioxide precursor layer.
(3) sol-gel method coating silicon dioxide aerogel film on vanadium dioxide film is utilized:
It weighs 2.04g methyltrimethoxysilane solid to be dissolved in 15ml anhydrous methanol, be added configured in advance
The ethanedioic acid solution 1.07ml of 0.001M, sealing magnetic stirs 30min at room temperature, after solution is sufficiently mixed, gained is molten
Liquid is placed in preservative film covering sealing, and ambient humidity, light and temperature is kept 60% and to be under room temperature aged 1d.
The ammonia spirit that concentration is 14.84mol/L is added dropwise dropwise into the solution after ageing and makes ammonia root in final colloidal sol
Ion concentration is 1.5 × 10-2Mol, the magnetic agitation 15min in draught cupboard notice that sealing not have the volatilization of solvent.Finally plus
Enter 1.7 × 10-3Mol glycerine stirs 15min, is aged 2d in the gel under room temperature for guaranteeing that humidity is 60%.
Gel after the aging made from the soda acid two-step method is broken up and is diluted in 22ml anhydrous methanol, is first stirred with magnetic force
15min is mixed, then stirs 2min with homogeneous blender, stirring rate is 15000 revs/min, and the liquid after gained homogeneous is stood
Half an hour obtains spin coating raw material.
Then spin coating raw material is spin-coated in the vanadium dioxide precursor film that the first step obtains with spin-coating method, specifically: it takes
Suitable spin coating raw material, is slowly added dropwise on high-speed rotating glass substrate, and wherein first order spin coating rate is 400rpm, continues
10 seconds, spin coating rate in the second level was 2200rpm, after continuing 30 seconds, then through being dried to obtain aerosil layer at 20 DEG C.It can
To control aerogel film thickness to be prepared by control infusion volume and the speed of rotation and time.
(4) heat treatment of composite membrane:
VO is sequentially coated with by above-mentioned2Precursor film, SiO2The substrate of glass of aerogel precursor body film be put into Muffle furnace into
Row heat treatment, heat treatment condition are as follows: vacuum atmosphere, heating rate are 30 DEG C/min, target temperature is 550 DEG C, heat treatment time
For 2h, energy saving coated glass is obtained.
Fig. 1 is the SiO on energy saving coated glass surface manufactured in the present embodiment2Aeroge-VO2The SEM of composite membrane section shines
Piece, it can be seen that VO2Film with a thickness of 80nm or so, and SiO2Aeroge is with a thickness of 1.3 μm.
Fig. 2 is energy saving coated glass manufactured in the present embodiment under 20 DEG C (solid lines) and 90 DEG C (dotted line), 300nm~
The light transmission rate map of 2500nm wave band, it can be seen that near infrared portion, rear transmitance has apparent variation before phase change,
Regulation amplitude reaches 46%.Meanwhile composite membrane is more than 51% in the highest transmitance of visible region, meets the indoor need to daylighting
It asks, illustrates that composite film coating structure has good thermochromic properties.
Table 1 is the thermal conductivity of simple glass and energy saving coated glass manufactured in the present embodiment, in terms of heat-proof quality, plated film
Glass overall thermal conductivity afterwards is reduced to 1.303 from 1.332, has heat-insulated performance.
Table 1
Claims (1)
1. a kind of preparation method of energy conservation coated glass, which comprises the following steps:
(1) hydrophilic treated of glass substrate:
The first step, configure dilute hydrochloric acid: hydrogen peroxide: deionized water is the acid solution that volume ratio is 1:2:5, and glass substrate is impregnated
20 min are wherein heated, are washed with deionized water after taking-up clean；
Second step, configure ammonium hydroxide: hydrogen peroxide: deionized water volume ratio is the alkaline solution of 1:2:5, then it is added in glass substrate
20 min are boiled in middle heating, use deionized water repeated flushing, thermal current drying after taking-up again；
(2) vanadium dioxide precursor layer is coated on the glass substrate using sol-gel method:
The vanadyl acetylacetonate for weighing 0.4972g in the balance is dissolved in 15ml anhydrous methanol, is configured to the vanadium of 0.125mol/L
Hydrochloric acid is added dropwise in solution, adjusts pH=3.5 of vanadium solution, magnetic force is sufficiently stirred at room temperature；It is eventually adding polyethylene
Pyrrolidones, the additional amount of polyvinylpyrrolidone accounts for the 4% of vanadium solution quality, after being sufficiently stirred, stands at room temperature old
Change one day and obtains vanadium colloidal sol；
After the vanadium colloidal sol of preparation is stirred, using the method for spin coating on the glass substrate of hydrophilic treated plated film；Wherein revolving speed point
For two stages, 300r/min rotates 10s, and high speed 2800r/min rotates 30s plated film；Baking oven of the obtained gel mould at 50 DEG C
It is dried 10min, obtains vanadium dioxide precursor layer；
(3) sol-gel method coating silicon dioxide aerogel film on vanadium dioxide film is utilized:
It weighs 2.04g methyltrimethoxysilane solid to be dissolved in 15 ml anhydrous methanols, is added and shifts to an earlier date configured 0.001M
Ethanedioic acid solution 1.07ml, at room temperature sealing magnetic stirring 30min acquired solution is placed in after solution is sufficiently mixed
Preservative film covering sealing keeps ambient humidity, light and temperature 60% and being under room temperature aged 1d；
The ammonia spirit that concentration is 14.84mol/L is added dropwise dropwise into the solution after ageing and makes ammonia radical ion in final colloidal sol
Content is 1.5 × 10-2Mol, the magnetic agitation 15min in draught cupboard notice that sealing not have the volatilization of solvent；It is eventually adding
1.7×10-3Mol glycerine stirs 15min, is aged 2d in the gel under room temperature for guaranteeing that humidity is 60%；
Gel after the aging made from the soda acid two-step method is broken up and is diluted in 22ml anhydrous methanol, magnetic agitation is first used
15min, then 2min is stirred with homogeneous blender, stirring rate is 15000 revs/min, and the liquid after gained homogeneous is stood half
Hour, obtain spin coating raw material；Then spin coating raw material is spin-coated in the vanadium dioxide precursor layer with spin-coating method, specifically:
Spin coating raw material is taken, is slowly added dropwise on high-speed rotating glass substrate, wherein first order spin coating rate is 400rpm, continues 10
Second, spin coating rate in the second level is 2200rpm, after continuing 30 seconds, then through being dried to obtain aerosil layer at 20 DEG C；
(4) heat treatment of composite membrane:
By it is above-mentioned be sequentially coated with vanadium dioxide precursor layer, the substrate of glass of aerosil layer be put into Muffle furnace into
Row heat treatment, heat treatment condition are as follows: vacuum atmosphere, heating rate are 30 DEG C/min, target temperature is 550 DEG C, heat treatment time
For 2h, energy saving coated glass is obtained；
The vanadium dioxide precursor layer on the energy conservation coated glass surface with a thickness of 80nm, the thickness of aerosil layer
It is 1.3 μm；
The thermal conductivity of the energy conservation coated glass is 1.303 W/mK, thermal diffusivity 0.7098mm2/s。
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| CN107285640A (en) * | 2017-06-08 | 2017-10-24 | 湖北大学 | Enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power and preparation method thereof |
| CN109135723A (en) * | 2017-06-15 | 2019-01-04 | 湖南尚成新材料科技有限责任公司 | A kind of aerogel composite and preparation method thereof with thermochromic function |
| CN109126643B (en) * | 2017-06-15 | 2020-06-02 | 湖南尚成新材料科技有限责任公司 | Self-light-modulation type transparent composite aerogel and preparation method thereof |
| CN108046616B (en) * | 2018-01-16 | 2021-02-23 | 天津摩根坤德高新科技发展有限公司 | Laminated glass containing aerogel and preparation method thereof |
| CN108483934B (en) * | 2018-03-29 | 2021-02-02 | 东南大学 | Tungsten bronze/silica gel heat insulation functional material and preparation method thereof |
| CN108530072B (en) * | 2018-04-28 | 2020-07-03 | 四川大学 | Composite window material and preparation method thereof |
| CN113321426A (en) * | 2021-04-20 | 2021-08-31 | 北方民族大学 | Design method of TiO2 heat-insulating film |
| CN113502106B (en) * | 2021-07-30 | 2022-07-29 | 大连工业大学 | VO (volatile organic compound) 2 /SiO 2 Aerogel composite film and preparation method thereof |
| CN114031315A (en) * | 2021-12-03 | 2022-02-11 | 江苏上玻玻璃有限公司 | Energy-saving LOW-E glass and preparation method thereof |
| CN115159860B (en) * | 2022-07-20 | 2023-07-18 | 贵州民族大学 | Preparation of H-SiO in a Mild aqueous solution 2 -VO 2 Method for (M) coating |
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| CN102167520A (en) * | 2011-01-21 | 2011-08-31 | 华南理工大学 | Method for preparing nano AZO-doped series transparent heat-insulation glass |
| CN102399072A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Preparation method of intelligent energy-saving coating |
| CN103771722A (en) * | 2012-10-22 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Transparent dimming structure with high thermal insulation function, and preparation method and application thereof |
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| CN102399072A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Preparation method of intelligent energy-saving coating |
| CN102167520A (en) * | 2011-01-21 | 2011-08-31 | 华南理工大学 | Method for preparing nano AZO-doped series transparent heat-insulation glass |
| CN103771722A (en) * | 2012-10-22 | 2014-05-07 | 中国科学院上海硅酸盐研究所 | Transparent dimming structure with high thermal insulation function, and preparation method and application thereof |
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